WO2015068385A1 - 変性プロピレン・α-オレフィン共重合体とその製造方法、それを含むコーティング材、成形用樹脂組成物およびホットメルト組成物 - Google Patents
変性プロピレン・α-オレフィン共重合体とその製造方法、それを含むコーティング材、成形用樹脂組成物およびホットメルト組成物 Download PDFInfo
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- WO2015068385A1 WO2015068385A1 PCT/JP2014/005567 JP2014005567W WO2015068385A1 WO 2015068385 A1 WO2015068385 A1 WO 2015068385A1 JP 2014005567 W JP2014005567 W JP 2014005567W WO 2015068385 A1 WO2015068385 A1 WO 2015068385A1
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- propylene
- olefin copolymer
- modified propylene
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
- C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene polymers
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
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- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
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- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
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- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
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- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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Definitions
- the present invention relates to a modified propylene / ⁇ -olefin copolymer and a method for producing the same, a coating material containing the same, a molding resin composition, and a hot melt composition.
- So-called polyolefin waxes containing low molecular weight olefin polymers are used in a wide range of applications such as coating agents in the form of emulsions and solutions, release agents used in combination with toners, resin modifiers, hot melt adhesives, etc. Yes.
- the polyolefin structure basically has no polar group, it is often used in combination with nonpolar and low polarity components. It is known that the reason why it is difficult to directly introduce a polar group into a polyolefin is that a transition metal catalyst serving as a catalyst for olefin polymerization is poisoned by the polar group and the polymerization activity is significantly reduced.
- polyolefin waxes are also known in which a method of producing a high-olefin polymer by thermal decomposition is known.
- polyolefin wax When polyolefin wax is used in combination with a polar resin such as acrylic or engineering plastic, it is often preferable to introduce a polar group into the polyolefin wax.
- a method for introducing a polar group a method of oxidizing a polyolefin wax with air, or a method of reacting a polyolefin wax with a radical initiator in the presence of a polar compound containing a double bond such as maleic anhydride is known. (For example, refer to Patent Document 1).
- Patent Document 2 as a method for introducing a polar group into a wax having 3 or more carbon atoms such as propylene wax, a polyolefin wax obtained by directly polymerizing with a transition metal catalyst or the like is polar containing a double bond such as maleic anhydride. It is disclosed that a method of reacting with a compound is preferred. Patent Document 2 discloses that when a polypropylene wax obtained by thermal decomposition is subjected to radical reaction with maleic anhydride, the viscosity increases. Further, it is also disclosed in Patent Document 2 and the like that when propylene-based wax is oxidized with air, decomposition becomes dominant and it tends to become oily.
- the market has recently tended to require low melting point polyolefin waxes. This is accompanied by a tendency that energy saving is important.
- the lowering of the melting point of the wax can be achieved, for example, when the temperature of the fixing drum of the copying machine is lowered when the wax is used as a toner, or when the wax is used as a hot melt adhesive. It is thought that effects such as lowering the adhesive temperature of the agent can be expected.
- JP 2004-059867 A Japanese Patent No. 4526603
- propylene-based waxes tend to be more rigid and harder than ethylene-based waxes.
- Known propylene-based waxes include polypropylene (PP) wax and propylene / ethylene copolymer (PER) wax.
- PP polypropylene
- PER propylene / ethylene copolymer
- the PER wax has a low melting point, there is a problem that it is easily rubberized and difficult to handle.
- the present inventors can produce a propylene-based wax having an appropriate amount of vinylidene groups by thermally decomposing a copolymer containing a propylene unit and an ⁇ -olefin unit having 4 or more carbon atoms;
- the resulting propylene-based wax is modified with a polar compound containing a double bond, so that it has a low melting point, has little stickiness, maintains crystallinity even when containing a polar group, and increases its hardness. It was found that a modified propylene-based wax can be obtained.
- the modified propylene-based wax thus obtained contains moderately polar groups at the molecular end, so that not only does it maintain good crystallinity and easily increase the hardness, but also has a high phase with other resins. It is considered that the solubility and the high affinity with the filler can also be obtained.
- an object of the present invention is to modify a propylene-based wax containing an ⁇ -olefin unit having 4 or more carbon atoms obtained by thermal decomposition with a polar compound containing a double bond, thereby having a low melting point and being solid. Therefore, it is an object of the present invention to provide a polar group-containing propylene-based wax that exhibits excellent performance such as maintaining crystallinity even when containing a polar group and capable of increasing the hardness.
- the present inventors diligently studied a method for solving the above problem. As a result, we came up with a solution based on the following ideas.
- the phenomenon that the viscosity is increased in the modification reaction of the pyrolytic polypropylene wax disclosed in Patent Document 2 is that hydrogen from carbon to which a branched methyl group of a propylene unit is bonded in the process of pyrolysis in the production of pyrolytic polypropylene wax.
- a propylene-based wax obtained by a thermal decomposition method and containing a propylene unit and an ⁇ -olefin unit having 4 or more carbon atoms can suppress a significant increase in viscosity even when reacted with a polar compound having a double bond. I found.
- the propylene-derived structural unit (a) is 60 to 95 mol%
- the ⁇ -olefin-derived structural unit (b) having 4 or more carbon atoms is 5 to 40 mol%
- a propylene / ⁇ -olefin copolymer (A1) satisfying all of the following (i) to (iv): at least one selected from an unsaturated carboxylic acid or a derivative thereof or an unsaturated sulfonic acid or a salt thereof
- a modified propylene / ⁇ -olefin copolymer (A) which is a seed-grafted copolymer and has an acid value of 0.5 to 100 KOH mg / g.
- Weight average molecular weight (Mw) measured by GPC is in the range of 3,000 to 40,000
- Melting point (Tm) measured by DSC is in the range of 60 to 110 ° C.
- DSC The half-value width of the measured crystal melting point peak is in the range of 1 to 20 ° C.
- the number of vinylidene groups per 1000 carbon atoms measured by 1 HNMR is 0.5 to 5
- the propylene / C4 or more ⁇ -olefin copolymer (A2) is composed of 60 to 95 mol% of propylene-derived structural unit (a ′) and a structural unit derived from ⁇ -olefin having 4 or more carbon atoms.
- (I ′) The weight average molecular weight (Mw) measured by GPC is in the range of 50,000 to 1,000,000.
- the melting point (Tm) measured by DSC is in the range of 60 to 120 ° C.
- the half-value width of the crystalline melting point peak measured by DSC is in the range of 1 to 20 ° C.
- the propylene / ⁇ -olefin copolymer (A1) further satisfies the following requirement (v): [1 ] The modified propylene / ⁇ -olefin copolymer (A) according to any one of [3] to [3]. (V) The melting peak ⁇ H measured by DSC is in the range of 40 to 100 J / g.
- the crystallization temperature of the modified propylene / ⁇ -olefin copolymer (A) is Tc (A), and the propylene
- Tc (A1) the crystallization temperature of the ⁇ -olefin copolymer (A1)
- Tc (A1) / Tc (A) the crystallization temperature ratio
- the modified propylene / ⁇ -olefin copolymer (A) according to any one of [1] to [4].
- the propylene / ⁇ -olefin copolymer (A1) having a half-value width of the measured crystal melting point peak in the range of 1 to 20 ° C. is at least selected from an unsaturated carboxylic acid or derivative thereof, or an unsaturated sulfonic acid or salt thereof.
- a modified propylene / ⁇ -olefin copolymer (A) comprising a step of graft-polymerizing one kind to obtain a modified propylene / ⁇ -olefin copolymer (A) having an acid value of 1 to 100 KOHmg / g. Production method.
- the propylene / ⁇ -olefin copolymer (A1) is obtained by thermally decomposing the propylene / C4 or more ⁇ -olefin copolymer (A2) at 300 to 450 ° C. for 5 minutes to 10 hours.
- the weight average molecular weight (Mw) measured by GPC is in the range of 50,000 to 1,000,000.
- the melting point (Tm) measured by DSC is in the range of 60 to 120 ° C.
- iii ′ The half-value width of the crystalline melting point peak measured by DSC is in the range of 1 to 20 ° C.
- a coating material comprising 1 to 100 parts by weight.
- the weight ratio of the modified propylene / ⁇ -olefin copolymer (A) to the other resin (B1) is 1/99 to 90/90 in total.
- 10 is a coating material.
- the coating material according to any one of [11] to [13], wherein the organic solvent includes at least one of a hydrocarbon solvent, an alcohol solvent, and an ester solvent.
- the modified propylene / ⁇ -olefin copolymer (A) according to any one of [1] to [5] or the modified propylene / ⁇ -olefin according to any one of [1] to [5] A paint comprising a copolymer (A) and another resin (B1).
- the modified propylene / ⁇ -olefin copolymer (A) according to any one of [1] to [5] or the modified propylene / ⁇ -olefin according to any one of [1] to [5] A primer comprising a copolymer (A) and another resin (B1).
- a primer comprising a copolymer (A) and another resin (B1).
- An adhesive comprising a copolymer (A) and another resin (B1).
- the modified propylene / ⁇ -olefin copolymer (A) according to any one of [1] to [5] or the modified propylene / ⁇ -olefin according to any one of [1] to [5] The adhesive containing a copolymer (A) and other resin (B1).
- a sintering aid comprising a copolymer (A) and another resin (B1).
- the modified propylene / ⁇ -olefin copolymer has a low melting point, is less sticky, maintains a crystallinity even when it contains a polar group, and can have high hardness. Therefore, the modified propylene / ⁇ -olefin copolymer of the present invention can be preferably used for various applications such as a coating material, a molding-like resin composition, and a hot melt composition.
- the coating material containing the modified propylene / ⁇ -olefin copolymer of the present invention is excellent in dispersibility and solubility in water and solvent, has a high solidification rate when applied, and can be highly concentrated. Also, when the modified propylene / ⁇ -olefin copolymer of the present invention is blended with other resins, the compatibility is good, so that varnish separation can be suppressed, coating unevenness can be reduced, and coating materials can be reduced. Blocking resistance can be imparted to the coating film surface. Therefore, the resin solution can be spray-coated without causing a separation phenomenon, and is useful for paints, primers, adhesives, and ink binders that can be spray-coated.
- the above coating material when the above coating material is made into a coating film, there is no stickiness on the surface of the coating film, and exhibits excellent adhesion to various molded articles, etc., so that plastic, metal, paper, wood, fiber, leather, glass, rubber, Used as a coating material for ceramics, concrete, paints, primers, adhesives, adhesives, binders for inks, etc., in various industrial materials and building materials fields.
- the modified propylene / ⁇ -olefin copolymer of the present invention is also used as a filler dispersant, pigment dispersant, sintering aid, binder for ceramics and metallurgical compounds in the coating material.
- the molding resin composition containing the modified propylene / ⁇ -olefin copolymer of the present invention has an excellent balance of mechanical properties such as impact strength, bending strength, and tensile strength.
- the hot melt composition containing the modified propylene / ⁇ -olefin copolymer of the present invention has good compatibility between the base polymer or tackifying resin and the modified propylene / ⁇ -olefin copolymer, and thus has good fluidity. It is excellent and has high adhesion to the substrate.
- the modified propylene / ⁇ -olefin copolymer (A) of the present invention is a propylene / ⁇ -olefin copolymer containing a polar group structural unit in a predetermined ratio. It can be.
- the polar group is preferably a polar group containing a hetero atom. More specifically, polar groups containing carbon, hydrogen, and oxygen are preferred embodiments, and more specifically ester groups, ether groups, carboxylic acid groups (including carboxylic anhydride groups), aldehyde groups, and ketone groups. Can be mentioned.
- the modified propylene / ⁇ -olefin copolymer (A) of the present invention is obtained by 1) pyrolyzing a propylene / ⁇ -olefin copolymer (A2) having 4 or more carbon atoms to produce a low molecular weight propylene / ⁇ -olefin copolymer.
- a step of obtaining a polymer (A1); 2) a modified propylene / ⁇ -olefin copolymer obtained by graft polymerizing a low molecular weight propylene / ⁇ -olefin copolymer (A1) with a polar compound containing a double bond (A) can be manufactured through a process.
- Step 1) Propylene / ⁇ -olefin copolymer (A2) having 4 or more carbon atoms is thermally decomposed to obtain a low molecular weight propylene / ⁇ -olefin copolymer (A1).
- a propylene / C4 or higher ⁇ -olefin copolymer (A2) is obtained under an inert atmosphere such as nitrogen.
- the temperature at which the propylene / C4 or higher ⁇ -olefin copolymer (A2) is thermally decomposed is preferably 300 to 450 ° C., more preferably 350 to 430 ° C., and particularly preferably 370 to 410 ° C.
- the thermal decomposition time is preferably 5 minutes to 10 hours, more preferably 10 minutes to 90 minutes. Increasing the pyrolysis time and / or increasing the temperature can lower the molecular weight and increase the amount of vinylidene groups.
- the resulting propylene / ⁇ -olefin copolymer (A1) may be purified by a method such as solvent fractionation in which fractionation is performed based on a difference in solubility in an organic solvent.
- the raw material propylene / ⁇ -olefin copolymer (C2) having 4 or more carbon atoms will be described later.
- ⁇ -olefin having 4 or more carbon atoms constituting the propylene / ⁇ -olefin copolymer (A1) include 1-butene, 1-hexene, 4-methyl / 1-pentene, 1-octene, 1-decene and the like can be exemplified, but an ⁇ -olefin having 4 to 10 carbon atoms is preferable, an ⁇ -olefin having 4 to 8 carbon atoms is more preferable, and 1-butene is particularly preferable.
- the propylene / ⁇ -olefin copolymer (A1) has a small amount of structural units derived from ethylene or the like as an olefin other than propylene and an ⁇ -olefin having 4 or more carbon atoms, for example, a total of 100 moles of (a) + (b). It may further be contained in an amount of 10 mol% or less per%.
- the structural unit derived from ethylene is not included from the viewpoint of the solubility of the coating material, the dispersibility, the blocking resistance of the coating film, etc., when the modified product is used as a coating material. This is one of the embodiments.
- the propylene / ⁇ -olefin copolymer (A1) is an olefin polymerizable monomer other than an ⁇ -olefin, such as vinyl acetate; unsaturated carboxylic acid such as acrylic acid or methacrylic acid; methyl acrylate, ethyl acrylate, or isobutyl acrylate.
- Unsaturated carboxylic acid esters such as n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, glycidyl methacrylate, dimethyl maleate; structural units derived from olefin polymerizable monomers such as styrene (a) + (b ) May be further included in an amount of 10 mol% or less per 100 mol%. However, from the viewpoint of the hardness of the propylene / ⁇ -olefin copolymer (A), it is preferable that these monomers are not included.
- the propylene / ⁇ -olefin copolymer (A1) content of propylene-derived structural units and ⁇ -olefin-derived structural units having 4 or more carbon atoms can be determined by analysis of 13 C-NMR spectrum.
- the upper limit of the weight average molecular weight (Mw) measured by GPC is 40,000, preferably 30,000, more preferably 20,000, particularly preferably. Can be 10,000.
- the lower limit of the weight average molecular weight (Mw) can be 3,000, preferably 5,000, more preferably 6,000, and particularly preferably 8,000.
- the coating material containing a modified product of the propylene / ⁇ -olefin copolymer (A1) having a weight average molecular weight (Mw) in the above range is considered to be capable of higher concentration and excellent in handling properties. Moreover, the coating film obtained is uniform, has excellent blocking resistance, and has good adhesion to the substrate. If the weight average molecular weight (Mw) is less than or equal to the above upper limit, the modified product of the propylene / ⁇ -olefin copolymer (A1) is excellent in solubility and dispersibility in the organic solvent, or in the resins used in combination. It is considered that the viscosity of the coating material becomes moderate, and the concentration can be further increased, or good handling properties can be maintained. Further, for the same reason, it is considered that a uniform coating film is obtained with little streaking and unevenness.
- the weight average molecular weight (Mw) of the propylene / ⁇ -olefin copolymer (A1) is not more than the upper limit, the modified product is easily crystallized. It is presumed that the solidification rate is increased, and as a result, blocking resistance is developed. Further, when the weight average molecular weight (Mw) of the propylene / ⁇ -olefin copolymer (A1) is not more than the upper limit, the coating film containing the modified product can easily follow the base material, or the shrinkage of the coating film It is considered that the adhesiveness may be suppressed and the adhesion with the substrate may be improved.
- the weight average molecular weight (Mw) of the propylene / ⁇ -olefin copolymer (A1) is not less than the above lower limit, the solid component due to the low molecular weight is reduced, and the coating film containing the modified product has blocking resistance. It seems to be good.
- the olefin of the low molecular weight propylene / ⁇ -olefin copolymer (A1) has many solid components and is considered difficult to handle as a coating film, but the weight average molecular weight (Mw) is within the above range. Therefore, it is thought that the coating film containing the modified product is excellent in blocking resistance.
- the Mw / Mn measured by GPC of the propylene / ⁇ -olefin copolymer (A1) is not particularly limited, and may be, for example, about 1 to 5, preferably about 2 to 4.
- the coating material containing the modified product of propylene / ⁇ -olefin copolymer (A1) having Mw / Mn in the above range has high stability, excellent blocking resistance of the coating film, and excellent balance of adhesion to the substrate. sell.
- the anti-blocking property of the coating film containing the modified product Tend to be better.
- Mw / Mn of the propylene / ⁇ -olefin copolymer (A1) exceeds 3.0; preferably about 3.1 to 5.0, more preferably about 3.1 to 4.0, Excellent affinity with other resins, fillers, and additives used for the coating material of the modified product, and the stability of the coating material is improved.
- the obtained coating film tends to be excellent in adhesion to the substrate.
- the weight average molecular weight (Mw) of the propylene / ⁇ -olefin copolymer (A1) can be measured by GPC. GPC measurement can be performed under the following conditions. Moreover, a weight average molecular weight (Mw) and a number average molecular weight (Mn) can be calculated
- the melting point (Tm) of the propylene / ⁇ -olefin copolymer (A1) obtained from the result of (ii) DSC is 60 to 110 ° C., preferably 60 to 90 ° C., more preferably 65 to 85 ° C., particularly preferably. Is in the range of 70-80 ° C.
- a modified product of the propylene / ⁇ -olefin copolymer (A1) having a melting point (Tm) in the above range has solubility, dispersibility, blocking resistance, and adhesion to a base material in an organic solvent or a resin used in combination. Excellent balance.
- the melting point (Tm) of the propylene / ⁇ -olefin copolymer (A1) can be measured by DSC-20 (manufactured by Seiko Denshi Kogyo Co., Ltd.) according to DSC (differential scanning calorimetry). About 10 mg of the sample is heated from ⁇ 20 ° C. to 200 ° C. at 10 ° C./min, and the temperature of the endothermic peak of the obtained curve can be obtained as the melting point. Prior to this temperature increase measurement, the sample (copolymer) was once heated to about 200 ° C., held for 5 minutes, and then cooled to room temperature ( ⁇ 20 ° C.) at 10 ° C./min. It is preferable to unify the thermal history of the (copolymer).
- the melting point of the modified propylene / ⁇ -olefin copolymer (A) is the content of the ⁇ -olefin having 4 or more carbon atoms or the ⁇ -olefin copolymer (A2) having 4 or more carbon atoms before pyrolysis. It can be adjusted according to production conditions (particularly the type of catalyst). In order to lower the melting point of the modified propylene / ⁇ -olefin copolymer (A), the content ratio of the ⁇ -olefin having 4 or more carbon atoms is increased, or the propylene / carbon number 4 or more before thermal decomposition is used. It is preferable that the catalyst used in the production of the ⁇ -olefin copolymer (A2) is a metallocene catalyst.
- the crystallization temperature (Tc) obtained from the result of DSC of the propylene / ⁇ -olefin copolymer (A1) is 20 to 80 ° C., preferably 30 to 70 ° C., more preferably 39 to 65 ° C., particularly preferably. It is in the range of 40 to 55 ° C.
- a modified product of the propylene / ⁇ -olefin copolymer (A1) having a crystallization temperature (Tc) in the above range is soluble in organic solvents or resins used in combination, dispersibility, blocking resistance, and adhesion to a substrate. Excellent balance of sex.
- the crystallization temperature (Tc) of the propylene / ⁇ -olefin copolymer can be measured by DSC-20 (manufactured by Seiko Denshi Kogyo Co., Ltd.) according to DSC (differential scanning calorimetry). About 10 mg of the sample is heated to about 200 ° C., held for 5 minutes, and then cooled to room temperature ( ⁇ 20 ° C.) at 10 ° C./min. And the temperature of the exothermic peak of the obtained curve can be obtained as the crystallization temperature.
- the propylene / ⁇ -olefin copolymer (A1) has (iii) a half-value width of the melting point peak measured by DSC of 1 to 20 ° C., preferably 5 to 20 ° C., more preferably 7 to 20 ° C., still more preferably 10 It is in the range of -15 ° C.
- a modified product of the propylene / ⁇ -olefin copolymer (A1) having a half-value width of the melting point peak in the above range has good solubility, dispersibility, and coating material stability in an organic solvent or a resin used in combination.
- the coating material has a high solidification rate and tends to have excellent blocking resistance.
- the half-value width of the melting point peak obtained from the DSC results is in the above range, which indicates that the distribution of ⁇ -olefin in the copolymer is uniform. It is thought that there is.
- the modified product of the propylene / ⁇ -olefin copolymer (A1) having a half width exceeding the above upper limit is considered to have a portion where ⁇ -olefins are densely packed and a portion where sparsely packed portions are present.
- the modified product of the propylene / ⁇ -olefin copolymer (A1) having a half width of less than or equal to the above lower limit has a narrow composition distribution, so it can be said that the compatibility with the resin and filler used together as a coating material is not necessarily good. Therefore, it is considered that the solubility and dispersibility tend to be inferior.
- the full width at half maximum can be obtained as a peak width (° C.) at a half amount position from the base line of the entire endothermic peak obtained by DSC to the endothermic peak top.
- the heat of fusion ( ⁇ H) obtained as a result of DSC of the propylene / ⁇ -olefin copolymer (A1) is 40 to 100 J / g, more preferably 45 to 80 J / g, still more preferably 45 to 70 J / g. Preferably it may be in the range of 45-60 J / g.
- the modified product of propylene / ⁇ -olefin copolymer (A1) having ⁇ H in the above range is excellent in the balance of solubility, dispersibility, stability and coating blocking resistance of the organic solvent or the resin used in combination.
- the modified product of the propylene / ⁇ -olefin copolymer (A1) can have high hardness despite the relatively low melting point (Tm) obtained by the DSC result, so that it is a coating material. When used in, etc., it is particularly excellent in the balance of solubility, dispersibility, and blocking resistance.
- the modified product of propylene / ⁇ -olefin copolymer (A1) has a melting peak (Tm) obtained from the result of DSC, but the melting peak ⁇ H is expected. It is estimated that it may be because it shows a large value outside.
- the amount of heat of fusion can be calculated as the amount of heat of fusion ( ⁇ H) (J / g) divided by the endothermic peak obtained by DSC and the baseline of the entire endothermic peak.
- the requirements (i) to (iii) of the propylene / ⁇ -olefin copolymer (A1) are the physical properties of the propylene / ⁇ -olefin copolymer (A2) having 4 or more carbon atoms before pyrolysis; Can be adjusted depending on the type of catalyst used in the production of the propylene / ⁇ -olefin copolymer (A2) having 4 or more carbon atoms.
- propylene / ⁇ -olefin copolymer (A1) for example, as propylene / ⁇ -olefin copolymer (A2) having 4 or more carbon atoms before pyrolysis It is preferable to use those produced under a metallocene catalyst.
- the number of vinylidene groups per 1000 carbon atoms, as measured by (iv) 1 HNMR, of the propylene / ⁇ -olefin copolymer (A1) is preferably 0.5 to 5.
- the propylene / ⁇ -olefin copolymer (A1) can contain more vinylidene groups in the molecular terminal portion than a polymer obtained by directly polymerizing monomers.
- the amount of the vinylidene group which is an unsaturated terminal of the propylene / ⁇ -olefin copolymer (A1) is preferably, for example, the number of vinylidene groups per 1000 carbon atoms measured by 1 H-NMR. Is 0.5 to 5/1000 carbon, more preferably 1 to 4/1000 carbon, and particularly preferably 2 to 3.5 / 1000 carbon.
- the polymer obtained by directly polymerizing the monomer obtains a desired molecular weight while suppressing a rise in molecular weight by coexisting a large amount of hydrogen during the polymerization, so that the resulting propylene / ⁇ -olefin copolymer (A1 ) Of vinylidene groups is reduced.
- the number of vinylidene groups in the propylene / ⁇ -olefin copolymer (A1) can be adjusted according to the thermal decomposition conditions. For example, in order to increase the number of vinylidene groups, it is preferable to increase the degree of thermal decomposition, that is, to increase the thermal decomposition ratio (Mw before thermal decomposition / Mw after thermal decomposition).
- the modified product of the propylene / ⁇ -olefin copolymer (A1) may be, for example, other resins used for coating materials,
- the affinity with the filler and additive is excellent, and the stability of the coating material containing the modified product becomes good.
- the obtained coating film is excellent in adhesiveness with a base material.
- the number of vinylidene groups possessed by the propylene / ⁇ -olefin copolymer (A1) can be measured by 1 H-NMR.
- 1 H-NMR a JNM-ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. was used and 20 mg of a sample was completely dissolved in about 0.5 ml of deuterated o-dichlorobenzene in an NMR sample tube (5 mm ⁇ ). , Measured at 120 ° C.
- Peak integrated intensity (C) of two protons derived from vinylidene groups observed at around 4.7 ppm when the total integrated intensity of the signal derived from the propylene / ⁇ -olefin copolymer (A1) is normalized to 2000 Can be applied to the following formula to calculate the number of vinylidene groups.
- Number of vinylidene groups L (pieces / 1000 carbons) C / 2
- the propylene / ⁇ -olefin copolymer (A1) has a crystallinity measured by X-ray diffraction of preferably 40 to 70%, more preferably 45 to 65%, and more preferably 50 to 58%. A range is particularly preferred.
- the degree of crystallinity of the propylene / ⁇ -olefin copolymer (A1) is higher than the above lower limit, the number of components causing solids decreases, so that the coating film containing the modified product may have good blocking resistance. .
- the amount is lower than the above upper limit, the amount of the crystal component derived from the propylene / ⁇ -olefin copolymer (A1), which is considered to hinder the solubility and dispersibility of the coating material, is reduced. It is considered that the property is improved.
- the crystallinity of the propylene / ⁇ -olefin copolymer (A1) can be measured by the following method. That is, the measurement sample is heated at 180 ° C. for 5 minutes with a hot press and then cooled with water with a cold press for 5 minutes to produce a 1 mm thick press sheet.
- 2 ⁇ is in the range of 5 ° to 35 ° by the transmission method using an X-ray diffractometer (RINT2500 manufactured by Rigaku Corporation) having a rotating sample stage under the conditions of Cu-K ⁇ ray and 50 kV-300 mA. Then, a wide angle X-ray diffraction profile is measured. From the obtained X-ray diffraction profile, the crystal-derived portion and the non-crystal-derived portion are separated, and the crystallinity is obtained from each diffraction intensity ratio.
- the propylene / ⁇ -olefin copolymer (A1) can be used not only as a raw material for the modified propylene / ⁇ -olefin copolymer (A) of the present invention but also for various applications.
- the propylene / ⁇ -olefin copolymer (A1) is a coating material, paint, primer, molding resin composition, resin modifier, hot melt adhesive composition, adhesive, pressure-sensitive adhesive, heat sealant, Ink binders, filler dispersants and pigment dispersants in paints, binders for ceramics and metallurgical compounds, printing ink antiwear agents, surface coating agents, additives for thermal transfer recording media, nonwoven fabric modifiers, toner additives, Polishing agent, mold release agent for resin molding, processing aid for rubber, paper quality improver, fiber processing aid, electrical insulation agent, natural wax compounding agent, polyolefin film antifogging agent, pigment dispersant (masterbatch) , Molding processing aids, rubber antioxidants, paper coatings, textile
- the propylene / ⁇ -olefin copolymer (A2) is preferably a propylene / ⁇ -olefin copolymer having 4 or more carbon atoms.
- ⁇ -olefin having 4 or more carbon atoms constituting the ⁇ -olefin copolymer (A2) having 4 or more carbon atoms include 1-butene, 1-hexene, 4-methyl / 1-pentene. , 1-octene, 1-decene and the like, preferably ⁇ -olefins having 4 to 10 carbon atoms, more preferably ⁇ -olefins having 4 to 8 carbon atoms, particularly preferably 1-butene. It is.
- the propylene / ⁇ -olefin copolymer (A2) having 4 or more carbon atoms (A2) contains a small amount of structural units derived from ethylene or the like as olefins other than propylene and ⁇ -olefins having 4 or more carbon atoms, such as 10 mol% or less. It may further be included in an amount of. On the other hand, it is also a preferred embodiment that a structural unit derived from ethylene is not included.
- the propylene / ⁇ -olefin copolymer (A2) having 4 or more carbon atoms contains 60 to 95 mol%, preferably 60 to 90 mol%, more preferably 65 to 88 mol% of the structural unit (a ′) derived from propylene.
- the weight average molecular weight (Mw) measured by GPC is 50,000 to 1,000,000, preferably 70,000 to 800,000, more preferably 100,000 to 600,000.
- the melting point (Tm) measured by DSC is in the range of 60 to 120 ° C., preferably 65 to 100 ° C., more preferably 70 to 90 ° C.
- the half-value width of the melting point peak measured by DSC is usually in the range of 1 to 20 ° C., preferably 2 to 18 ° C., more preferably 3 to 15 ° C., and further preferably 4 to 12 ° C.
- the method for measuring the weight average molecular weight, the melting point (Tm), and the half width of the melting point peak can be the same as the method for measuring the weight average molecular weight, the melting point (Tm) and the half width of the melting point peak, respectively.
- the propylene / ⁇ -olefin copolymer (A2) having 4 or more carbon atoms has a melting peak ⁇ H measured by DSC of preferably 30 to 100 J / g, more preferably 35 to 75 J / g, still more preferably 35 to It is 65 J / g, particularly preferably in the range of 40 to 55 J / g.
- the method for measuring the melting peak ⁇ H may be the same as the method for measuring the melting peak ⁇ H described above.
- the density of the ⁇ -olefin copolymer (A2) having 4 or more carbon atoms (A2) measured according to the density gradient tube method of JIS K 7112 is preferably in the range of 850 to 910 kg / m 3 .
- the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) of the ⁇ -olefin copolymer (A2) having 4 or more carbon atoms is usually 3 or less, preferably 1.8. To 3.0, more preferably 1.9 to 2.5.
- the method for measuring the molecular weight distribution (Mw / Mn) can be the same as the method for measuring the molecular weight distribution (Mw / Mn) described above.
- a copolymer obtained by thermally decomposing a propylene / ⁇ -olefin copolymer that does not satisfy the requirements (i ′) to (iii ′) has a tendency to widen the full width at half maximum of the melting point peak measured by DSC. May exceed 20 ° C. Moreover, ⁇ H of the melting peak measured by DSC may be small, for example, less than 40 J / g.
- a copolymer (A1) obtained by pyrolyzing an ⁇ -olefin copolymer (A2) having 4 or more carbon atoms that satisfies the above requirements (i ′) to (iii ′) is obtained by DSC.
- the spread of the measured half width is not large, for example, in the range of 1 to 20 ° C.
- the ⁇ H of the melting peak measured by DSC increases and tends to be in the range of 40 to 100 J / g, for example.
- the copolymer (A2) having a small width at half maximum is obtained by, for example, thermally decomposing the copolymer (A2) because there is little difference in the amount of ⁇ -olefin between molecules.
- the copolymer (A1) is considered to have little difference in the amount of ⁇ -olefin between the respective molecules. For this reason, it is considered that the copolymer (A1) obtained by thermally decomposing the copolymer (A2) is unlikely to be deteriorated in crystallinity. Rather, crystallinity may increase due to thermal decomposition.
- a copolymer having a large half-value width has a large difference in the amount of ⁇ -olefin between molecules, for example, so that a molecule having a large amount of ⁇ -olefin is likely to undergo thermal decomposition.
- the copolymer obtained by thermally decomposing the copolymer is considered to partially produce a component having an extremely low molecular weight and a relatively large amount of ⁇ -olefin. And it is estimated that such a component may have a function of reducing the crystallinity of the produced polymer.
- the ⁇ -olefin copolymer (A2) having 4 or more carbon atoms can be produced by various known production methods, for example, a method using a high pressure method, a Ziegler catalyst or a metallocene catalyst.
- conventionally known catalysts such as JP-A-57-63310, JP-A-58-83006, JP-A-3-706, JP-A-3476793, JP-A-4-218508, Magnesium-supported titanium catalysts described in JP-A No. 2003-105022, etc., WO 01/53369 pamphlet, WO 01/27124 pamphlet, WO 2004/087775 pamphlet, JP Hei 3-
- the metallocene catalyst described in Japanese Patent No. 193796 or Japanese Patent Application Laid-Open No. 02-41303 can be suitably used.
- the propylene / ⁇ -olefin copolymer (A2) having 4 or more carbon atoms (A2) has a low melting point and a uniform molecular weight distribution, so that a propylene / ⁇ -olefin copolymer (A1) can be easily obtained.
- the metallocene catalyst is preferably used.
- Step 2 The propylene / ⁇ -olefin copolymer (A1) obtained in the above 1) is graft-polymerized with a polar compound containing a double bond to produce a modified propylene / ⁇ -olefin copolymer (A).
- the polar compound containing a double bond is preferably at least one selected from an unsaturated carboxylic acid or derivative thereof, or an unsaturated sulfonic acid or salt thereof.
- maleic anhydride As a particularly preferred example of the polar compound containing a double bond, maleic anhydride can be mentioned.
- Maleic anhydride has a relatively high reactivity with the above-mentioned propylene / ⁇ -olefin copolymer (A1), and itself tends to have a large structural change due to polymerization and tends to be stable as a basic structure. For this reason, there is an advantage that a modified propylene / ⁇ -olefin copolymer (A) having a stable quality is easily obtained.
- the modified propylene / ⁇ -olefin copolymer (A) of the present invention is grafted on the propylene / ⁇ -olefin copolymer (A1) with a polar compound containing a double bond corresponding to the polar group structural unit. It can be obtained by denaturation.
- the graft modification of the propylene / ⁇ -olefin copolymer (A1) can be performed by a known method.
- the propylene / ⁇ -olefin copolymer (A1) is dissolved in an organic solvent, and then a polar compound containing a double bond such as an unsaturated carboxylic acid and a radical initiator are added to the resulting solution.
- a polar compound containing a double bond such as an unsaturated carboxylic acid and a radical initiator are added to the resulting solution.
- examples thereof include a method of reacting at a temperature of 350 ° C., preferably 80 to 190 ° C., for 0.5 to 15 hours, preferably 1 to 10 hours.
- the organic solvent is not particularly limited as long as it is an organic solvent that can dissolve the propylene / ⁇ -olefin copolymer.
- organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane and heptane.
- an extruder or the like is used, preferably without using a solvent, and a propylene / ⁇ -olefin copolymer (A1) and a double bond such as an unsaturated carboxylic acid are contained.
- the method of making it react with a polar compound is mentioned.
- the reaction conditions in this case are such that the reaction temperature is usually not lower than the melting point of the propylene / ⁇ -olefin copolymer (A1), specifically 100 to 350 ° C.
- the reaction time can usually be 0.5 to 10 minutes.
- organic peroxides organic peroxides such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexyne- 3,1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5- Dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperbenzoate, t-butylperphenylacetate, t-butylperisobutyrate, t-butylper-sec-octoate, t-butylperpivalate , Cumyl perpivalate and t- Chi
- dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t Dialkyl peroxides such as -butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferred.
- the radical initiator is usually used in a proportion of 0.001 to 1 part by weight based on 100 parts by weight of the propylene / ⁇ -olefin copolymer (A1) before modification.
- the propylene / ⁇ -olefin copolymer (A1) which is a thermal decomposition product of a copolymer (A2) containing a propylene unit and an ⁇ -olefin unit having 4 or more carbon atoms, is graft-modified.
- the propylene / ⁇ -olefin copolymer (A1) mainly contains “molecules having a vinylidene group at the terminal portion” generated by main chain cleavage; “vinyl having high reactivity at the terminal portion” “Molecules having a group” as well as “molecules having an internal double bond with low reactivity at the terminal portion” are also considered to be included.
- the propylene / ⁇ -olefin copolymer (A1) which is a pyrolysis product containing propylene units and ⁇ -olefin units having 4 or more carbon atoms, is a homopolypropylene wax (PP wax) pyrolysis product or propylene / ethylene.
- PP wax homopolypropylene wax
- PER wax thermal decomposition product of wax
- the formation probability of “internal double bond” is high and the formation probability of “vinyl group” is low. Therefore, it is considered that, during the graft modification reaction, the crosslinking reaction due to the vinyl group at the molecular end portion can be suppressed and the increase in viscosity can be reduced.
- the upper limit of the weight average molecular weight (Mw) measured by GPC of the modified propylene / ⁇ -olefin copolymer (A) is 50,000, preferably 40,000, more preferably 25,000, particularly preferably 18.
- the lower limit of the weight average molecular weight (Mw) may be 3,000, preferably 5,000, more preferably 8,000, particularly preferably 12,000.
- a modified propylene / ⁇ -olefin copolymer (A) having a weight average molecular weight (Mw) in the above range When a modified propylene / ⁇ -olefin copolymer (A) having a weight average molecular weight (Mw) in the above range is used, a higher concentration can be achieved and a coating material having excellent handling properties can be obtained. Moreover, the coating film obtained is uniform, has excellent blocking resistance, and has good adhesion to the substrate.
- the modified propylene / ⁇ -olefin copolymer (A) having a weight average molecular weight (Mw) of not more than the above upper limit is considered to be excellent in solubility and dispersibility in an organic solvent or resins used in combination. For this reason, it is considered that the viscosity of the coating material becomes moderate, and the concentration can be further increased, or good handling properties can be maintained. Further, for the same reason, it is considered that a uniform coating film is obtained with little streaking and
- the modified propylene / ⁇ -olefin copolymer (A) having a weight average molecular weight (Mw) of not more than the upper limit is more easily crystallized and has a solidification rate in the drying step. It is presumed that the anti-blocking property is developed as a result of increasing the speed.
- the modified propylene / ⁇ -olefin copolymer (A) having a weight average molecular weight (Mw) below the upper limit makes it easy for the coating film containing it to follow the substrate, and the shrinkage of the coating film is low. It is considered that the adhesion to the base material can be improved due to the suppressed effect.
- the modified propylene / ⁇ -olefin copolymer (A) having a weight average molecular weight (Mw) of not less than the above lower limit is considered to have good blocking resistance due to the effect of reducing the solid component due to the low molecular weight.
- the olefin of the low molecular weight modified propylene / ⁇ -olefin copolymer (A) has many solid components and is considered difficult to handle as a coating film, but the weight average molecular weight (Mw) is within the above range. By doing, the coating film which is excellent in blocking resistance is easy to be obtained.
- the melting point (Tm) obtained from the result of DSC of the modified propylene / ⁇ -olefin copolymer (A) is 55 to 105 ° C., preferably 60 to 95 ° C., more preferably 65 to 85 ° C., particularly preferably 67 It can be in the range of ⁇ 80 ° C.
- the modified propylene / ⁇ -olefin copolymer (A) having a melting point (Tm) in the above range has a good balance of solubility and dispersibility in organic solvents or resins used in combination, blocking resistance, and adhesion to a substrate. Excellent.
- the crystallization temperature (Tc) of the modified propylene / ⁇ -olefin copolymer (A) obtained as a result of DSC is 15 to 80 ° C., preferably 25 to 70 ° C., more preferably 30 to 70 ° C., particularly preferably. May be in the range of 40-50 ° C.
- the modified propylene / ⁇ -olefin copolymer (A) having a crystallization temperature (Tc) in the above range has solubility and dispersibility in organic solvents or resins used in combination, blocking resistance, and adhesion to a substrate. Excellent balance.
- the modified propylene / ⁇ -olefin copolymer (A) tends to have less decrease in crystallinity due to modification than the modified propylene wax obtained by the direct polymerization method. Accordingly, when the crystallization temperature of the propylene / ⁇ -olefin copolymer (A1) is Tc (A1) and the crystallization temperature of the modified propylene / ⁇ -olefin copolymer (A) is Tc (A),
- the ratio Tc (A1) / Tc (A) of the crystallization temperature can be in the range of 1.0 to 1.6, preferably 1.0 to 1.5, particularly preferably 1.1 to 1.3.
- the modified propylene / ⁇ -olefin copolymer (A) having a crystallization temperature ratio Tc (A) / Tc (A1) in the above range is soluble, dispersible, and blocking resistant in an organic solvent or a resin used in combination. Excellent balance of adhesion time with coating and solidification time of substrate.
- the crystallization temperature ratio Tc (A1) / Tc (A) is in the above-mentioned range means that the change in the crystallization temperature is small even when the crystallization temperature is modified. That is, it is suggested that the modification has a small effect on crystallinity.
- the polar group structural units are grafted to the main chain, so that it is expected that the crystallinity of the main chain tends to be lowered, and thereby the crystallization temperature tends to be lowered.
- the modified propylene / ⁇ -olefin copolymer (A) of the present invention most of the polar group structural units are composed of vinylidene groups or internal dimers in the molecular terminal portion of the propylene / ⁇ -olefin copolymer (A1). It is thought that it is added to the double bond.
- the modified propylene / ⁇ -olefin copolymer (A) of the present invention has little decrease in crystallinity accompanying an increase in the amount of modification.
- the modified propylene / ⁇ -olefin copolymer (A) can exhibit excellent blocking resistance while having excellent solubility and dispersibility in solvents and water, and adhesion to a substrate. it is conceivable that.
- the modified propylene / ⁇ -olefin copolymer (A) of the present invention is used as a coating material such as a primer, it is considered that the coating film can be solidified (crystallized) in a short time.
- the half width of the melting point peak measured by (iii) DSC of the modified propylene / ⁇ -olefin copolymer (A) is 1 to 40 ° C., preferably 5 to 30 ° C., more preferably 10 to 25 ° C. Preferably it can be in the range of 12-22 ° C.
- the modified propylene / ⁇ -olefin copolymer (A) having a half-value width of the melting point peak in the above range is excellent in solubility and dispersibility in an organic solvent or a resin to be used together. For example, when used in a coating material or the like, The stability of the coating material is improved. In addition, the solidification rate of the coating is high and the blocking resistance tends to be excellent.
- the half-value width of the melting point peak obtained from the DSC results is in the above range, indicating that the distribution of ⁇ -olefin in the copolymer is uniform. It is thought that it is.
- the modified propylene / ⁇ -olefin copolymer (A) having a half-width exceeding the above upper limit is considered to have a portion where ⁇ -olefin is densely contained and a portion where sparsely contained ⁇ . The portion where the olefin is densely becomes sticky and may cause deterioration of the blocking resistance.
- the modified propylene / ⁇ -olefin copolymer (A) having a half-value width equal to or lower than the lower limit has a narrow composition distribution, and thus cannot be said to have good compatibility with resins and fillers used together as a coating material. It is considered that the solubility and dispersibility tend to be inferior.
- the heat of fusion ( ⁇ H) of the modified propylene / ⁇ -olefin copolymer (A) obtained as a result of DSC is preferably 20 to 100 J / g, more preferably 25 to 80 J / g, still more preferably 30 to 65 J. / G, most preferably in the range of 35-60 J / g.
- the modified propylene / ⁇ -olefin copolymer (A) having ⁇ H in the above range is excellent in the balance of solubility in organic solvents or resins used in combination, dispersibility, coating material stability, and blocking resistance of the coating film. .
- the modified propylene / ⁇ -olefin copolymer (A) can have a high hardness despite the relatively low melting point (Tm) obtained as a result of DSC.
- Tm melting point
- the modified propylene / ⁇ -olefin copolymer (A) when used as a coating material, it is particularly excellent in terms of the balance of solubility, dispersibility, and blocking resistance. The reason for this is not clear, but the modified propylene / ⁇ -olefin copolymer (A) has an unexpected melting peak ⁇ H despite the relatively low melting point (Tm) obtained from the DSC results. It is presumed to indicate a large value.
- the Mw, melting point (Tm), crystallization temperature (Tc), half-value width of the melting peak, and ⁇ H of the melting peak of the modified propylene / ⁇ -olefin copolymer (A) can be measured in the same manner as described above. .
- the acid value of the modified propylene / ⁇ -olefin copolymer (A) is preferably 0.5 to 100 KOH mg / g, more preferably 3 to 65 KOH mg / g, and 5 to 55 KOH mg / g. Is more preferable, and 10 to 50 KOH mg / g is particularly preferable.
- the acid value of the modified propylene / ⁇ -olefin copolymer (A) can be adjusted by the modification amount of the propylene / ⁇ -olefin copolymer (A1).
- the amount of modification of the propylene / ⁇ -olefin copolymer (A1) it is considered that the effect of modification can be sufficiently obtained.
- the modified propylene / ⁇ -olefin copolymer (A) is obtained from the propylene / ⁇ -olefin copolymer (A1) obtained by thermal decomposition, most of the polar group structural units are composed of propylene / ⁇ -olefin copolymer. It is thought that it has added to the vinylidene group or internal double bond of the molecule
- the penetration of the modified propylene / ⁇ -olefin copolymer (A) is preferably 8 dmm or less, more preferably 5 dmm or less, particularly preferably 3 dmm or less from the viewpoint of blocking resistance and the like. preferable.
- the penetration of the modified propylene / ⁇ -olefin copolymer (A) can be measured by the following method. That is, in accordance with JIS K 2207, a sample of the modified propylene / ⁇ -olefin copolymer (A) melted so as to avoid partial overheating and to prevent bubbles from entering at a room temperature of 15 to 30 ° C. in a range of 1-1. Let stand for 5 hours to solidify. Thereafter, the temperature is maintained at 25 ° C. in a thermostatic bath, and the length that the specified needle enters the sample surface in 5 seconds after the temperature is stabilized is determined as the penetration (dmm).
- the modified propylene / ⁇ -olefin copolymer (A) of the present invention tends to have a small decrease in crystallization temperature even when the amount of modification increases. Accordingly, when the modified propylene / ⁇ -olefin copolymer (A) is used as a coating material such as a primer, the coating film can be solidified (crystallized) in a short time.
- the half crystallization time of the modified propylene / ⁇ -olefin copolymer (A) is not particularly limited, but is usually 2000 seconds or shorter, preferably 1500 seconds or shorter, more preferably 1000 seconds or shorter, particularly preferably 700 seconds or shorter. Most preferably, it is 550 seconds or less.
- the modified propylene / ⁇ -olefin copolymer (A) having a semi-crystallization time of 2000 seconds or less is short in coating film solidification time and excellent in workability when applied to a substrate. . Moreover, it is excellent in the balance of the blocking resistance of a coating film, and the adhesiveness to a base material.
- the half crystallization time is 30 seconds or more, preferably 50 seconds or more, more preferably 70 seconds or more, still more preferably 90 seconds or more, particularly preferably 150 seconds or more, and most preferably 300 seconds or more.
- the half crystallization time is 30 seconds or longer, it is possible to suppress the occurrence of streaks and unevenness and deterioration of the coatability when the substrate is coated.
- the adhesiveness of the obtained coating film to the base material is not easily lost. The reason is not clear, but if the semi-crystallization time is too short, the leveling property is inferior in the drying process of the coating film, so the adhesion of the coating film to the substrate is uneven and the coating film adhesion is reduced. It is thought to be due to.
- the half crystallization time can be measured by the following method. Using a differential scanning calorimeter (Perkin Elmer, DSC7), about 5 mg of the sample is set and left at 200 ° C. for 5 minutes to completely melt the sample. Thereafter, isothermal crystallization is performed by rapidly cooling to 50 ° C. at a temperature lowering rate of 320 ° C./min. The time from the start of cooling until the heat of crystallization reaches 1 ⁇ 2 of the total calorific value is defined as the half crystallization time.
- DSC7 differential scanning calorimeter
- Semi-crystallization time can be adjusted by the amount of ⁇ -olefin or acid introduced.
- the modified propylene / ⁇ -olefin copolymer (A) is obtained by modifying the propylene / ⁇ -olefin copolymer (A1) obtained by thermal decomposition as described above, most of the polar group structural units are: It is considered that the propylene / ⁇ -olefin copolymer (A1) is attached to a vinylidene group or an internal double bond at the molecular end portion. Therefore, it is considered that the modified propylene / ⁇ -olefin copolymer (A) has a high crystallization rate and can shorten the semi-crystallization time.
- the resin composition of the present invention includes the modified propylene / ⁇ -olefin copolymer (A) of the present invention, and may further include another resin (B1) as necessary.
- Other resins (B1) include olefin resins, styrene resins, polyurethane, polyester, polyamide, polycarbonate, polyvinyl alcohol, polyvinyl acetate, epoxy resins, acrylic resins, rosin resins, alkyd resins, urea resins, melamine resins, Phenol resin, coumarone resin, ketone resin, cellulose resin, chlorinated polyolefin, or a mixed resin thereof can be used.
- olefin resins and styrene resins are preferable, and olefin elastomers and styrene elastomers are particularly preferable.
- a resin composition is used as a primer, polyurethane, an epoxy resin, and an acrylic resin are preferable, and an acrylic resin is particularly preferable from the viewpoint of easily obtaining adhesion with the overcoat layer.
- a propylene elastomer is preferable.
- the propylene-based elastomer include propylene / 1-butene copolymer, acid-modified propylene / 1-butene copolymer, and the like.
- the styrenic elastomer a block copolymer containing 10 to 60 mol% of a styrene unit is preferable; examples thereof include Tuftec (manufactured by Asahi Kasei), Septon (manufactured by Kuraray), Kraton (manufactured by Shell), and the like. Can be mentioned.
- These olefin-based elastomers and styrene-based elastomers are also excellent in adhesion to olefin-based coated substrates.
- the other resin (B1) may be obtained by graft copolymerization of a polar monomer as necessary.
- polar monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, unsaturated carboxylic acids and anhydrides and derivatives thereof, and vinyl ester compounds.
- unsaturated carboxylic acids and their anhydrides are preferred in order to enhance solvent solubility and adhesion to the substrate to be coated.
- the stability of the coating material using the resin composition of the present invention, the coating property, The blocking resistance of the coating film made of the resin composition and the adhesion to the substrate to be coated can be improved.
- the resin composition of the present invention when used, the low molecular weight component of the modified propylene / ⁇ -olefin copolymer (A) is compatible with the other resin (B1). It is considered that the viscosity of the resin can be effectively reduced and the stability and coating property of the coating material can be improved.
- the weight ratio of the modified propylene / ⁇ -olefin copolymer (A) to the other resin (B1) is usually 1/99 to 90/10, preferably 1/99 to 50/50, more preferably 2/98 to 30/70, and still more preferably 8/92 to 25/75. If it is within the range of the above values, the stability and coating property of the coating material using the resin composition of the present invention will be improved, the blocking resistance of the coating film comprising this resin composition, and the adhesion to the substrate. The properties such as the strength and heat resistance of other resins can be kept good.
- the resin composition of the present invention includes a propylene / ⁇ -olefin copolymer (A1), a propylene / ⁇ -olefin copolymer having 4 or more carbon atoms (A2) as necessary, as long as the object of the present invention is not impaired.
- additives such as a hydrochloric acid absorbent, an antioxidant, and a copper damage inhibitor may be further contained.
- the resin composition of the present invention can be produced by dry blending or melt blending using any of various methods.
- a modified propylene / ⁇ -olefin copolymer (A), another resin (B1), and other optional components can be used simultaneously or in any order in a tumbler, V-type blender, now.
- a method of blending with a turmixer, Banbury mixer, kneading roll, single-screw or twin-screw extruder is suitably used.
- the modified propylene / ⁇ -olefin copolymer (A), the other resin (B1), and other optional components are once dispersed or dissolved in an arbitrary solvent, followed by natural drying or forced heating drying.
- blending may be performed by drying by an appropriate method.
- Modified Propylene / ⁇ -Olefin Copolymer (A) The modified propylene / ⁇ -olefin copolymer (A) of the present invention and the resin composition of the present invention can be used in various applications such as coating materials and molding resins. It can be used in compositions, hot melt compositions, paints, primers, adhesives, pressure-sensitive adhesives, sintering aids, and the like.
- composition for the above-mentioned use containing the modified propylene / ⁇ -olefin copolymer (A) of the present invention is within the range not impairing the purpose of the present invention, and other thermoplastic resins, weather resistance stabilizers, Stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, nucleating agent, lubricant, pigment, filler, dye, plasticizer, anti-aging agent, hydrochloric acid absorbent, antioxidant, copper damage inhibitor Etc. may further be included.
- the first coating material of the present invention contains a modified propylene / ⁇ -olefin copolymer (A) and water or an organic solvent.
- the modified propylene / ⁇ -olefin copolymer (A) may be the modified propylene / ⁇ -olefin copolymer (A) of the present invention.
- the organic solvent is not particularly limited but is preferably an aromatic hydrocarbon such as benzene, toluene or xylene; an aliphatic hydrocarbon such as hexane, heptane, octane or decane; cyclohexane, cyclohexene, methylcyclohexane or ethylcyclohexane.
- Alicyclic hydrocarbons such as aromatic hydrocarbons (aliphatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons are collectively referred to as hydrocarbon solvents); halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene, etc.
- Alcohol-based solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; ketone-based solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone pentanone, hexanone, isophorone, and acetophenone; Cellsolves such as methyl cellosolve and ethyl cellosolve; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate; ether solvents such as tetrahydrofuran are selected alone or two or more selected, Can be used.
- ketone-based solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone pentanone, hexanone, isophorone, and acetophen
- an organic solvent having a solubility parameter described later in a specific range is preferable.
- the organic solvent having a solubility parameter within a preferable range include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane.
- Alicyclic hydrocarbons such as hexane; alcohols having 4 to 12 carbon atoms such as isopropyl alcohol, dodecanol and butanol; esters having 4 to 12 carbon atoms such as ethyl acetate, butyl acetate and diethyl phthalate; N-methylpyrrolidone And pyrrolidones. These can be used alone or in combination of two or more.
- the organic solvent is preferably a hydrocarbon solvent, an alcohol solvent, or an ester solvent, more preferably a hydrocarbon solvent or an alcohol solvent, and more preferably an aliphatic hydrocarbon or an alicyclic ring from the viewpoint of environmental problems.
- Group hydrocarbons tend to be preferably used; particularly preferred are methylcyclohexane and ethylcyclohexane.
- solubility Parameter SP value, unit (cal / cm 3 ) 1/2
- the SP value is preferably 7.0 to 12.0, and 7.2. Is more preferably 12.0, more preferably 7.5-9.5, particularly preferably 7.7-9.0, and more preferably 7.7-8.5. Most preferred.
- the SP value of the organic solvent is within the above range, the modified propylene / ⁇ -olefin copolymer (A) is excellent in solubility and dispersibility in the organic solvent, and is excellent in stability as a coating material.
- the modified propylene / ⁇ -olefin copolymer (A) is easily completely dissolved at room temperature, so that the workability is excellent. A uniform coating film can be obtained.
- Solubility parameter (SP value) is Polymer Handbook, Fourth Edition (Edited by: Brandrup, J .; Immergut, Edmund H .; Grulke, Eric A .; Abe, Akihiro; Bloch, Daniel R. 1999), WILEY -This is the value described in INTERSCIENCE.
- the SP value of the mixed solvent is obtained by adding the SP value of each solvent component constituting the mixed solvent multiplied by the volume fraction. Further, the SP value of the homopolymer is calculated by the following SP value calculation formula based on the molecular attractive constant G of the structural unit forming the polymer.
- d the density (g / l) of the homopolymer
- ⁇ G the sum of the molecular attractive constants in the molecules of the structural unit
- M the molecular weight (g / mol) of the structural unit.
- the modified propylene / ⁇ -olefin copolymer (A) may be dispersed or dissolved in a solvent as a coating material. Even if the modified propylene / ⁇ -olefin copolymer (A) is in a dispersed state at a temperature of less than 50 ° C., it is preferably completely dissolved in an organic solvent at a temperature of 50 ° C. or more. It is more preferable to dissolve completely in the range of, and it is particularly preferable to completely dissolve at room temperature or higher and lower than 40 ° C. Since the modified propylene / ⁇ -olefin copolymer (A) is in a dissolved state at a low temperature, a good film forming state can be obtained at a low coating temperature.
- a dispersed state it is preferable that a non-uniform state such as sedimentation is not visually confirmed after standing for 1 day at a concentration of 10% by weight of an olefin resin in a methylcyclohexane medium.
- a method for dissolving or dispersing the modified propylene / ⁇ -olefin copolymer (A) in water or an organic solvent is not particularly limited, but the modified propylene / ⁇ -olefin copolymer (A) is dissolved in water or an organic solvent with stirring.
- the mixture of the modified propylene / ⁇ -olefin copolymer (A) and water or an organic solvent is heated to a completely or incompletely dissolved state and then gradually cooled to form fine particles. The method of doing is mentioned.
- the solvent composition is set so as to precipitate in advance at 60 to 100 ° C., and the average cooling rate during this period is adjusted to 1 to 20 ° C./hour, preferably 2 to 10 ° C./hour.
- the average cooling rate during this period is adjusted to 1 to 20 ° C./hour, preferably 2 to 10 ° C./hour.
- the poor solvent may be added to further perform the precipitation.
- it can also be used as a coating material in which water or an organic solvent is once removed and then dissolved and dispersed in an arbitrary solvent.
- the coating material of the present invention may be partly or wholly dissolved in the resin as well as those in which the modified propylene / ⁇ -olefin copolymer (A) is dispersed in various water or organic solvents. .
- the modified propylene / ⁇ -olefin copolymer (A) is 60 revolutions at a temperature of 23 ° C. in the coating material at a concentration of 10% by weight (for example, 10 parts by weight of olefin resin with respect to 90 parts by weight of methylcyclohexane).
- the viscosity is preferably 500 mPa ⁇ s or less.
- a preferred lower limit is 0.5 mPa ⁇ s, more preferably 1 mPa ⁇ s.
- a preferable upper limit is 300 mPa ⁇ s, more preferably 30 mPa ⁇ s, and particularly preferably 10 mPa ⁇ s.
- a rotational viscosity of 60 in this range is preferable because it can be applied to various coating methods.
- the viscosity is not more than the above upper limit, the coating material is excellent in stability and handling properties. In addition, streaks and unevenness are suppressed, and a coating film having a uniform thickness can be obtained.
- it is equal to or more than the above lower limit, it becomes easy to secure the coating thickness, and the penetration of the coating material into the base material and the deterioration of the base material can be suppressed.
- the content of the modified propylene / ⁇ -olefin copolymer (A) in the first coating material of the present invention is usually 0.1 to 100 parts by weight with respect to 100 parts by weight of water or an organic solvent.
- the upper limit is preferably 55 parts by weight, more preferably 40 parts by weight, still more preferably 25 parts by weight, and particularly preferably 15 parts by weight.
- the lower limit is preferably 3 parts by weight, more preferably 8 parts by weight.
- the coating material When the modified propylene / ⁇ -olefin copolymer (A) is below the above upper limit with respect to 100 parts by weight of water or an organic solvent, the coating material is excellent in stability and handling properties. In addition, streaks and unevenness are suppressed, and a coating film having a uniform thickness can be obtained. On the other hand, when it is at least the above lower limit, it becomes easy to ensure the thickness of the coating film and is excellent in drying property. Further, the penetration of the coating material into the base material and the deterioration of the base material can be suppressed.
- the second coating material of the present invention contains a modified propylene / ⁇ -olefin copolymer (A), another resin (B1), and water or an organic solvent.
- the modified propylene / ⁇ -olefin copolymer (A) and the organic solvent can be defined in the same manner as described above.
- Other resins (B1) include olefin resins, styrene resins, polyurethane, polyester, polyamide, polycarbonate, polyvinyl alcohol, polyvinyl acetate, epoxy resins, acrylic resins, rosin resins, alkyd resins, urea resins, melamine resins, Phenol resin, coumarone resin, ketone resin, cellulose resin, chlorinated polyolefin, or a mixed resin thereof can be used.
- olefin resins and styrene resins are preferable, and olefin elastomers and styrene elastomers are particularly preferable.
- a 2nd coating material is used as a primer, a polyurethane, an epoxy resin, and an acrylic resin are preferable from the viewpoint of making it easy to acquire adhesiveness with an overcoat layer, and an acrylic resin is especially preferable.
- a propylene elastomer is preferable.
- the propylene-based elastomer include propylene / 1-butene copolymer, acid-modified propylene / 1-butene copolymer, and the like.
- the styrenic elastomer a block copolymer containing 10 to 60 mol% of a styrene unit is preferable; examples thereof include Tuftec (manufactured by Asahi Kasei), Septon (manufactured by Kuraray), Kraton (manufactured by Shell), and the like. Can be mentioned.
- These olefin-based elastomers and styrene-based elastomers are also excellent in adhesion to olefin-based coated substrates.
- the other resin (B1) may be obtained by graft copolymerization of a polar monomer as necessary.
- polar monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, unsaturated carboxylic acids and anhydrides and derivatives thereof, and vinyl ester compounds.
- unsaturated carboxylic acids and their anhydrides are preferred in order to enhance solvent solubility and adhesion to the substrate to be coated.
- the stability of the coating material of the present invention, the coating property, the blocking resistance of the coating film, the coating Adhesion with the work substrate can be improved.
- the coating material of the present invention since the low molecular weight component is compatible with the above-mentioned resin, the viscosity of the resin is effectively reduced, and the stability of the coating material and the coating material are reduced. It is thought that workability can be improved.
- followability to a to-be-coated base material increases, it is guessed that adhesiveness with a to-be-coated base material improves.
- the method for dissolving or dispersing the modified propylene / ⁇ -olefin copolymer (A) and the other resin (B1) in water or an organic solvent is not particularly limited, but the modified propylene / ⁇ -olefin copolymer is stirred.
- a method of dissolving and dispersing (A) and another resin (B1) in water or an organic solvent, or under stirring, a modified propylene / ⁇ -olefin copolymer (A), another resin (B1) and water or organic A method of gradually cooling the mixture of solvents from a state in which the solvent mixture is heated and completely or incompletely dissolved to form fine particles is exemplified.
- the order in which the modified propylene / ⁇ -olefin copolymer (A) and the other resin (B1) are dissolved or dispersed in water or an organic solvent is not particularly limited, either one of which is dissolved in water or an organic solvent first. After the dispersion, the other is dissolved or dispersed in water or an organic solvent, or both are simultaneously dissolved or dispersed in water or an organic solvent.
- the modified propylene / ⁇ -olefin copolymer (A) and other resins ( A resin composition containing B1) may be dissolved or dispersed in water or an organic solvent.
- the solvent composition is set so as to precipitate in advance at 60 to 100 ° C., and the average cooling rate during this period is adjusted to 1 to 20 ° C./hour, preferably 2 to 10 ° C./hour.
- the average cooling rate during this period is adjusted to 1 to 20 ° C./hour, preferably 2 to 10 ° C./hour.
- the poor solvent may be added to further perform the precipitation.
- it can also be used as a coating material in which water or an organic solvent is once removed and then dissolved and dispersed in an arbitrary solvent.
- the coating material of the present invention is not limited to a state in which the modified propylene / ⁇ -olefin copolymer (A) and the other resin (B1) are dispersed in various water or organic solvents, but also part or all of the resin. May be dissolved.
- the total amount of the modified propylene / ⁇ -olefin copolymer (A) and the other resin (B1) in the second coating material of the present invention is usually 0.1 to 100 parts by weight of water or an organic solvent.
- the upper limit is preferably 70 parts by weight, more preferably 40 parts by weight, and particularly preferably 30 parts by weight.
- the lower limit is preferably 3 parts by weight, more preferably 8 parts by weight.
- the weight ratio of the modified propylene / ⁇ -olefin copolymer (A) and the other resin (B1) in the second coating material of the present invention is usually 1/99 to 90/10, preferably 1/99. 99 to 50/50, more preferably 2/98 to 30/70, and still more preferably 8/92 to 25/75. If it is within the above range, the stability of the coating material of the present invention, the coating property, the blocking resistance of the coating film, the adhesion with the substrate, and the strength and heat resistance of other resins are improved. These characteristics can be kept good.
- the coating material of the present invention (the first and second coating materials of the present invention) can be applied to the surface of a substrate to be coated such as a resin molded product. You may apply
- the coating method of the coating material of the present invention is not particularly limited, but it is preferably applied by spraying, brushing, coater, etc.
- it can be applied by spraying on the surface to be coated with a spray gun.
- the application can usually be easily performed at room temperature.
- there is no particular limitation on the drying method after coating and it can be dried by an appropriate method such as natural drying or forced heating drying.
- the surface of the substrate to be coated is applied to the surface of the substrate by electrostatic coating, spray coating, brush coating, or the like.
- Other paints can be applied.
- the coating may be applied by a method of overcoating after undercoating.
- the coating material of this invention is a solvent type thermoplastic acrylic resin coating material, a solvent type thermosetting acrylic resin coating material, an acrylic modified alkyd resin coating material, a polyester coating material, an epoxy resin coating material, and a polyurethane resin coating material.
- a primer coating film having high paint adhesion can be formed by pre-coating the substrate to be coated.
- the coating film After applying the coating material to the substrate to be coated, the coating film is cured according to a normal method of heating with nichrome wire, infrared rays, high frequency, etc., and a molded product having a desired coating film on the surface can be obtained.
- the method for curing the coating film can be appropriately selected depending on the material and shape of the substrate to be coated, the properties of the paint used, and the like. While improving the adhesiveness to the surface of various to-be-coated base materials, it can also be used in order to form the coating film which is more excellent in sharpness etc.
- the coating material of the present invention can be used as a substrate to be coated, for example, high-pressure polyethylene, medium-low-pressure polyethylene, polypropylene, poly-4-methyl-pentene, polystyrene and other polyolefins, ethylene / propylene copolymer, ethylene / butene copolymer. It can be suitably used for a molded article made of an olefin copolymer such as a polymer and a propylene / butene copolymer. In particular, it can be preferably used for molded articles made of polypropylene, ethylene / propylene copolymer, ethylene / butene copolymer, and propylene / butene copolymer.
- the coating material of the present invention includes, in addition to the above-mentioned molded products made of polyolefin or olefin copolymer, molded products made of polypropylene and synthetic rubber, polyamide resins, unsaturated polyester resins, polybutylene terephthalate resins, polycarbonate resins, etc. It can also be used for surface treatment of molded articles such as automotive bumpers, and further steel sheets and electrodeposition-treated steel sheets. In addition, the surface is coated with paint, primer, adhesive, etc. mainly composed of polyurethane resin, fatty acid-modified polyester resin, oil-free polyester resin, melamine resin, epoxy resin, etc. In addition, it can be used to form a coating film having excellent sharpness, low-temperature impact properties, and the like.
- the coating material of the present invention includes molded articles made of polyolefin such as polypropylene, molded articles such as automobile bumpers made of polypropylene and synthetic rubber, SMC molded articles using unsaturated polyester resin, epoxy resin, etc., R of polyurethane resin -RIM molded article, glass fiber reinforced polyamide resin molded article, polyurethane resin molded article, cationic electrodeposition coated steel sheet and the like are suitable for improving the adhesion of the paint to the surface of these molded articles.
- the coating layer (for example, primer layer) coated with the coating material of the present invention contains the low-melting modified propylene / ⁇ -olefin copolymer (A), it can be heat-sealed at a low temperature.
- the coating layer (for example, primer layer) coated with the coating material of the present invention can be solidified (crystallized) in a short time.
- the reason for this is not clear, but it is considered that the modified propylene / ⁇ -olefin copolymer (A) has a polar group at the molecular end portion, and therefore the decrease in crystallization temperature is small.
- the coating layer (for example, primer layer) coated with the coating material of the present invention can have high blocking resistance.
- the reason for this is not clear, but in general, when a propylene / ⁇ -olefin copolymer is modified, most of the polar group structural units are grafted to the main chain. It is expected to lower the crystallization temperature or cause a decrease in hardness.
- the modified propylene / ⁇ -olefin copolymer (A) is considered to contain a large number of polar groups at the molecular ends, it has a high crystallization temperature despite its relatively low melting point (Tm). It is considered that it has excellent blocking properties as a result.
- simulated long-chain polymer chain, and can suppress the seepage of a low molecular weight body is also considered.
- the coating layer (for example, primer layer) coated with the coating material of the present invention can have high coating film adhesion.
- the coating material containing the modified propylene / ⁇ -olefin copolymer (A) is considered to be excellent in adhesion to the substrate to be coated because of its low viscosity.
- the modified propylene / ⁇ -olefin copolymer (A) is considered to contain many polar groups at the molecular end, the main chain has high crystallinity and the coating film itself has high strength. it is conceivable that.
- the interface between the coating film and the substrate to be coated is less likely to break, and excellent coating film adhesion is exhibited.
- a part of the modified propylene / ⁇ -olefin copolymer (A) is considered to be crosslinked during the synthesis process. It is considered that the molecular weight of the cross-linked portion is increased due to thermal fusion or the like, and the strength of the coat layer is increased.
- the molding resin composition of the present invention comprises at least one resin (B2) selected from the group consisting of a thermoplastic resin and a thermosetting resin, an inorganic reinforcing material (C), and a modified propylene.
- -It contains an ⁇ -olefin copolymer (A).
- thermoplastic resin may be at least one resin selected from the group consisting of a polycarbonate resin, a thermoplastic polyester resin, an ABS resin, a polyacetal resin, a polyamide resin, a polyphenylene oxide resin, and a polyimide resin.
- the thermosetting resin may be at least one resin selected from the group consisting of an epoxy resin, a thermosetting unsaturated polyester resin, and a phenol resin. That is, these thermoplastic resins and thermosetting resins can be used alone or in combination of two or more.
- the polycarbonate resin is typically an aromatic polycarbonate resin obtained by reacting an aromatic diol (for example, bisphenol A) and phosgene, and may preferably be diethylene glycol diallyl carbonate.
- aromatic diol for example, bisphenol A
- phosgene for example, bisphenol A
- diethylene glycol diallyl carbonate such polycarbonate resins are commercially available, and examples thereof include trade names such as NOVAREX (Mitsubishi Engineering Plastics Co., Ltd.), Panlite (Teijin Chemicals Co., Ltd.), Lexan (SABIC Innovative Plastics (same)), and the like. it can.
- the thermoplastic polyester resin is typically a resin obtained by polycondensation of a dicarboxylic acid and a diol, preferably polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, polycyclohexane terephthalate, etc. It can be.
- Such thermoplastic polyester resins are commercially available, and examples thereof include trade name Rynite (DuPont).
- the ABS resin is typically an impact-resistant resin obtained by graft polymerization of acrylonitrile and styrene to polybutadiene, preferably 5 to 40% by weight of the polybutadiene component, and the graft amount of the styrene component and the acrylonitrile component.
- the ratio (styrene / acrylonitrile) can be 70/30 to 80/20.
- Such ABS resin is commercially available, and examples thereof include trade names such as Stylac (Asahi Kasei Chemicals Co., Ltd.) and Psycolac (Ube Saikon Co., Ltd.).
- the polyacetal resin is typically a resin obtained by ring-opening polymerization of formalin or trioxane together with ethylene oxide as required in the presence of a cationic catalyst, and is a resin having a polyoxymethylene chain as a main skeleton. But preferably it can be of the copolymer type.
- Such polyacetal resins are commercially available, and examples thereof include the trade name Iupital (Mitsubishi Engineering Plastics Co., Ltd.).
- the polyamide resin is typically a resin obtained by polycondensation of a diamine and a dicarboxylic acid or ring-opening polymerization of caprolactam, preferably a polycondensation reaction product of an aliphatic diamine and an aliphatic or aromatic dicarboxylic acid. It can be.
- Such polyamide resins are commercially available, and examples thereof include trade names such as Leona (Asahi Kasei Chemicals Co., Ltd.) and Zytel (DuPont Co., Ltd.).
- the polyphenylene oxide resin is typically a resin obtained by oxidative coupling of 2,6-dimethylphenol in the presence of a copper catalyst, and has been modified by a technique such as blending this resin with another resin. Modified polyphenylene oxide resins are also included. In the present invention, a blend modified product of a styrenic polymer is preferable.
- Such polyphenylene oxide resins are commercially available, and examples thereof include trade names such as Zylon (Asahi Kasei Chemicals Co., Ltd.) and Iupiace (Mitsubishi Engineering Plastics Co., Ltd.).
- the polyimide resin is typically a resin obtained by polycondensation of tetracarboxylic acid and diamine to form an imide bond in the main skeleton, preferably formed from pyromellitic anhydride and diaminodiphenyl ether. It is possible.
- a polyimide resin is commercially available, and examples thereof include a trade name Vespel (DuPont).
- the epoxy resin is typically a resin obtained by reacting an aromatic diol (for example, bisphenol A) and epichlorohydrin in the presence of an alkali, preferably a bisphenol A type epoxy resin having an epoxy equivalent of 170 to 5000, It may be a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, or the like.
- epoxy resins are commercially available, and examples thereof include trade names such as Epomic (Mitsui Chemicals), Epicron (Dainippon Ink Chemical Co., Ltd.), Sumi Epoxy (Sumitomo Chemical Co., Ltd.), and the like. .
- thermosetting unsaturated polyester resin is typically a resin obtained by esterifying an aliphatic unsaturated dicarboxylic acid and an aliphatic diol, and preferably an unsaturated dicarboxylic acid such as maleic acid or fumaric acid. It may be a resin obtained by an esterification reaction between an acid and a diol such as ethylene glycol or diethylene glycol.
- Such thermosetting unsaturated polyester resins are commercially available, and examples thereof include trade name Rigolac (Showa High Polymer Co., Ltd.), Sumicon (Sumitomo Bakelite Co., Ltd.) and the like.
- the phenol resin includes both a so-called novolak type and a resol type, but a novolak type cured with hexamethylenetetramine and a solid resol mainly composed of a dimethylene ether bond are preferable.
- a phenol resin is commercially available, and examples thereof include trade names Sumicon PM (Sumitomo Bakelite Co., Ltd.), Nikkaline (Nippon Synthetic Chemical Industry Co., Ltd.), and the like.
- polycarbonate resin polybutylene terephthalate, which is a kind of thermoplastic polyester resin, and a combination of polycarbonate resin and ABS resin are preferable.
- the content of at least one resin (B2) selected from the group consisting of thermoplastic resins and thermosetting resins is preferably 50 to 95 parts by weight with respect to 100 parts by weight of the resin composition, and 70 to The amount is more preferably 95 parts by weight, and further preferably 80 to 95 parts by weight.
- the inorganic reinforcing material (C) may be at least one selected from glass fibers, carbon fibers, and fillers.
- An inorganic reinforcement material (C) can also be used by 1 type, and may be used in combination of 2 or more type.
- the type of glass fiber is not particularly limited, but roving glass, chopped strand glass, milled glass, or the like can be used.
- the length of the glass fiber may be broken when mixed with the resin by an extruder or the like, and is not particularly limited, but is preferably 0.3 mm to 10 mm, and preferably 2 mm to 7 mm from the viewpoint of workability.
- the length of the glass fiber in the resin composition is preferably 2 mm to 5 mm.
- the average fiber diameter of the glass fiber is not particularly limited, but is 1 to 25 ⁇ m, preferably 5 to 17 ⁇ m.
- the aspect ratio (average fiber length / fiber diameter) of the glass fibers in the resin composition is preferably 25 or less, but glass fibers having different aspect ratios can be mixed and used at an appropriate ratio. is there.
- the cross-sectional shape of the glass fiber is not particularly limited, and may be circular, eyebrows, gourds, ellipses, cylinders, and the like.
- the glass fiber may be surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like.
- silane coupling agent examples include vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and ⁇ -glycid.
- the glass fiber may be subjected to a bundling treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like.
- the olefin resin or urethane resin used for the bundling treatment is used in a range that does not affect the physical properties of the entire composition.
- the glass fiber may be coated with a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof by a plating method or a vapor deposition method.
- a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof by a plating method or a vapor deposition method.
- the shape and type of carbon fiber are not particularly limited.
- the shape of the carbon fiber includes a chopped strand, a roving strand, a milled fiber, and the like; the type may be either pitch-based or polyacrylonitrile-based.
- the carbon fiber may be obtained by spinning or molding a raw material composition and then carbonizing, or may be obtained basically without passing through a spinning step, such as a vapor phase growth method.
- a spinning step such as a vapor phase growth method.
- the carbon fiber may be surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like, as described above.
- the carbon fiber may be subjected to a sizing treatment with a sizing agent such as an epoxy resin and a urethane resin, as described above.
- the fiber diameter of carbon fiber is generally in the range of 6 to 18 ⁇ m, preferably 0.5 to 15 ⁇ m, particularly preferably 1 to 10 ⁇ m.
- the cut length of the chopped strand is preferably 1 to 15 mm, more preferably 2 to 10 mm, and most preferably 3 to 8 mm. Further, the chopped strand is crushed during the molding.
- the aspect ratio (L / D), which is the ratio of the length L in the fiber axis direction of the carbon fiber in the resin composition to the fiber diameter D, is preferably in the range of 15 to 100, and more preferably in the range of 20 to 50.
- Fillers include calcium carbonate, silica, kaolin, clay, titanium oxide, barium sulfate, zinc oxide, amorphous fillers such as aluminum hydroxide, alumina, magnesium hydroxide, plate shapes such as talc, mica, or glass flakes. Fillers, wollastonite, potassium titanate, basic magnesium sulfate, sepiolite, zonotlite, acicular fillers such as aluminum borate, fillers such as metal powder, metal flakes, carbon black, and carbon fine particles are used. Other glass beads, glass powder, etc. are used. These fillers may be used alone or in combination, or those whose surfaces are subjected to carbon coating or silane coupling treatment may be used alone or in combination.
- glass fibers and carbon fibers are preferable, and glass fibers are particularly preferable from the viewpoint of affinity with the modified propylene / ⁇ -olefin copolymer (A) of the present invention.
- the content ratio of at least one resin (B2) selected from the group consisting of a thermoplastic resin and a thermosetting resin and the inorganic reinforcing material (C) is 100/0 to 50/50 by weight. In order to improve the rigidity of the product, it is preferable to contain an inorganic reinforcing material (C).
- the content ratio of at least one resin (B2) selected from the group consisting of a thermoplastic resin and a thermosetting resin and the inorganic reinforcing material (C) is preferably 95/5 to 55/45, more preferably 93/7 to 65/35, particularly preferably 92/8 to 85/15.
- the modified propylene / ⁇ -olefin copolymer (A) may be the modified propylene / ⁇ -olefin copolymer (A) of the present invention.
- the content of the modified propylene / ⁇ -olefin copolymer (A) is 100 in total of at least one resin (B2) selected from the group consisting of a thermoplastic resin and a thermosetting resin and an inorganic reinforcing material (C). 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, more preferably 0.1 to 7 parts by weight, and 0.2 to 5 parts by weight with respect to parts by weight. More preferably it is.
- the content of the modified propylene / ⁇ -olefin copolymer (A) is less than 0.01 parts by weight, it is difficult to obtain good moldability and impact resistance. The mechanical properties of the molded body are likely to deteriorate.
- the molding resin composition of the present invention may contain any additive such as brominated bisphenol, brominated epoxy resin, brominated polystyrene, brominated polycarbonate, triphenyl phosphate, phosphonic acid amide, as long as the effects of the present invention are not impaired.
- flame retardants such as red phosphorus, flame retardant aids such as antimony trioxide and sodium antimonate, heat stabilizers such as phosphate esters and phosphites, antioxidants such as hindered phenols, etc.
- Heat-resistant agent weathering agent, light stabilizer, mold release agent, flow modifier, colorant, lubricant, antistatic agent, crystal nucleating agent, plasticizer and foaming agent, anti-slip agent, anti-blocking agent, anti-fogging agent
- a nucleating agent, a pigment, a filler, a dye, a plasticizer, and the like may be further included as necessary.
- the method for producing the molding resin composition of the present invention may be any method.
- the above components may be combined simultaneously or in any order in a tumbler, V-type blender, Nauter mixer, Banbury mixer, kneading roll, single unit.
- a method of mixing with a twin or twin screw extruder is appropriately used.
- the resin composition thus obtained is molded by various known methods such as injection molding, extrusion molding and compression molding, and can be preferably molded by injection molding from the viewpoint of design and moldability.
- the molded product of the molding resin composition of the present invention has an excellent balance of impact strength (toughness), elastic modulus (rigidity), and tensile strength.
- the reason for this is not clear, but since the modified propylene / ⁇ -olefin copolymer (A) contains many polar groups at the molecular end, it is finely dispersed as a rubber component in the molding resin composition. It is thought that the impact strength is improved.
- the modified propylene / ⁇ -olefin copolymer (A) contains a large number of polar groups at the molecular end, so that the crystallinity of the main chain is high, so that the elastic modulus and tensile strength can be maintained at high values. It is considered a thing.
- the polar group at the molecular end of the modified propylene / ⁇ -olefin copolymer (A) has high mobility, it easily interacts with the glass fiber (inorganic reinforcing material (C)), and the glass fiber is opened. The effect is considered high. Thereby, it is considered that the glass fiber is easily finely dispersed in the molding resin composition, and the modified propylene / ⁇ -olefin copolymer (A) is effectively oriented on the surface of the glass fiber.
- At least one resin (B2) selected from a thermoplastic resin and a thermosetting resin and the modified propylene / ⁇ -olefin copolymer oriented on the glass fiber surface It is considered that interfacial peeling occurs effectively with the coalesced (A) and exhibits excellent impact strength.
- the modified propylene / ⁇ -olefin copolymer (A) contains a large number of polar groups at the molecular end, it is highly compatible with at least one resin (B2) selected from thermoplastic resins and thermosetting resins. It is considered to have solubility. Thereby, since it also has a pseudo adhesion function between at least one resin (B2) selected from a thermoplastic resin and a thermosetting resin and the glass fiber surface, a molded article having a high elastic modulus and tensile strength can be obtained. It is thought that it is easy to obtain.
- Hot melt composition The hot melt composition of the present invention comprises a base polymer (B3), a tackifier (D), and a modified propylene / ⁇ -olefin copolymer (A).
- the base polymer (B3) may be a polymer usually used for hot melt adhesives, and examples thereof include the following. 1) Polyethylene 2) Ethylene-vinyl acetate copolymer (EVA) 3) Modified EVA polymers such as saponified EVA and graft-modified EVA 4) Ethylene / (meth) acrylate copolymers such as ethylene / (meth) ethyl acrylate (EEA) 5) Ethylene / (meth) acrylic acid copolymer A partially neutralized ionomer resin. Specific examples include those marketed by Mitsui-DuPont Polychemicals under the trade name: High Milan.
- Polyamide Reaction product of dibasic acid and diamine, for example, 2 fatty acids such as soybean oil, tung oil, tall oil, etc.
- the reaction product of dimer acid which is a monomer and alkyl diamine such as ethylenediamine and diethylenetriamine, and nylons such as nylon 12 and the like. Specific examples thereof include Daiamide (Daicel Chemical Industries), Platilon (Toa Gosei Chemical Industry), Amilan (Toray), and the like.
- Polyester For example, ester resins 200 and 300 (Toyobo), Vita 1200, 300 (Goodyear) and the like can be mentioned.
- Propylene polymer atactic polypropylene, propylene / ⁇ -olefin copolymer having 4 or more carbon atoms (however, Mw is higher than 40000) and the like.
- Copolymer comprising vinyl aromatic compound and conjugated diene compound, and hydrogenated product thereof: specifically, styrene / butadiene random copolymer, styrene / isoprene random copolymer, butadiene / polystyrene block copolymer , Polystyrene / polyisoprene block copolymer, polystyrene / polyisoprene / polystyrene triblock copolymer, polystyrene / polybutadiene / polystyrene triblock copolymer, poly ( ⁇ -methylstyrene) / polybutadiene / poly ( ⁇ -methylstyrene) A triblock copolymer, these hydrogenated materials, etc. can be mentioned.
- the base polymer (B3) is preferably an ethylene-vinyl acetate copolymer (EVA), an ethylene / propylene copolymer, an ethylene / propylene / (meth) acrylic acid terpolymer, or a propylene-based polymer.
- Ethylene-vinyl acetate copolymer (EVA) is particularly preferable.
- base polymers (B3) can be obtained as commercial products.
- Califlex TR-1101, TR-1107, TR-4113 manufactured by Shell Chemical Co., Ltd.
- Clayton G-6500, G-6521, G-1650, G-1652, G-1657 manufactured by Shell Chemical Co., Ltd.
- Solbrene And hydrogenated sorbulene manufactured by Philips.
- the base polymer (B3) may be used alone or in combination of two or more.
- a tackifier (D) can be mix
- the tackifier (D) include aliphatic hydrogenated tackifiers, rosins, modified rosins or esterified products thereof, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, aliphatic Ingredients and aromatic copolymerized petroleum resins, low molecular weight styrene resins, isoprene resins, alkylphenol resins, terpene resins, coumarone / indene resins and the like are included.
- the tackifier (D) may be used alone or in combination of two or more.
- the tackifier (D) can be appropriately selected according to the base polymer (B3).
- EVA ethylene-vinyl acetate copolymer
- the content of the tackifier (D) is preferably 10 to 300 parts by weight with respect to 100 parts by weight of the base polymer (B3) in order to easily develop an adhesive force while maintaining an appropriate melt viscosity. Therefore, the amount is more preferably 50 to 200 parts by weight.
- the modified propylene / ⁇ -olefin copolymer (A) may be the modified propylene / ⁇ -olefin copolymer (A) of the present invention. It is considered that the modified propylene / ⁇ -olefin copolymer (A) can lower the melt viscosity without impairing the adhesiveness of the composition.
- the content of the modified propylene / ⁇ -olefin copolymer (A) is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the base polymer (B3), and melt viscosity is maintained while maintaining good adhesiveness.
- the amount is more preferably 20 to 80 parts by weight, for example, in order to make it easy to lower the amount.
- the hot melt composition of the present invention may further contain an unmodified polyolefin such as a sazol wax (H-1: manufactured by Sazol Co., Ltd.) blended in a normal hot melt adhesive.
- an unmodified polyolefin such as a sazol wax (H-1: manufactured by Sazol Co., Ltd.) blended in a normal hot melt adhesive.
- the hot melt composition of the present invention if necessary, within a range that does not impair the purpose of the present invention, such as various compounding agents such as a softening agent, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, Add additives such as anti-blocking agents, anti-fogging agents, nucleating agents, lubricants, pigments, fillers, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants, copper damage inhibitors as necessary. be able to.
- various compounding agents such as a softening agent, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent
- Add additives such as anti-blocking agents, anti-fogging agents, nucleating agents, lubricants, pigments, fillers, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants, copper damage inhibitors as necessary. be able to.
- the hot melt composition of the present invention can be obtained by supplying each of the above components to a mixer such as a Brabender, heating and melt-mixing; and molding it into a desired shape, for example, a granular shape, a flake shape, a rod shape, etc. it can.
- a mixer such as a Brabender, heating and melt-mixing
- a desired shape for example, a granular shape, a flake shape, a rod shape, etc. it can.
- the hot melt composition of the present invention is, for example, heated and melted and applied to an article to be coated such as cloth, kraft paper, aluminum foil, and polyester film by a usual method to form a hot melt adhesive layer. Can be used.
- the hot melt composition of the present invention contains a modified propylene / ⁇ -olefin copolymer (A) having a low melting point, so that it can be melted even at a low temperature.
- A modified propylene / ⁇ -olefin copolymer
- the solidified product of the hot melt composition of the present invention can have high strength.
- the polar group at the molecular end of the modified propylene / ⁇ -olefin copolymer (A) has high mobility and is likely to interact with the base polymer (B3) such as EVA; ⁇ Modified propylene / ⁇ -olefin copolymer (A), EVA, etc. because ⁇ -olefin copolymer (A) has a hybrid structure of polyolefin chains and polar groups, and has a structure similar to EVA This is considered to be because the compatibility with the base polymer (B3) was increased.
- the weight average molecular weight (Mw) of the polymer was measured by GPC. GPC measurement was performed under the following conditions. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined based on the following conversion method by creating a calibration curve using commercially available monodisperse standard polystyrene.
- the melting point (Tm) was measured by DSC-20 (manufactured by Seiko Denshi Kogyo Co., Ltd.) according to DSC (Differential Scanning Calorimetry). That is, about 10 mg of a sample was heated from ⁇ 20 ° C. to 200 ° C. at 10 ° C./min, and the temperature of the endothermic peak of the obtained curve was obtained as the melting point. Prior to this temperature increase measurement, the sample (copolymer) was once heated to about 200 ° C., held for 5 minutes, and then cooled to room temperature ( ⁇ 20 ° C.) at 10 ° C./min. Unified the thermal history of (copolymer).
- Heat of fusion ( ⁇ H) J / g was calculated from the area delimited by the endothermic peak obtained by DSC and the baseline of the entire endothermic peak.
- Crystallization temperature (Tc) The crystallization temperature (Tc) of the polymer was measured by DSC-20 (manufactured by Seiko Denshi Kogyo Co., Ltd.) according to DSC (Differential Scanning Calorimetry). That is, about 10 mg of sample was heated to about 200 ° C., held for 5 minutes, and then cooled to room temperature ( ⁇ 20 ° C.) at 10 ° C./min, and the temperature of the exothermic peak of the obtained curve was crystallized. Calculated as temperature.
- the propylene / 1-butene copolymers (A1-1) and (A1-2), which are the pyrolysis products in Production Examples 1 to 3, are the propylene / ethylene copolymers (X2- It was found that the increase in molecular weight during the denaturation reaction was smaller than in 2). The reason for this is not clear, but the propylene / 1-butene copolymers (A-1) to (A-3) of Production Examples 1 to 3 are not only propylene but also ⁇ - having 4 or more carbon atoms such as butene.
- an olefin unit it is considered that an internal double bond which is considered to be less reactive than that of forming a vinyl group can be formed, and as a result, the crosslinking reaction can be suppressed.
- the modified propylene / 1-butene copolymers (A-1) to (A-3) of Production Examples 1 to 3 are the same as the modified propylene / ethylene copolymers (X-1) to (X—) of Production Examples 4 to 6. Compared with 3), it showed a low penetration (high hardness) while having a low melting point. As can be seen from the fact that the crystallization temperature Tc and the heat of fusion ( ⁇ H) are high despite the low melting point, the modified propylene / 1-butene copolymers (A-1) to (A-3) This is considered to be due to the property of being easily crystallized. Further, the modified propylene / 1-butene copolymers (A-1) to (A-3) are expected to have less sticky components because the half-value width of the melting point peak is small, and this also exhibits high hardness. It is considered a factor.
- the modified propylene / 1-butene copolymers (A-1) to (A-3) of Production Examples 1 to 3 are easily crystallized is not clear, usually, when modified, most of the polar group structural units are In order to graft onto the main chain, it is expected that the crystallinity of the main chain tends to be lowered and thereby the crystallization temperature tends to be lowered.
- the modified propylene / 1-butene copolymers (A-1) to (A-3) are obtained by modifying a thermally decomposed product of the propylene / 1-butene copolymer.
- the pyrolyzed product of propylene / 1-butene copolymer is considered to contain more vinylidene groups at the molecular end portion than the directly polymerized product of propylene / ethylene copolymer. Therefore, the modified propylene / 1-butene copolymers (A-1) to (A-3) obtained by modifying the thermal decomposition product of the propylene / 1-butene copolymer are the same as those of the propylene / ethylene copolymer. Since it contains more polar groups at the molecular end than the modified propylene / ethylene copolymer (X-1) of Production Example 4 obtained by modifying the polymer, it is considered that crystallization is facilitated.
- the modified propylene / 1-butene copolymers (A-1) to (A-3) of Production Examples 1 to 3 have a higher crystallization temperature than the modified propylene / ethylene copolymer (X-1) of Production Example 4. It can be seen that the ratio Tc (A) / Tc (A1) is small; that is, the degree of decrease in the crystallization temperature accompanying modification is small. The reason for this is not clear, but as described above, the modified propylene / 1-butene copolymers (A-1) to (A-3) of Production Examples 1 to 3 are the heat of propylene / 1-butene copolymer. It is obtained by modifying the degradation product.
- the pyrolyzed product of propylene / 1-butene copolymer is considered to contain more vinylidene groups at the molecular end portion than the directly polymerized product of propylene / ethylene copolymer. Therefore, the modified propylene / 1-butene copolymers (A-1) to (A-3) obtained by modifying the thermal decomposition product of the propylene / 1-butene copolymer are the same as those of the propylene / ethylene copolymer. This is presumably because the molecular end portion contains more polar groups than the modified propylene / ethylene copolymer (X-1) of Production Example 4 obtained by modifying the polymerized product, and crystallization is not inhibited.
- the modified propylene / 1-butene copolymers (A-1) to (A-3) of Production Examples 1 to 3 are more semi-crystallized than the modified propylene / ethylene copolymer (X-1) of Production Example 4. Shows that time is short.
- the modified propylene / 1-butene copolymers (A-1) to (A-3) obtained by modifying the pyrolysis product of propylene / 1-butene copolymer are propylene / ethylene copolymer.
- the obtained water-dispersed composition had a solid content concentration of 40% and an average particle size of 0.3 ⁇ m.
- the average particle size was a value of 50% volume average particle size measured by a dynamic light scattering nanotrack particle size analyzer “Microtrack UPA-EX150 (Nikkiso Co., Ltd.)”.
- the internal temperature is maintained at 75 ° C., 2 g of potassium persulfate is added as a polymerization initiator, and after dissolution, 250 g of ion exchange water, 1 g of sodium lauryl sulfate, 9 g of acrylamide, 200 g of styrene, 220 g of 2-ethylhexyl acrylate, 9 g of methacrylic acid was added dropwise to the reaction vessel over 6 hours to polymerize. After completion of dropping, the mixture was aged and neutralized for 5 hours to obtain an aqueous dispersion of an acrylic resin. The obtained acrylic resin aqueous dispersion had a solid content concentration of 40% and an average particle size of 0.2 ⁇ m.
- a white top coating was applied so that the film thickness after drying was 80 ⁇ m, and the coating film was formed, left at room temperature for 10 minutes, and then heated at 80 ° C. or 120 ° C. The sample was placed in an oven for 30 minutes to produce a test piece.
- Example 2 Comparative Examples 1 to 4
- a water-dispersed composition was obtained in the same manner as in Example 1 except that the composition of the water-dispersed composition and the average particle size of the resin particles were changed as shown in Table 3, and the same evaluation was performed.
- Table 3 shows the evaluation results of Examples 1-2 and Comparative Examples 1-4.
- the primer layers obtained from the water-dispersed compositions of Examples 1 and 2 containing the modified propylene / ⁇ -olefin copolymer (A) of the present invention are the water layers of Comparative Examples 1 to 4. It turns out that it has higher peel strength than the primer layer obtained from the dispersion-type composition. The reason for this is not clear, but it is considered that the modified propylene / ⁇ -olefin copolymer (A) of the present invention was sufficiently heat-sealed at the baking temperature and sufficiently solidified.
- modified propylene / ⁇ -olefin copolymer (A) of the present invention is considered to contain a large number of polar groups at the molecular end, the crystallinity of the main chain is increased, resulting in a high coating film itself. It is thought that it became strong. Furthermore, the modified propylene / ⁇ -olefin copolymer (A) of the present invention is partially crosslinked in the synthesis process to increase the molecular weight, and the molecular entanglement of the portion is further increased by thermal fusion. It is also considered that the peel strength has increased.
- the polymer was degassed and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours to obtain a propylene elastomer having Mw of 240,000 and Tm of 91 ° C.
- Acid-modified wax Modified propylene / 1-butene copolymer (A-1) obtained in Production Example 1
- Example 3 54 g of the polar monomer graft crosslinked resin produced above and 6 g of the modified propylene / 1-butene copolymer (A-1) obtained in Production Example 1 were simultaneously dissolved in 240 g of methylcyclohexane, and the solid content was 20% by mass. A solvent-dispersed composition was obtained.
- Example 4 48 g of the polar monomer graft crosslinked resin produced above and 12 g of the modified propylene / 1-butene copolymer (A-1) obtained in Production Example 1 were simultaneously dissolved in 240 g of methylcyclohexane, and a solvent having a solid content of 20%. A dispersed composition was obtained.
- the static stability, coating property, and adhesive strength of the obtained solvent-dispersed composition were evaluated by the following methods.
- the solvent-dispersed compositions of Examples 3 and 4 containing the modified propylene / ⁇ -olefin copolymer (A) of the present invention are better than the solvent-dispersed composition of Comparative Example 5 It can be seen that it has a high adhesion strength while having excellent static stability and coating properties. The reason for this is not clear, but the reason why the coated surfaces after heating in Examples 3 and 4 are uniform is that the modified propylene / ⁇ -olefin copolymer (A) of the present invention has a low melting point. This is considered to be due to sufficient heat fusion at the temperature.
- the adhesive strength of Examples 3 and 4 is high because the modified propylene / ⁇ -olefin copolymer (A) of the present invention contains a large number of polar groups at the molecular end, and thus the crystallization rate is large and sufficient. This is thought to be because the entanglement of the molecules that had already become high molecular weight in the synthesis process was further increased by thermal fusion. Furthermore, since the modified propylene / ⁇ -olefin copolymer (A) of the present invention is considered to contain a large number of polar groups at the molecular end, the main chain crystallinity increases, resulting in a high coating film itself. It is thought that it became strong.
- Solvent-soluble composition [Example 5] In a 200 ml Erlenmeyer flask, 90 parts by mass of methylcyclohexane (SP value 7.8) as an organic solvent and 10 parts by mass of the modified propylene / 1-butene copolymer (A-1) obtained in Production Example 1 as a wax were added. The mixture was stirred and stirred at room temperature using a stirrer with a heater to obtain a solvent-soluble composition.
- SP value 7.8 methylcyclohexane
- A-1 modified propylene / 1-butene copolymer obtained in Production Example 1 as a wax
- Example 6 to 10 Comparative Examples 6 to 11
- a solvent-soluble composition was obtained in the same manner as in Example 5 except that the types of the organic solvent and wax were changed as shown in Table 5 or 6.
- Example 12 A solvent-soluble composition was prepared in the same manner as in Example 5 except that the types of the organic solvent and the wax were changed as shown in Table 6. However, since the composition gelled at room temperature, the viscosity, coating property, blocking resistance, and coating film adhesion of the composition could not be evaluated.
- a PC (polycarbonate) film or PA6 (polyamide 6) film is used as a substrate, and the adhesion between the coating film after drying at 160 ° C. for 30 seconds and the substrate is determined. evaluated.
- a PP (polypropylene) film was used as a substrate, and the adhesion between the coating film after drying at 100 ° C. for 60 seconds and the substrate was evaluated.
- AL (aluminum) and SUS (stainless steel) were used as the base material, and the adhesion between the coating film after drying at 120 ° C. for 60 seconds and the base material was evaluated.
- the evaluation criteria were the same as described above.
- compositions of Examples 5 to 10 have high solubility and static stability with respect to the compositions of Comparative Examples 6 to 12, and have excellent coating properties, blocking resistance, and coating film adhesion. Show. The reason for this is not clear, but since the modified propylene / ⁇ -olefin copolymer (A) contained in the compositions of Examples 5 to 10 has a low melting point, it can be easily melted at the drying temperature, and can be coated. It is thought that workability has been improved.
- the modified propylene / ⁇ -olefin copolymer (A) is considered to contain many polar groups at the molecular end portion, it has a high crystallization temperature despite its relatively low melting point (Tm). As a result, it is considered that it has excellent blocking resistance. Furthermore, the ends of the two molecules interact with each other to form a pseudo-long polymer chain and suppress the seepage of the low molecular weight substance, which is considered to be excellent in blocking resistance.
- the coating film adhesion can be high is considered that the coating material containing the modified propylene / ⁇ -olefin copolymer (A) has a low viscosity.
- the modified propylene / ⁇ -olefin copolymer (A) is considered to contain a large number of polar groups at the molecular end, so that the main chain has high crystallinity and the coating film itself has high strength. is expected. Further, it is considered that a part of the modified propylene / ⁇ -olefin copolymer (A) is crosslinked during the synthesis process, and the molecular chain is likely to be entangled by thermal fusion or the like in the crosslinked and polymerized part. As a result, it is considered that the interface between the coating film and the substrate to be coated is less likely to break, and excellent coating film adhesion is exhibited.
- Molding resin composition (raw material)
- Inorganic reinforcement (C): Glass fiber for polycarbonate (Nittobo Co., Ltd .: Chopped strand CS (F) 3PE455S) wax: Modified propylene / 1-butene copolymer of Production Example 1 (A-1) Modified propylene / ethylene copolymer (X-3) of Production Example 6
- aromatic polycarbonate resin Teijin Limited: Panlite L-1225Y
- glass fiber for polycarbonate (Nittobo Co., Ltd .: chopped strand CS (F) 3PE455S)
- modified propylene / 1-butene 3 parts by weight of copolymer (A-1) was melt-kneaded using a co-rotating twin-scre
- the obtained pellets were dried at 120 ° C. for 8 hours, and then using an injection molding machine (Niigata Machine Techno, Niigata NN100), cylinder temperature 280 ° C., screw rotation speed 60 rpm, injection pressure 130 MPa, mold temperature Injection molding was performed under the condition of 90 ° C., and a test piece was prepared according to each JIS test. The impact strength, flexural modulus, and tensile strength of the prepared test pieces were evaluated by the methods shown below.
- the impact strength was measured by a Charpy impact test.
- the prepared test piece is based on JIS K-7111, hammer weight 2J, hammer rotation moment 1.08N ⁇ J, hammer lifting angle 50 °, impact speed 2.9m / s, rotation axis to impact point
- the Charpy impact value was measured under the condition of a distance of 0.23 m.
- the bending elastic modulus was measured by a bending test. That is, the elastic modulus and strength of the prepared test piece were measured according to JIS K-7171 under the conditions of a load range of 50 kg, a test speed of 2 mm / min, and a bending span of 64 mm.
- the tensile strength was measured by a tensile test. That is, the yield / break strength and elongation of the produced test piece were measured under the conditions of a load range of 1000 kg, a test speed of 500 mm / min, and a grip span of 115 mm based on JIS K-7162-1A.
- Example 11 As shown in Table 7, the test piece of Example 11 containing the modified propylene / ⁇ -olefin copolymer (A) of the present invention had a higher impact strength and bending than the test piece of Comparative Example 14 not containing it. It can be seen that the balance between elastic modulus and tensile strength is excellent. The reason for this is not clear, but since the modified propylene / ⁇ -olefin copolymer (A) contains many polar groups at the molecular end, it is finely dispersed as a rubber component in the polycarbonate (B2). It is thought to improve impact strength.
- the modified propylene / ⁇ -olefin copolymer (A) contains a large number of polar groups at the end of the molecule, so the crystallinity of the main chain is increased, so that the flexural modulus and tensile strength remain high. It is considered possible.
- the polar group at the molecular end of the modified propylene / ⁇ -olefin copolymer (A) has high mobility, it is likely to interact with the glass fiber (C), and the glass fiber opening effect is considered high. It is done. Thereby, it is considered that the glass fiber is easily finely dispersed in the polycarbonate (B2), and the modified propylene / ⁇ -olefin copolymer (A) is effectively oriented on the surface of the glass fiber. As a result, when an impact is applied to the molding resin composition, interfacial delamination occurs effectively between the polycarbonate (B2) and the modified propylene / ⁇ -olefin copolymer (A) oriented on the glass fiber surface. It is considered that excellent impact strength is exhibited.
- the modified propylene / ⁇ -olefin copolymer (A) contains many polar groups at the molecular end, it is considered to have high compatibility with the polycarbonate (B2). Thereby, since it has a pseudo adhesion function between the polycarbonate (B2) and the glass fiber (C) surface, it is considered that a molded product having a high flexural modulus and tensile strength can be easily obtained.
- Hot melt composition (raw material) Base polymer (B3): EVA # 220 (Ethylene-vinyl acetate copolymer manufactured by Mitsui DuPont Chemical) Tackifier (D): Aliphatic petroleum resin: manufactured by Nippon Zeon Co., Ltd., Quinton M1 wax: Modified propylene / 1-butene copolymer of Production Example 1 (A-1) Modified propylene / ethylene copolymer (X-1) of Production Example 4 Modified propylene / ethylene copolymer (X-2) of Production Example 5 Unmodified propylene / ethylene wax (Sazol Wax, Sazol Wax (trade name) H1)
- Example 12 40 parts by mass of ethylene-vinyl acetate copolymer (EVA # 220: Mitsui DuPont Polychemical Co., Ltd.) as the base polymer (B3) and aliphatic petroleum resin (Quinton M1 manufactured by Nippon Zeon Co., Ltd.) 40 as the tackifier (D) 1 part by mass and 20 parts by mass of the modified propylene / 1-butene copolymer (A-1) of Production Example 1 as a modified propylene / ⁇ -olefin copolymer (A) are melt-mixed at 180 ° C. to obtain a hot melt composition A product was prepared.
- EVA # 220 Mitsui DuPont Polychemical Co., Ltd.
- aliphatic petroleum resin Quinton M1 manufactured by Nippon Zeon Co., Ltd.
- Example 13 A hot melt composition was prepared in the same manner as in Example 12 except that the modified propylene / ⁇ -olefin copolymer (A) was changed to the wax shown in Table 8.
- the melt viscosity and adhesive strength of the obtained hot melt composition were measured by the following methods.
- the obtained hot melt composition was applied to a thickness of 15 ⁇ m on one surface of an aluminum foil (thickness: 50 ⁇ m).
- the aluminum foil is bent and the coated surfaces are bonded together, and heat sealing is performed under the conditions of an upper bar of 170 ° C., a lower bar of 70 ° C., a pressure of 1 kg / cm 2 at the time of pressure bonding, and a hot melt adhesive layer.
- an adhesive piece with an aluminum foil attached thereto was produced. This adhesive piece was cut into a width of 25 mm to make a sample, a T-type peel test was performed at a measurement temperature of 20 ° C.
- the hot-melt composition of Example 12 containing the modified propylene / ⁇ -olefin copolymer (A) of the present invention has good fluidity, and Comparative Examples 13 to 15 It can be seen that the adhesive strength is higher than that of the composition. The reason for this is not clear, but the modified propylene / ⁇ -olefin copolymer (A) contained in the composition of Example 12 exhibits a good fluidity because of its low melting point; Since it contains a large number of polar groups present, it is considered that it interacts well with EVA and exhibits high compatibility.
- a propylene-based wax containing an ⁇ -olefin unit having 4 or more carbon atoms obtained by thermal decomposition and a polar compound containing a double bond are reacted with each other to exhibit excellent performance such as a low melting point.
- a group-containing propylene-based wax can be provided.
- the modified propylene / ⁇ -olefin copolymer has a low melting point, little stickiness, and maintains crystallinity even when containing a polar group, and has high hardness. Therefore, the modified propylene / ⁇ -olefin copolymer of the present invention can be preferably used for various applications such as a coating material, a molding-like resin composition, and a hot melt adhesive composition.
- the modified propylene / ⁇ -olefin copolymer of the present invention is excellent in dispersibility and solubility in water and solvents. Therefore, the coating material containing the modified propylene / ⁇ -olefin copolymer has a high solidification rate after application, can be highly concentrated, and has good compatibility when blended with other resins. Therefore, varnish separation can be suppressed, coating unevenness can be reduced, or blocking resistance can be imparted to the coated surface of the coating material. Therefore, the resin solution can be spray-coated without causing a separation phenomenon, and is useful for paints, primers, adhesives, and ink binders that can be spray-coated.
- the coating material has no stickiness on the surface of the coating film and exhibits excellent adhesion to various molded articles, etc., so it can be applied to plastics, metals, paper, wood, fibers, leather, glass, rubber, ceramics, concrete, etc.
- coating materials paints, primers, adhesives, pressure-sensitive adhesives, ink binders, etc., they are used in various industrial materials and building materials. It is also used as a filler dispersant, pigment dispersant, sintering aid, binder for ceramics and metallurgical compounds in paints.
- the molding resin composition containing the modified propylene / ⁇ -olefin copolymer of the present invention has an excellent balance of mechanical properties such as impact strength, bending strength, and tensile strength.
- the hot melt adhesive composition containing the modified propylene / ⁇ -olefin copolymer of the present invention has good compatibility between the modified propylene / ⁇ -olefin copolymer and the base polymer or tackifying resin, so In addition to excellent properties, it has high adhesion to the substrate.
- the modified propylene / ⁇ -olefin copolymer of the present invention can also be used for various applications other than those described above.
- olefin-based paints for example, olefin-based paints, resin modifiers, heat sealants, printing ink antiwear agents, surface coating agents, additives for thermal transfer recording media, nonwoven fabric modifiers, toner additives, polishes, release for resin molding Molding agent, rubber processing aid, paper quality improver, fiber processing aid, electrical insulation agent, natural wax compounding agent, polyolefin film antifogging agent, pigment dispersant (masterbatch), molding processing aid, rubber It can be used in various applications such as antioxidants, paper coatings, fiber finishes, PVC lubricants, additives for asphalt, nucleating agents for expanded polystyrene, lost wax and candles.
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Abstract
Description
特許文献2に開示されている熱分解ポリプロピレンワックスの変性反応において粘度が高くなる現象は、熱分解ポリプロピレンワックスの製造にあたり、熱分解する工程で、プロピレン単位の分岐メチル基が結合した炭素からの水素引き抜きによりラジカルが発生することをきっかけに主鎖開裂が起こり、開裂して生成する2つの末端の一方がビニリデン基(CH2=CRC-)となり、他方が第二級炭素ラジカルを有する構造(・CRC-)となると考えられるところ;この第二級炭素ラジカルに隣接する第一級水素の引き抜きによって、反応性の高いビニル基(CH2=CH-)が形成される場合があり、このビニル基が酸変性工程で二重結合を有する極性化合物を介して架橋する反応が併発している可能性があるのではないかと考えた。
そこで、プロピレンだけではなく、ブテンなどの炭素数4以上のα-オレフィン単位を導入することにより、ビニル基を形成させるよりも、反応性が低いと考えられる内部オレフィン型の二重結合を形成させることが出来、その結果、前記の架橋反応を抑制できるのではないかと考え、検討した。その結果、熱分解法で得られ、かつプロピレン単位と炭素数4以上のα-オレフィン単位とを含むプロピレン系ワックスは、二重結合を有する極性化合物と反応させても、著しい粘度上昇を抑制できることを見出した。
(i)GPCで測定した重量平均分子量(Mw)が3,000~40,000の範囲にある
(ii)DSCで測定した融点(Tm)が60~110℃の範囲にある
(iii)DSCで測定した結晶融点ピークの半値幅が1~20℃の範囲にある
(iv)1HNMRにより測定した、1000個の炭素原子あたりのビニリデン基の個数が0.5~5個である
[2] 前記プロピレン・α-オレフィン共重合体(A1)が、プロピレン・炭素数4以上のα-オレフィン共重合体(A2)を熱分解して得られる、[1]に記載の変性プロピレン・α-オレフィン共重合体(A)。
[3] 前記プロピレン・炭素数4以上のα-オレフィン共重合体(A2)が、プロピレン由来の構成単位(a’)を60~95モル%、炭素数4以上のα-オレフィン由来の構成単位(b’)を5~40モル%〔(a')+(b')=100モル%とする〕含み、かつ下記(i')~(iii')の全てを満たす、[2]に記載の変性プロピレン・α-オレフィン共重合体(A)。
(i')GPCで測定した重量平均分子量(Mw)が50,000~1,000,000の範囲にある
(ii')DSCで測定した融点(Tm)が60~120℃の範囲にある
(iii')DSCで測定した結晶融点ピークの半値幅が1~20℃の範囲にある
[4] 前記プロピレン・α-オレフィン共重合体(A1)が、下記要件(v)をさらに満たす、[1]~[3]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)。
(v)DSCで測定した融解ピークのΔHが40~100J/gの範囲にある
[5] 前記変性プロピレン・α-オレフィン共重合体(A)の結晶化温度をTc(A)とし、前記プロピレン・α-オレフィン共重合体(A1)の結晶化温度をTc(A1)としたとき、結晶化温度の比Tc(A1)/Tc(A)が、1.0~1.6の範囲である、[1]~[4]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)。
(i)GPCで測定した重量平均分子量(Mw)が3,000~40,000の範囲にある
(ii)DSCで測定した融点(Tm)が60~110℃の範囲にある
(iii)DSCで測定した結晶融点ピークの半値幅が1~20℃の範囲にある
前記プロピレン・α-オレフィン共重合体(A1)に、不飽和カルボン酸もしくはその誘導体または不飽和スルホン酸もしくはその塩から選ばれる少なくとも1種をグラフト重合させて、酸価が1~100KOHmg/gである変性プロピレン・α-オレフィン共重合体(A)を得る工程とを含む、変性プロピレン・α-オレフィン共重合体(A)の製造方法。
[7] 前記プロピレン・炭素数4以上のα-オレフィン共重合体(A2)を300~450℃で5分~10時間熱分解して前記プロピレン・α-オレフィン共重合体(A1)を得る、[6]に記載の変性プロピレン・α-オレフィン共重合体(A)の製造方法。
[8] 前記プロピレン・α-オレフィン共重合体(A1)が、下記要件(iv)をさらに満たす、[6]または[7]に記載の変性プロピレン・α-オレフィン共重合体(A)の製造方法。
(iv)1HNMRにより測定した、1000個の炭素原子あたりのビニリデン基の個数が0.5~5個である
[9] 前記プロピレン・炭素数4以上のα-オレフィン共重合体(A2)が、プロピレン由来の構成単位(a’)を60~95モル%、炭素数4以上のα-オレフィン由来の構成単位(b’)を5~40モル%〔(a')+(b')=100モル%とする〕含み、かつ下記(i')~(iii')の全てを満たす、[6]~[8]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)の製造方法。
(i')GPCで測定した重量平均分子量(Mw)が50,000~1,000,000の範囲にある
(ii')DSCで測定した融点(Tm)が60~120℃の範囲にある
(iii')DSCで測定した結晶融点ピークの半値幅が1~20℃の範囲にある
[11] 水または有機溶媒100重量部と、前記水または有機溶媒に溶解または分散された[1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)0.1~100重量部とを含む、コーティング材。
[12] 水または有機溶媒100重量部と、前記水または有機溶媒に溶解または分散された[1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)および他の樹脂(B1)を合計0.1~100重量部とを含み、前記変性プロピレン・α-オレフィン共重合体(A)と前記他の樹脂(B1)の重量比は、1/99~90/10である、コーティング材。
[13] 前記有機溶媒のSP値が7~12である、[11]または[12]に記載のコーティング材。
[14] 前記有機溶媒が、炭化水素系溶媒、アルコール系溶媒、エステル系溶媒から少なくとも一種を含む、[11]~[13]のいずれかに記載のコーティング材。
[15] 前記変性プロピレン・α-オレフィン共重合体(A)が、50℃以上に加熱されると前記有機溶媒に完全に溶解する、[11]~[14]のいずれかに記載のコーティング材。
[16] 熱可塑性樹脂および熱硬化性樹脂からなる群から選択される少なくとも1種の樹脂(B2)100~50重量部と、無機強化材(C)0~50重量部(ただし、成分(B2)と成分(C)との合計を100重量部とする)と、[1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)を0.01~10重量部と、を含む、成形用樹脂組成物。
[17] ベースポリマー(B3)100重量部と、粘着付与剤(D)10~300重量部と、[1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)1~100重量部とを含む、ホットメルト組成物。
[18] [1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)、もしくは、[1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)および他の樹脂(B1)を含む、塗料。
[19] [1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)、もしくは、[1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)および他の樹脂(B1)を含む、プライマー。
[20] [1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)、もしくは、[1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)および他の樹脂(B1)を含む、接着剤。
[21] [1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)、もしくは、[1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)および他の樹脂(B1)を含む、粘着剤。
[22] [1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)、もしくは、[1]~[5]のいずれかに記載の変性プロピレン・α-オレフィン共重合体(A)および他の樹脂(B1)を含む、焼結助剤。
本発明の変性プロピレン・α-オレフィン共重合体を含む成形用樹脂組成物は、衝撃強度、曲げ強度、引張強度等の力学特性のバランスに優れる。
本発明の変性プロピレン・α-オレフィン共重合体を含むホットメルト組成物は、ベースポリマーや粘着付与樹脂と変性プロピレン・α-オレフィン共重合体との相容性が良好であるため、流動性に優れるとともに、基材との密着性が高い。
本発明の変性プロピレン・α-オレフィン共重合体(A)は、極性基構造単位を所定の割合で含むプロピレン・α-オレフィン共重合体でありうる。極性基は、ヘテロ原子を含む極性基であることが好ましい。より具体的には、炭素、水素、酸素を含む極性基が好ましい態様であり、更に具体的にはエステル基、エーテル基、カルボン酸基(無水カルボン酸基を含む)、アルデヒド基、ケトン基を挙げることができる。
プロピレン・炭素数4以上のα-オレフィン共重合体(A2)を熱分解して、低分子量のプロピレン・α-オレフィン共重合体(A1)を得る。
プロピレン・α-オレフィン共重合体(A1)は、プロピレン由来の構成単位(a)を60~95モル%、好ましくは60~90モル%、更に好ましくは65~88モル%、より好ましくは70~85モル%、特に好ましくは75~82モル%と;
炭素数4以上のα-オレフィン由来の構成単位(b)を5~40モル%、好ましくは10~40モル%、更に好ましくは12~35モル%、より好ましくは15~30モル%、特に好ましくは18~25モル%〔(a)+(b)=100モル%とする〕とを含む。
プロピレン・α-オレフィン共重合体(A1)は、(i)GPCで測定した重量平均分子量(Mw)の上限が、40,000、好ましくは30,000、更に好ましくは20,000、特に好ましくは10,000でありうる。重量平均分子量(Mw)の下限は、3,000、好ましくは5,000、更に好ましくは6,000、特に好ましくは8,000でありうる。
プロピレン・α-オレフィン共重合体(A1)の、GPCで測定したMw/Mnは、特に制限はなく、例えば1~5程度、好ましくは2~4程度でありうる。Mw/Mnが上記範囲にあるプロピレン・α-オレフィン共重合体(A1)の変性物を含むコーティング材は、安定性が高く、塗膜の耐ブロッキング性、基材との密着性のバランスに優れうる。例えば、プロピレン・α-オレフィン共重合体(A1)のMw/Mnが1.1~3.0、好ましくは2.0~3.0の場合は、その変性物を含む塗膜の耐ブロッキング性により優れる傾向がある。プロピレン・α-オレフィン共重合体(A1)のMw/Mnが3.0を超える場合;好ましくは3.1~5.0程度、より好ましくは3.1~4.0程度である場合は、その変性物のコーティング材に使用する他の樹脂、フィラー、添加剤との親和性に優れ、コーティング材の安定性が良好となる。また、得られる塗膜は、基材との密着性に優れる傾向にある。
[測定条件]
装置:ゲル浸透クロマトグラフAlliance GPC2000型(Waters社製)
有機溶媒:o-ジクロロベンゼン
カラム:TSKgel GMH6-HT×2、TSKgel GMH6-HTLカラム×2(何れも東ソー社製)
流速:1.0 ml/分
試料:0.15mg/mL o-ジクロロベンゼン溶液
温度:140℃
分子量換算 :PP換算/汎用較正法
なお、汎用較正の計算には、Mark-Houwink粘度式の係数を用いることができる。PS、PPのMark-Houwink係数はそれぞれ、文献(J.Polym.Sci.,Part A-2,8,1803(1970)、Makromol.Chem.,177,213(1976))に記載の値を用いることができる。
プロピレン・α-オレフィン共重合体(A1)の、(ii)DSCの結果により得られる融点(Tm)は、60~110℃、好ましくは60~90℃、更に好ましくは65~85℃、特に好ましくは70~80℃の範囲にある。融点(Tm)が上記範囲にあるプロピレン・α-オレフィン共重合体(A1)の変性物は、有機溶媒、あるいは併用する樹脂に対する溶解性、分散性、耐ブロッキング性、基材との密着性のバランスに優れる。
プロピレン・α-オレフィン共重合体(A1)の、DSCの結果により得られる結晶化温度(Tc)は、20~80℃、好ましくは30~70℃、更に好ましくは39~65℃、特に好ましくは40~55℃の範囲にある。結晶化温度(Tc)が上記範囲にあるプロピレン・α-オレフィン共重合体(A1)の変性物は、有機溶媒、あるいは併用する樹脂に対する溶解性、分散性、耐ブロッキング性、基材との密着性のバランスに優れる。
プロピレン・α-オレフィン共重合体(A1)は、(iii)DSCで測定した融点ピークの半値幅が1~20℃、好ましくは5~20℃、より好ましくは7~20℃、更に好ましくは10~15℃の範囲にある。
特に、半値幅が上記上限を超えるプロピレン・α-オレフィン共重合体(A1)の変性物は、α-オレフィンが密に入っている部分と疎に入っている部分とが存在すると考えられ、特にα-オレフィンが密に入っている部分がべたつきの原因となり、耐ブロッキング性の悪化を引き起こすことがある。
一方、半値幅が上記下限以下となるプロピレン・α-オレフィン共重合体(A1)の変性物は、組成分布が狭いために、コーティング材として併用する樹脂やフィラー類に対する相性が必ずしも良好とは言えず、溶解性や分散性が劣る傾向になるものと考えられる。
プロピレン・α-オレフィン共重合体(A1)のDSCの結果により得られる融解熱量(ΔH)は、40~100J/g、より好ましくは45~80J/g、さらに好ましくは45~70J/g、最も好ましくは45~60J/gの範囲にありうる。
プロピレン・α-オレフィン共重合体(A1)の、(iv)1HNMRにより測定される、1000個の炭素原子あたりのビニリデン基の個数は、好ましくは0.5~5個である。
ビニリデン基の数L(個/1000炭素)=C/2
プロピレン・α-オレフィン共重合体(A1)は、X線回折により測定した結晶化度が、40~70%であることが好ましく、45~65%であることがより好ましく、50~58%の範囲であることが特に好ましい。プロピレン・α-オレフィン共重合体(A1)の結晶化度が上述下限より高い場合、ベタの原因となる成分が少なくなるため、その変性物を含む塗膜が良好な耐ブロッキング性を有しうる。上述上限より低い場合、コーティング材の溶解性、分散性を阻害すると考えられるプロピレン・α-オレフィン共重合体(A1)由来の結晶成分の量が低減するために、コーティング材の安定性、塗工性が良好になると考えられる。
プロピレン・α-オレフィン共重合体(A2)は、プロピレン・炭素数4以上のα-オレフィン共重合体であることが好ましい。
炭素数4以上のα-オレフィン由来の構成単位(b’)を5~40モル%、好ましくは10~40モル%、更に好ましくは12~35モル%、より好ましくは15~30モル%、特に好ましくは18~25モル%の量〔(a’)+(b’)=100モル%とする〕とを含み、
(i’)GPCで測定した重量平均分子量(Mw)が50,000~1,000,000であり、好ましくは70,000~800,000、より好ましくは100,000~600,000の範囲にあり、
(ii’)DSCで測定した融点(Tm)が60~120℃、好ましくは65~100℃、更に好ましくは70~90℃の範囲にあり、
(iii’)DSCで測定した融点ピークの半値幅が通常、1~20℃、好ましくは2~18℃、より好ましくは3~15℃、更に好ましくは4~12℃の範囲にある。
前記1)で得られたプロピレン・α-オレフィン共重合体(A1)に、二重結合を含む極性化合物をグラフト重合させて、変性プロピレン・α-オレフィン共重合体(A)を得る。
二重結合を含む極性化合物は、不飽和カルボン酸もしくはその誘導体または不飽和スルホン酸もしくはその塩から選ばれる少なくとも1種であることが好ましい。具体的には、アクリル酸、メタクリル酸、α-エチルアクリル酸、マレイン酸、フマール酸、イタコン酸、シトラコン酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、エンドシス-ビシクロ〔2,2,1〕ヘプトー5-エン-2,3-ジカルボン酸(ナジック酸〔商標〕)等の不飽和カルボン酸;これらの酸ハライド、アミド、イミド、酸無水物、エステル等の誘導体;およびスチレンスルホン酸、アリルスルホン酸、2-(メタ)アクリルアミド-2-メチルプロパンスルホン酸、(メタ)アクリルアミドプロパンスルホン酸、スルホプロピル(メタ)アクリレート、(メタ)アクリロイルオキシナフタレンスルホン酸、ビニルスルホン酸などの不飽和スルホン酸もしくはその塩などが挙げられる。これらの中でも、不飽和ジカルボン酸もしくはその酸無水物が好適であり、特にマレイン酸、ナジック酸(商標)、またはこれらの酸無水物が好適である。
本発明の変性プロピレン・α-オレフィン共重合体(A)は、前述の通り、プロピレン・α-オレフィン共重合体(A1)を、極性基構造単位に対応する二重結合を含む極性化合物でグラフト変性して得ることができる。
〔Mw〕
変性プロピレン・α-オレフィン共重合体(A)の、GPCで測定される重量平均分子量(Mw)の上限は、50,000、好ましくは40,000、更に好ましくは25,000、特に好ましくは18,000であり;重量平均分子量(Mw)の下限は、3,000、好ましくは5,000、更に好ましくは8,000、特に好ましくは12,000でありうる。
変性プロピレン・α-オレフィン共重合体(A)の、DSCの結果により得られる融点(Tm)は、55~105℃、好ましくは60~95℃、更に好ましくは65~85℃、特に好ましくは67~80℃の範囲でありうる。融点(Tm)が上記範囲にある変性プロピレン・α-オレフィン共重合体(A)は、有機溶媒、あるいは併用する樹脂に対する溶解性や分散性、耐ブロッキング性、基材との密着性のバランスに優れる。
変性プロピレン・α-オレフィン共重合体(A)の、DSCの結果により得られる結晶化温度(Tc)は、15~80℃、好ましくは25~70℃、更に好ましくは30~70℃、特に好ましくは40~50℃の範囲でありうる。結晶化温度(Tc)が上記範囲にある変性プロピレン・α-オレフィン共重合体(A)は、有機溶媒、あるいは併用する樹脂に対する溶解性や分散性、耐ブロッキング性、基材との密着性のバランスに優れる。
変性プロピレン・α-オレフィン共重合体(A)は、直接重合法で得られたプロピレン系ワックスの変性物よりも、変性による結晶性の低下が少ない傾向にある。従って、プロピレン・α-オレフィン共重合体(A1)の結晶化温度をTc(A1)とし、変性プロピレン・α-オレフィン共重合体(A)の結晶化温度をTc(A)としたとき、結晶化温度の比Tc(A1)/Tc(A)は、1.0~1.6、好ましくは1.0~1.5、特に好ましくは1.1~1.3の範囲でありうる。
変性プロピレン・α-オレフィン共重合体(A)の、(iii)DSCで測定される融点ピークの半値幅は、1~40℃、好ましくは5~30℃、より好ましくは10~25℃、更に好ましくは12~22℃の範囲にありうる。融点ピークの半値幅が上記範囲にある変性プロピレン・α-オレフィン共重合体(A)は、有機溶媒、あるいは併用する樹脂に対する溶解性、分散性に優れ、例えばコーティング材等に用いた場合に、コーティング材の安定性が良好となる。また、コーティングの固化速度が速く、耐ブロッキング性に優れる傾向にある。
変性プロピレン・α-オレフィン共重合体(A)の、DSCの結果により得られる融解熱量(ΔH)は、好ましくは20~100J/g、より好ましくは25~80J/g、さらに好ましくは30~65J/g、最も好ましくは35~60J/gの範囲にありうる。ΔHが上記範囲にある変性プロピレン・α-オレフィン共重合体(A)は、有機溶媒、あるいは併用する樹脂に対する溶解性、分散性、コーティング材の安定性、塗膜の耐ブロッキング性のバランスに優れる。
変性プロピレン・α-オレフィン共重合体(A)の酸価は、0.5~100KOHmg/gであることが好ましく、3~65KOHmg/gであることがより好ましく、5~55KOHmg/gであることがさらに好ましく、10~50KOHmg/gであることが特に好ましい。変性プロピレン・α-オレフィン共重合体(A)の酸価は、プロピレン・α-オレフィン共重合体(A1)の変性量によって調整することができる。例えば、変性プロピレン・α-オレフィン共重合体(A)の酸価を高めるためには、プロピレン・α-オレフィン共重合体(A1)の変性量を多くすることが好ましい。極性基構造単位の割合を一定以上とすることで、変性による効果が十分に得られやすいと考えられる。
酸価(mgKOH/g)=(N/10 KOH滴定量(ml)×F×5.61)/(試料(g)×0.01)
変性プロピレン・α-オレフィン共重合体(A)の針入度は、8dmm以下であることが好ましく、5dmm以下を満たすことが更に好ましく、3dmm以下であることが、耐ブロッキング性などの点から特に好ましい。
変性プロピレン・α-オレフィン共重合体(A)の半結晶化時間は、特に制限はないが、通常、2000秒以下、好ましくは1500秒以下、より好ましくは1000秒以下、特に好ましくは700秒以下、最も好ましくは550秒以下である。半結晶化時間が2000秒以下である変性プロピレン・α-オレフィン共重合体(A)は、コーティング材として用いた場合、基材に塗工した際の、塗膜固化時間が短く作業性に優れる。また、塗膜の耐ブロッキング性と基材への密着性のバランスに優れる。
示差走査熱量測定装置(パーキンエルマー社製、DSC7)を用い、試料を約5mgセットして、200℃の状態で5分間放置することにより試料を完全に溶融させる。その後、320℃/分の降温速度で50℃まで急冷して等温結晶化を行う。冷却開始から結晶化熱が全発熱量の1/2に到達するまでの時間を半結晶化時間とする。
本発明の樹脂組成物は、本発明の変性プロピレン・α-オレフィン共重合体(A)を含み、必要に応じて他の樹脂(B1)をさらに含んでもよい。
他の樹脂(B1)としては、オレフィン系樹脂、スチレン系樹脂、ポリウレタン、ポリエステル、ポリアミド、ポリカーボネート、ポリビニルアルコール、ポリ酢酸ビニル、エポキシ樹脂、アクリル樹脂、ロジン樹脂、アルキド樹脂、尿素樹脂、メラミン樹脂、フェノール樹脂、クマロン樹脂、ケトン樹脂、セルロース系樹脂、塩素化ポリオレフィン、或いはこれらの混合樹脂等を用いることができる。特に、変性プロピレン・α-オレフィン共重合体(A)との相溶性の観点では、オレフィン系樹脂やスチレン系樹脂が好ましく、オレフィン系エラストマーやスチレン系エラストマーが特に好ましい。後述するように樹脂組成物をプライマーとして用いた場合に、上塗り層との密着性を得やすくする観点では、ポリウレタン、エポキシ樹脂、アクリル樹脂が好ましく、特にアクリル樹脂が好ましい。
本発明の変性プロピレン・α-オレフィン共重合体(A)および本発明の樹脂組成物は、種々の用途、例えば、コーティング材、成形用樹脂組成物、ホットメルト組成物、塗料、プライマー、接着剤、粘着剤、焼結助剤などに用いることができる。
本発明の第1のコーティング材は、変性プロピレン・α-オレフィン共重合体(A)と、水または有機溶媒とを含む。
変性プロピレン・α-オレフィン共重合体(A)は、本発明の変性プロピレン・α-オレフィン共重合体(A)でありうる。
有機溶媒としては、特に制限はないが、好ましくはベンゼン、トルエン、キシレン等の芳香族炭化水素;ヘキサン、ヘプタン、オクタン、デカン等の脂肪族系炭化水素;シクロヘキサン、シクロヘキセン、メチルシクロヘキサン、エチルシクロへキサン等の脂環族炭化水素(芳香族炭化水素、脂肪族系炭化水素および脂環族炭化水素をまとめて炭化水素系溶媒ともいう);トリクロルエチレン、ジクロルエチレン、クロルベンゼン等のハロゲン化炭化水素;メタノール、エタノール、イソプロピルアルコール、ブタノール、ペンタノール、ヘキサノール、プロパンジオール、フェノール等のアルコール系溶媒;アセトン、メチルイソブチルケトン、メチルエチルケトンペンタノン、ヘキサノン、イソホロン、アセトフェノン等のケトン系溶媒;メチルセルソルブ、エチルセルソルブ等のセルソルブ類;酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル、ギ酸ブチル等のエステル系溶媒;テトラヒドロフラン等のエーテル系溶媒を単独使用または2種類以上選択して、使用することができる。
SP=dΣG/M
ここで、dは単独重合体の密度(g/l)であり、ΣGは構成単位の分子中の分子引力定数の総和であり、Mは構成単位の分子量(g/mol)である。
他の樹脂(B1)としては、オレフィン系樹脂、スチレン系樹脂、ポリウレタン、ポリエステル、ポリアミド、ポリカーボネート、ポリビニルアルコール、ポリ酢酸ビニル、エポキシ樹脂、アクリル樹脂、ロジン樹脂、アルキド樹脂、尿素樹脂、メラミン樹脂、フェノール樹脂、クマロン樹脂、ケトン樹脂、セルロース系樹脂、塩素化ポリオレフィン、或いはこれらの混合樹脂等を用いることができる。特に、変性プロピレン・α-オレフィン共重合体(A)との相溶性の観点より、オレフィン系樹脂やスチレン系樹脂が好ましく、オレフィン系エラストマーやスチレン系エラストマーが特に好ましい。あるいは、第2のコーティング材をプライマーとして用いた場合に、上塗り層との密着性を得やすくする観点から、ポリウレタン、エポキシ樹脂、アクリル樹脂が好ましく、特にアクリル樹脂が好ましい。
本発明の成形用樹脂組成物は、熱可塑性樹脂および熱硬化性樹脂からなる群から選択される少なくとも1種の樹脂(B2)と、無機強化材(C)と、変性プロピレン・α-オレフィン共重合体(A)とを含む。
熱可塑性樹脂は、ポリカーボネート樹脂、熱可塑性ポリエステル樹脂、ABS樹脂、ポリアセタール樹脂、ポリアミド樹脂、ポリフェニレンオキシド樹脂およびポリイミド樹脂からなる群から選択される少なくとも1種の樹脂でありうる。熱硬化性樹脂は、エポキシ樹脂、熱硬化性不飽和ポリエステル樹脂およびフェノール樹脂からなる群から選択される少なくとも1種の樹脂でありうる。即ち、これらの熱可塑性樹脂および熱硬化性樹脂は、1種単独で使用することもできるし、2種以上を組み合せて使用することもできる。
無機強化材(C)は、ガラス繊維、カーボン繊維、フィラー類から選択される少なくとも1種でありうる。無機強化材(C)は、1種で用いることもできるし、2種以上を組み合せて用いてもよい。
変性プロピレン・α-オレフィン共重合体(A)は、本発明の変性プロピレン・α-オレフィン共重合体(A)でありうる。
本発明のホットメルト組成物は、ベースポリマー(B3)と、粘着付与剤(D)と、変性プロピレン・α-オレフィン共重合体(A)とを含む。
ベースポリマー(B3)は、ホットメルト接着剤に通常使用されるポリマーであってよく、以下のものを例示することができる。
1)ポリエチレン
2)エチレン-酢酸ビニル共重合体(EVA)
3)ケン化EVA、グラフト変性EVA等の変性EVAポリマー
4)エチレン・(メタ)エチルアクリレート(EEA)などのエチレン・(メタ)アクリレート共重合体
5)エチレン・(メタ)アクリル酸共重合体を部分中和してなるアイオノマー樹脂。具体的には、三井・デュポンポリケミカル社から商品名:ハイミランで上市されているものなどが挙げられる。
6)エチレン・プロピレン共重合体、エチレン・プロピレン・(メタ)アクリル酸ターポリマー
7)ポリアミド:二塩基酸とジアミンの反応生成物であり、たとえば、大豆油、桐油、トール油等の脂肪酸の2量体であるダイマー酸と、エチレンジアミン、ジエチレントリアミン等のアルキルジアミンとの反応生成物、ならびにナイロン12等のナイロン類等が挙げられる。これらの具体例として、ダイアミド(ダイセル化学工業)、プラチロン(東亜合成化学工業)、アミラン(東レ)等を挙げることができる。
8)ポリエステル:例えば、エステルレジン200および300(東洋紡)、Vita1200、300(グッドイヤー社)等を挙げることができる。
9)プロピレン系ポリマー:アタクチックポリプロピレン、プロピレン・炭素数4以上のα-オレフィン共重合体(但し、Mw:40000より高い)等が挙げられる。
10)ビニル芳香族化合物と共役ジエン化合物からなる共重合体、およびその水添物:具体的には、スチレン・ブタジエンランダム共重合体、スチレン・イソプレンランダム共重合体、ブタジエン・ポリスチレンブロック共重合体、ポリスチレン・ポリイソプレンブロック共重合体、ポリスチレン・ポリイソプレン・ポリスチレントリブロック共重合体、ポリスチレン・ポリブタジエン・ポリスチレントリブロック共重合体、ポリ(α-メチルスチレン)・ポリブタジエン・ポリ(α-メチルスチレン)トリブロック共重合体、およびこれらの水添物等を挙げることができる。
粘着付与剤(D)は、ベースポリマー(B3)の溶融時の粘度を調整し、ホットタック性や濡れ性を向上させるために配合されうる。粘着付与剤(D)の例には、脂肪族系水添タッキファイヤー、ロジン、変性ロジンまたはこれらのエステル化物、脂肪族系石油樹脂、脂環族系石油樹脂、芳香族系石油樹脂、脂肪族成分と芳香族成分の共重合石油樹脂、低分子量スチレン系樹脂、イソプレン系樹脂、アルキルフェノール樹脂、テルペン樹脂、クマロン・インデン樹脂等が含まれる。粘着付与剤(D)は、1種単独でも2種以上を組み合わせて用いてもよい。
変性プロピレン・α-オレフィン共重合体(A)は、本発明の変性プロピレン・α-オレフィン共重合体(A)としうる。変性プロピレン・α-オレフィン共重合体(A)は、組成物の接着性を損なうことなく、溶融粘度を低下させうると考えられる。
実施例及び比較例における物性値等は、以下の測定方法により求めた。
重合体のプロピレン由来の構成単位、及び炭素数4以上のα-オレフィン由来の構成単位の含有割合は、13C-NMRスペクトルの解析により求めた。
重合体の重量平均分子量(Mw)は、GPCにより測定した。GPC測定は、以下の条件で行った。また、重量平均分子量(Mw)と数平均分子量(Mn)は、市販の単分散標準ポリスチレンを用いて検量線を作成し、下記の換算法に基づいて求めた。
[測定条件]
装置:ゲル浸透クロマトグラフAlliance GPC2000型(Waters社製)
有機溶媒:o-ジクロロベンゼン
カラム:TSKgel GMH6-HT×2、TSKgel GMH6-HTLカラム×2(何れも東ソー社製)
流速:1.0 ml/分
試料:0.15mg/mL o-ジクロロベンゼン溶液
温度:140℃
分子量換算 :PP換算/汎用較正法
なお、汎用較正の計算には、Mark-Houwink粘度式の係数を用いた。PS、PPのMark-Houwink係数はそれぞれ、文献(J.Polym.Sci.,Part A-2,8,1803(1970)、Makromol.Chem.,177,213(1976))に記載の値を用いた。
融点(Tm)は、DSC(示差走査型熱量測定法)に従い、DSC-20(セイコー電子工業社製)によって測定した。即ち、試料約10mgを-20℃から200℃まで10℃/分で昇温し、得られたカーブの吸熱ピークの温度を融点として求めた。この昇温測定の前に、一旦、試料(共重合体)を200℃程度まで昇温し、5分間保持した後、10℃/分で常温(-20℃)まで降温する操作を行い、試料(共重合体)の熱履歴を統一した。
上記DSCにより得られた吸熱ピーク全体のベースラインから吸熱ピークトップまでの高さの半量の位置におけるピーク幅(℃)を半値幅として求めた。
上記DSCにより得られた吸熱ピークと吸熱ピーク全体のベースラインとで区切られた面積から融解熱量(ΔH)(J/g)を算出した。
重合体の結晶化温度(Tc)は、DSC(示差走査型熱量測定法)に従い、DSC-20(セイコー電子工業社製)によって測定した。即ち、試料約10mgを200℃程度まで昇温し、5分間保持した後、10℃/分で常温(-20℃)まで降温する操作を行い、得られたカーブの発熱ピークの温度を結晶化温度として求めた。
プロピレン・α-オレフィン共重合体(A1)が有する分子末端部分のビニリデン基の数は、1H-NMRにより測定した。1H-NMRについては、日本電子製JNM-ECX400P型核磁気共鳴装置を用い、試料20mgをNMRサンプル管(5mmφ)中で重水素化o-ジクロロベンゼン約0.5mlに完全に溶解させた後、120℃にて測定した。プロピレン・α-オレフィン共重合体(A1)由来シグナルの全積分強度を2000に規格化した場合における、4.7ppm付近に観測されるビニリデン基に由来する2プロトン分のピーク積分強度(C)を下記式に当てはめて、ビニリデン基の数を算出した。
ビニリデン基の数L(個/1000炭素)=C/2
重合体の試料をホットプレスで180℃×5分加熱後、コールドプレスで水冷×5分冷却することにより、1mm厚のプレスシートを作製した。得られたプレスシートについて、回転試料台を有するX線回折装置(リガク製RINT2500)を用い、Cu-Kα線、50kV-300mAの条件で、透過法にて、2θが5°~35°の範囲で、広角X線回折プロファイルを測定した。得られたX線回折プロファイルより、結晶由来部分と非結晶由来部分とを分離して、各回折強度比より結晶化度を求めた。
混合キシレン:n―ブタノール=1:1質量比の混合溶媒に、精秤した重合体の試料を溶解させて試料溶液を得た。次いで、この試料溶液を、予め標定されたN/10水酸化カリウムのアルコール溶液(特級水酸化カリウム7gにイオン交換水5gを添加し、1級エチルアルコールで1L(リットル)とし、N/10塩酸と1%フェノールフタレイン溶液にて力価=Fを標定したもの)で滴定し、その中和量から次式に従って算出した。
酸価(mgKOH/g)=(N/10 KOH滴定量(ml)×F×5.61)/(試料(g)×0.01)
JIS K 2207に従って、部分的な過熱を避け、泡が入らないように溶融させた変性プロピレン・α-オレフィン共重合体(A)の試料を、15~30℃の室温に1~1.5時間放置し固化させた。その後、恒温槽で25℃に保ち、温度が安定した後に試料表面に規定の針が5秒間で進入する長さを針入度(dmm)として求めた。
示差走査熱量測定装置(パーキンエルマー社製、DSC7)を用い、試料を約5mgセットして、200℃の状態で5分間放置することにより試料を完全に溶融させた。その後、320℃/分の降温速度で50℃まで急冷して等温結晶化を行った。冷却開始から結晶化熱が全発熱量の1/2に到達するまでの時間を半結晶化時間(秒)とした。
〔プロピレン・1-ブテン共重合体(A2-1)〕
充分に窒素置換した2000mlの重合装置に、900mlの乾燥ヘキサン、1-ブテン65gとトリイソブチルアルミニウム(1.0mmol)を常温で仕込んだ後、重合装置内温を70℃に昇温し、プロピレンで0.7MPaに加圧した。次いで、ジメチルメチレン(3-tert-ブチル-5-メチルシクロペンタジエニル)フルオレニルジルコニウムジクロリド0.002mmolとアルミニウム換算で0.6mmolのメチルアルミノキサン(東ソー・ファインケム社製)を接触させたトルエン溶液を重合器内に添加し、内温62℃、プロピレン圧0.7MPaを保ちながら30分間重合し、20mlのメタノールを添加し重合を停止した。脱圧後、2Lのメタノール中で重合溶液から重合体を析出し、真空下130℃、12時間乾燥し、プロピレン・1-ブテン共重合体(A2-1)を得た。
充分に窒素置換した2000mlの重合装置に、900mlの乾燥ヘキサン、1-ブテン30gとトリイソブチルアルミニウム(1.0mmol)を常温で仕込んだ後、重合装置内温を70℃に昇温し、プロピレンで0.7MPaに加圧した。次いで、ジメチルメチレン(3-tert-ブチル-5-メチルシクロペンタジエニル)フルオレニルジルコニウムジクロリド0.002mmolとアルミニウム換算で0.6mmolのメチルアルミノキサン(東ソー・ファインケム社製)を接触させたトルエン溶液を重合器内に添加し、内温62℃、プロピレン圧0.7MPaを保ちながら30分間重合し、20mlのメタノールを添加し重合を停止した。脱圧後、2Lのメタノール中で重合溶液から重合体を析出し、真空下130℃、12時間乾燥し、プロピレン・1-ブテン共重合体(A2-2)を得た。
プロピレン・エチレン共重合体(X2-2)として、SM668(タイタンケミカル社)を用いた。
[製造例1]
1)プロピレン・1-ブテン共重合体(A1-1)の製造
攪拌装置、窒素導入管、コンデンサーを備えた1.5Lステンレス製熱分解装置に、上記製造した原料プロピレン・1-ブテン共重合体(A2-1)を200g入れ、系内を充分に窒素置換した。次に、窒素を流入したまま熱分解装置内の温度を380℃まで昇温し樹脂を溶融した後、攪拌を開始した。系内の樹脂温度が所定温度に達してから4.5時間加熱し熱分解を実施した。その後、常温まで冷却することにより、プロピレン・1-ブテン共重合体(A1-1)を得た。
2)変性プロピレン・1-ブテン共重合体(A-1)の製造
得られたプロピレン・1-ブテン共重合体(A1-1)200gをトルエン1000ml中に入れ、160℃で耐圧オートクレーブ中で完全に溶解させた。これに、70℃の無水マレイン酸16.3gおよび常温のジターシャリーブチルパーオキサイド(日本油脂社製、パーブチルD)27.7gを同時にそれぞれ1.5時間かけて供給し、1時間熟成後、真空度を1mmHgとして溶剤を除去し、表2に示す物性を有する変性プロピレン・1-ブテン共重合体(A-1)を得た。
1)プロピレン・1-ブテン共重合体(A1-1)の製造
製造例1と同様にしてプロピレン・1-ブテン共重合体(A1-1)を得た。
2)変性プロピレン・1-ブテン共重合体(A-2)の製造
得られたプロピレン・1-ブテン共重合体(A1-1)200gをトルエン1000ml中に入れ、160℃で耐圧オートクレーブ中で完全に溶解させた。これに、70℃の無水マレイン酸6.8gおよび常温のジターシャリーブチルパーオキサイド(日本油脂社製、パーブチルD)11.6gを同時にそれぞれ1.5時間かけて供給し、1時間熟成後、真空度を1mmHgとして溶剤を除去し、表2に示す物性を有する変性プロピレン・1-ブテン共重合体(A-2)を得た。
1)プロピレン・1-ブテン共重合体(A1-2)の製造
原料として、上記製造したプロピレン・1-ブテン共重合体(A2-2)を用い、熱分解装置内の温度を395℃とした以外は製造例1と同様に熱分解して、プロピレン・1-ブテン共重合体(A1-2)を得た。
2)変性プロピレン・1-ブテン共重合体(A-3)の製造
次いで、得られたプロピレン・1-ブテン共重合体(A1-2)と無水マレイン酸とを製造例1と同様に変性反応させて、表2に示される変性プロピレン・1-ブテン共重合体(A-3)を得た。
1)プロピレン・エチレン共重合体(X1-1)の製造
乾燥した反応容器を窒素で洗浄し、100Ndm3の水素および10dm3の液状プロピレンで満たした。次いで、メチルアルミノキサンのトルエン溶液30cm3および300gのエチレンを添加し、この混合物を30℃で15分間攪拌した。一方、ジメチルシリル-ビスインデニルジルコニウム-ジクロライドをメチルアルミノキサンのトルエン溶液15cm3に溶解させ、15分間放置して予備活性化した。次いで、得られた溶液を反応容器に導入し、残量のエチレンを一様に添加しながら、60℃の重合温度で60分間重合反応させた。それにより、プロピレン・エチレン共重合体(X1-1)を得た。
2)変性プロピレン・エチレン共重合体(X-1)の製造
得られたプロピレン・エチレン共重合体(X1-1)と無水マレイン酸とを製造例1と同様に変性反応させて、表2に示される変性プロピレン・1-ブテン共重合体(X-1)を得た。
1)プロピレン・エチレン共重合体(X1-2)の製造
原料として、上記製造したプロピレン・エチレン共重合体(X2-2)を用いた以外は製造例1と同様に熱分解して、プロピレン・エチレン共重合体(X1-2)を得た。
2)変性プロピレン・エチレン共重合体(X-2)の製造
得られたプロピレン・エチレン共重合体(X1-2)と無水マレイン酸とを製造例1と同様に変性反応させて、表2に示される変性プロピレン・エチレン共重合体(X-2)を得た。
1)プロピレン・エチレン共重合体(X1-3)の製造
プロピレン・エチレン共重合体(X1-3)として、三井ハイワックスTM110P(三井化学(株)製)を原料として用いた。
2)変性プロピレン・エチレン共重合体(X-3)の製造
得られたプロピレン・エチレン共重合体(X1-3)と無水マレイン酸とを製造例1と同様に変性反応させて、表2に示される変性プロピレン・エチレン共重合体(X-3)を得た。
3-1.水分散型組成物
〔実施例1〕
〔酸変性プロピレン・1-ブテン共重合体の製造〕
プロピレン・1-ブテン共重合体(A2-1)を100重量部に無水マレイン酸1重量部、重合開始剤にパーヘキシン25B(日油株式会社製)を0.3重量部とを混合したものを2軸スクリュー押出機(池貝鉄工株式会社製、PCM-30,L/D=40)を用いて加熱温度220℃、16kg/時間で変性を行い、酸変性プロピレン・1-ブテン共重合体を得た。
前述のプロピレン・1-ブテン共重合体(A2-1)を70重量部、上記で得られた酸変性プロピレン・1-ブテン共重合体を30重量部、製造例1で得られた変性プロピレン・1-ブテン共重合体(A-1)を10重量部、オレイン酸カリウム4重量部とを混合したものを、2軸スクリュー押出機(池貝鉄工株式会社製、PCM-30,L/D=40)のホッパーより3000g/時間の速度で供給し、同押出機のベント部に設けた供給口より、2-アミノ-2-メチル-1-プロパノールの30%水溶液を連続的に供給し、加熱温度230℃で連続的に押出した。押出された樹脂混合物は、同二軸押出機の先端に連結された40mmφ一軸押出機(L/D=27、バレル温度:130℃)の先端より押し出すことにより、水分散型組成物を得た。
攪拌機、温度計、還流冷却装置、及び窒素導入管を備えた反応容器に、イオン交換水300gおよびラウリル硫酸ナトリウム1gを仕込み、攪拌下、窒素置換しながら75℃まで昇温した。内温を75℃に保持し、重合開始剤として過硫酸カリウム2gを添加し、溶解後、予めイオン交換水250g、ラウリル硫酸ナトリウム1g、アクリルアミド9gにスチレン200g、2-エチルヘキシルアクリレート220g、メタクリル酸9gを攪拌下に加えて作製した乳化物を、反応容器に連続的に6時間かけて滴下して重合させた。滴下終了後、5時間熟成、中和して、アクリル樹脂の水分散体を得た。得られたアクリル樹脂の水分散体は、固形分濃度:40%、平均粒径:0.2μmであった。
そして、得られたプライマー層の表面を目視観察し、以下の基準でプライマー層の外観を評価した。
〔プライマー層の外観の評価〕
○:若干白化が生じることもあるが、光沢がある
×:白化や亀裂があり、光沢がない
〔剥離強度の評価〕
1)処理温度80℃の場合
○:600g/cm以上
△:400g/cm以上600g/cm未満
×:400g/cm未満
2)処理温度120℃の場合
○:1000g/cm以上
△:800g/cm以上1000g/cm未満
×:800g/cm未満
水分散型組成物の組成および樹脂粒子の平均粒径を表3に示されるように変更した以外は実施例1と同様にして水分散型組成物を得て、同様の評価を行った。
(原料)
<極性モノマーグラフト架橋樹脂の調製>
プロピレン系エラストマーの合成
充分に窒素置換した2リットルのオートクレーブに、ヘキサンを900ml、1-ブテンを85g仕込み、トリイソブチルアルミニウムを1ミリモル加え、70℃に昇温した後、プロピレンを供給して全圧7kg/cm2Gにし、メチルアルミノキサン0.30ミリモル、上記製造例と同様の方法で製造されたrac-ジメチルシリレン-ビス{1-(2-メチル-4-フェニルインデニル)}ジルコニウムジクロライドをZr原子に換算して0.001ミリモル加え、プロピレンを連続的に供給して全圧を7kg/cm2Gに保ちながら30分間重合を行った。重合後、脱気して大量のメタノール中でポリマーを回収し、110℃で12時間減圧乾燥し、Mw240,000、Tm91℃のプロピレン系エラストマーを得た。
次いで、上記プロピレン系エラストマー(合成品)50質量部、スチレン系エラストマー(タフテックH1051、旭化成社SEBS、スチレン含量:40質量部、Mw:72,000)50質量部に対し、極性モノマー(無水マレイン酸)1.0質量部、ラジカル重合開始剤(パーへキシン25B )0.2質量部加え、充分混合した後、2軸押出機(日本プラコン社製、30mm押出機、L/D=42、同方向回転、ベント2箇所設置、0.08MPaにベントを減圧)を用いて、押出温度220℃ 、回転数500回転/分、押出量16kg/時間で押出変性を行い、極性モノマーグラフト架橋樹脂を得た。
製造例1で得られた変性プロピレン・1-ブテン共重合体(A-1)
上記製造した極性モノマーグラフト架橋樹脂54gと、製造例1で得られた変性プロピレン・1-ブテン共重合体(A-1)6gとを、メチルシクロヘキサン240gに同時に溶解し、固形分20質量%の溶媒分散型組成物を得た。
上記製造した極性モノマーグラフト架橋樹脂48gと、製造例1で得られた変性プロピレン・1-ブテン共重合体(A-1)12gとを、メチルシクロヘキサン240gに同時に溶解し、固形分20%の溶媒分散型組成物を得た。
製造例1で得られた変性プロピレン・1-ブテン共重合体(A-1)を用いず、上記製造した極性モノマーグラフト架橋樹脂60gをメチルシクロヘキサン240gに溶解し、固形分20%の溶媒分散型組成物を得た。
得られた溶媒分散型組成物を一週間静置した後、静置安定性を以下の基準で評価した。
○:分離なし
△:やや分離あり
×:顕著に分離あり
得られた溶媒分散型組成物を、バーコーターを使用して、アルミ箔上に乾燥厚みが2μmとなるよう塗布した後、風乾させた。この塗布物を、170℃にセットしたエア・オーブン中で20秒間加熱した。得られた塗布物の塗膜の外観を、以下の基準で評価した。
○:塗膜にスジやムラがなく、均一である
×:塗膜にスジやムラある
得られた溶媒分散型組成物を、バーコーターを使用して、アルミ箔上に乾燥厚みが2μmとなるよう塗布した後、風乾させてヒートシール層を形成した。次いで、ヒートシール層上に、PPシートを配置し、100℃または140℃で1秒間熱圧着(ヒートシール)させた。得られた積層物の、ヒートシール層とアルミ箔との界面の接着強度を、180°剥離試験(速度100mm/分)により測定した。
〔実施例5〕
200ml三角フラスコに、有機溶媒としてメチルシクロヘキサン(SP値7.8)90質量部と、ワックスとして製造例1で得られた変性プロピレン・1-ブテン共重合体(A-1)10質量部とを投入し、ヒーター付きスターラーを用いて室温にて攪拌して、溶媒溶解型組成物を得た。
有機溶媒とワックスの種類を表5または6に示されるように変更した以外は実施例5と同様にして溶媒溶解型組成物を得た。
有機溶媒とワックスの種類を表6に示されるように変更した以外は実施例5と同様にして溶媒溶解型組成物を調整した。しかしながら、常温で組成物がゲル化するために、組成物の粘度、塗工性、耐ブロッキング性、塗膜密着性を評価することができなかった。
溶媒溶解型組成物を調製する過程でスターラーを適宜停止させて、以下基準により、常温における溶解性を評価した。
◎:速やかに溶解し、透明となる
○:60分後に溶解し、透明となる
△:一部溶解せず、分散する
×:膨潤またはゲル化して、溶解しない
次いで、上記溶解型組成物が40℃になるまでヒーターにて加温し、その後、1時間攪拌し、再度スターラーを停止させて、常温と同一の基準により、40℃における溶解性を評価した。同様の方法で、50℃における溶解性を評価した。
得られた溶媒溶解型組成物の常温における60回転粘度を、B型粘度計にて測定した。30秒後の読み取り値を、粘度(mPa・s)とした。
得られた溶媒溶解型組成物を、常温にて1日静置後の状態を以下基準により評価した。
○:溶解、もしくは相分離に時間がかかる
×:相分離が速い、もしくは再分散が困難である
PET(ポリエチレンテレフタレート)フィルム上に、膜厚可変型アプリケーターを用いて、塗膜の厚さが5μmになるように塗布後、常温乾燥および160℃×30秒乾燥後の塗膜の表面状態をそれぞれ観察し、以下の基準で評価した。
◎:透明、均一
○:濁りがあるが均一
△:一部にムラあり
×:スジ、ムラがはっきりとしている
上記塗工性の評価において、160℃×30秒乾燥後の塗膜表面のブロッキングを、以下基準により評価した。
○:ブロッキングなし
△:ややブロッキングあり
×:ブロッキングあり
上記塗工性の評価において、160℃×30秒乾燥後の塗膜と基材であるPETとの密着性を、以下基準により評価した。
○:こすっても塗膜の剥がれがなく、上記基材に密着している
△:こすると塗膜の一部が剥がれる
×:容易に塗膜が剥がれる
さらに、上記塗工性の評価において、基材としてPP(ポリプロピレン)フィルムを用い、100℃×60秒乾燥後の塗膜と基材の密着性を評価した。
さらに、上記塗工性の評価において、基材としてAL(アルミニウム)、SUS(ステンレス)を用い、120℃×60秒乾燥後の塗膜と基材の密着性を評価した。評価基準は、いずれも前述と同様とした。
(原料)
熱可塑性樹脂(B2):
芳香族ポリカーボネート樹脂(帝人(株)、パンライトL-1225Y)
無機強化材(C):
ポリカーボネート用グラスファイバー(日東紡(株):チョップドストランドCS(F)3PE455S)
ワックス:
製造例1の変性プロピレン・1-ブテン共重合体(A-1)
製造例6の変性プロピレン・エチレン共重合体(X-3)
芳香族ポリカーボネート樹脂(帝人(株):パンライトL-1225Y)90重量部、ポリカーボネート用グラスファイバー(日東紡(株):チョップドストランドCS(F)3PE455S)10重量部、および変性プロピレン・1-ブテン共重合体(A-1)3重量部を、同方向回転二軸押出機 HK25D((株)パーカーコーポレーション:φ25mm,L/D=41)を用いて溶融混練して、シリンダー温度280℃のもと押出してペレット化した樹脂組成物を得た。
衝撃強度は、シャルピー衝撃試験にて測定した。即ち、作製した試験片を、JIS K-7111に基づき、ハンマー重量2J、ハンマー回転周りのモーメント1.08N・J、ハンマー持ち上げ角度50°、衝撃速度2.9m/s、回転軸から打撃点までの距離0.23mの条件でシャルピー衝撃値を測定した。
曲げ弾性率は、曲げ試験により測定した。即ち、作製した試験片を、JIS K-7171に準じて、荷重レンジ50kg、試験速度2mm/min、曲げスパン64mmの条件で弾性率および強度を測定した。
引張強度は、引張試験により測定した。即ち、作製した試験片を、JIS K-7162-1Aに基づき、荷重レンジ1000kg、試験速度500mm/min、つかみスパン115mmの条件で降伏・破断強度および伸びを測定した。
樹脂組成物の組成を表7に示されるように変更した以外は実施例11と同様にして樹脂組成物を得た。
(原料)
ベースポリマー(B3):
EVA#220(三井デュポンケミカル社製エチレン-酢酸ビニル共重合体)
粘着付与剤(D):
脂肪族系石油樹脂:日本ゼオン社製、クイントンM1
ワックス:
製造例1の変性プロピレン・1-ブテン共重合体(A-1)
製造例4の変性プロピレン・エチレン共重合体(X-1)
製造例5の変性プロピレン・エチレン共重合体(X-2)
未変性プロピレン・エチレンワックス(サゾールワックス社、サゾールワックス(商標名)H1)
ベースポリマー(B3)としてエチレン-酢酸ビニル共重合体(EVA#220:三井デュポンポリケミカル社)40質量部と、粘着付与剤(D)として脂肪族系石油樹脂(日本ゼオン社製クイントンM1)40質量部と、変性プロピレン・αーオレフィン共重合体(A)として製造例1の変性プロピレン・1-ブテン共重合体(A-1)20質量部とを、180℃で溶融混合し、ホットメルト組成物を調製した。
変性プロピレン・αーオレフィン共重合体(A)を、表8に示されるワックスに変更した以外は実施例12と同様にしてホットメルト組成物を調製した。
得られたホットメルト組成物の140℃、160℃、または180℃における流動性を目視観察して、以下基準で評価した。
○:流動性あり
×:固化
得られたホットメルト組成物を、アルミ箔(厚さ:50μm)の片面に15μmの厚さに塗工した。次いで、アルミ箔を折り曲げて、塗工面同士を貼り合わせ、上部バー170℃、下部バー70℃、圧着時圧力1kg/cm2、2秒の条件でヒートシールを行い、ホットメルト接着剤層を介してアルミ箔を貼り合わせた接着片を作製した。この接着片を、25mm幅に切断して試料とし、20℃の測定温度下、引張速度:300mm/minでT型剥離試験を行い、以下の基準に基づき接着強度を測定した。
○:接着力350g/25mm以上
×:接着力350g/25mm未満
本発明によれば、変性プロピレン・α-オレフィン共重合体は、低融点でありながら、ベタ付きが少なく、極性基を含有しても結晶性を維持し、高硬度である。従って、本発明の変性プロピレン・α-オレフィン共重合体は、コーティング材や、成形様樹脂組成物、ホットメルト接着剤組成物などの各種用途に好ましく用いることができる。
本発明の変性プロピレン・α-オレフィン共重合体を含む成形用樹脂組成物として、衝撃強度、曲げ強度、引張強度等の力学特性のバランスに優れる。
本発明の変性プロピレン・α-オレフィン共重合体を含むホットメルト接着剤組成物は、変性プロピレン・α-オレフィン共重合体とベースポリマーや粘着付与樹脂との相容性が良好であるため、流動性に優れるとともに、基材との密着性が高い。
本発明の変性プロピレン・α-オレフィン共重合体は、上記以外の種々の用途に用いることもできる。例えば、オレフィン系塗料、樹脂改質剤、ヒートシール剤、印刷インキ耐磨耗剤、表面コーティング剤、熱転写記録媒体向け添加剤、不織布改質剤、トナー添加剤、艶出し剤、樹脂成形用離型剤、ゴム用加工助剤、紙質向上剤、繊維加工助剤、電気絶縁剤、天然ワックスの配合剤、ポリオレフィンフィルムの防曇剤、顔料分散剤(マスターバッチ)、成形加工助剤、ゴム用酸化防止剤、ペーパーコーティング、繊維仕上剤、塩ビ用滑剤、アスファルト用添加剤、発泡ポリスチレン用増核剤、ロストワックス、ろうそくの一成分等種々の用途に用いることができる。
Claims (22)
- プロピレン由来の構成単位(a)を60~95モル%、炭素数4以上のα-オレフィン由来の構成単位(b)を5~40モル%〔(a)+(b)=100モル%とする〕含み、下記(i)~(iv)を全て満たすプロピレン・α-オレフィン共重合体(A1)に、不飽和カルボン酸もしくはその誘導体または不飽和スルホン酸もしくはその塩から選ばれる少なくとも1種をグラフトした共重合体であり、
酸価が0.5~100KOHmg/gである、変性プロピレン・α-オレフィン共重合体(A)。
(i)GPCで測定した重量平均分子量(Mw)が3,000~40,000の範囲にある
(ii)DSCで測定した融点(Tm)が60~110℃の範囲にある
(iii)DSCで測定した結晶融点ピークの半値幅が1~20℃の範囲にある
(iv)1HNMRにより測定した、1000個の炭素原子あたりのビニリデン基の個数が0.5~5個である - 前記プロピレン・α-オレフィン共重合体(A1)が、プロピレン・炭素数4以上のα-オレフィン共重合体(A2)を熱分解して得られる、請求項1に記載の変性プロピレン・α-オレフィン共重合体(A)。
- 前記プロピレン・炭素数4以上のα-オレフィン共重合体(A2)が、プロピレン由来の構成単位(a’)を60~95モル%、炭素数4以上のα-オレフィン由来の構成単位(b’)を5~40モル%〔(a’)+(b’)=100モル%とする〕含み、かつ下記(i’)~(iii’)の全てを満たす、請求項2に記載の変性プロピレン・α-オレフィン共重合体(A)。
(i')GPCで測定した重量平均分子量(Mw)が50,000~1,000,000の範囲にある
(ii')DSCで測定した融点(Tm)が60~120℃の範囲にある
(iii')DSCで測定した結晶融点ピークの半値幅が1~20℃の範囲にある - 前記プロピレン・α-オレフィン共重合体(A1)が、下記要件(v)をさらに満たす、請求項1~3のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)。
(v)DSCで測定した融解ピークのΔHが40~100J/gの範囲にある - 前記変性プロピレン・α-オレフィン共重合体(A)の結晶化温度をTc(A)とし、前記プロピレン・α-オレフィン共重合体(A1)の結晶化温度をTc(A1)としたとき、結晶化温度の比Tc(A1)/Tc(A)が、1.0~1.6の範囲である、請求項1~4のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)。
- プロピレン・炭素数4以上のα-オレフィン共重合体(A2)を熱分解して、プロピレン由来の構成単位(a)を60~95モル%、炭素数4以上のα-オレフィン由来の構成単位(b)を5~40モル%〔(a)+(b)=100モル%とする〕含み、下記(i)~(iii)を全て満たすプロピレン・α-オレフィン共重合体(A1)を得る工程と、
(i)GPCで測定した重量平均分子量(Mw)が3,000~40,000の範囲にある
(ii)DSCで測定した融点(Tm)が60~110℃の範囲にある
(iii)DSCで測定した結晶融点ピークの半値幅が1~20℃の範囲にある
前記プロピレン・α-オレフィン共重合体(A1)に、不飽和カルボン酸もしくはその誘導体または不飽和スルホン酸もしくはその塩から選ばれる少なくとも1種をグラフト重合させて、酸価が1~100KOHmg/gである変性プロピレン・α-オレフィン共重合体(A)を得る工程とを含む、変性プロピレン・α-オレフィン共重合体(A)の製造方法。 - 前記プロピレン・炭素数4以上のα-オレフィン共重合体(A2)を300~450℃で5分~10時間熱分解して前記プロピレン・α-オレフィン共重合体(A1)を得る、請求項6に記載の変性プロピレン・α-オレフィン共重合体(A)の製造方法。
- 前記プロピレン・α-オレフィン共重合体(A1)が、下記要件(iv)をさらに満たす、請求項6または7に記載の変性プロピレン・α-オレフィン共重合体(A)の製造方法。
(iv)1HNMRにより測定した、1000個の炭素原子あたりのビニリデン基の個数が0.5~5個である - 前記プロピレン・炭素数4以上のα-オレフィン共重合体(A2)が、プロピレン由来の構成単位(a’)を60~95モル%、炭素数4以上のα-オレフィン由来の構成単位(b’)を5~40モル%〔(a')+(b')=100モル%とする〕含み、かつ下記(i')~(iii')の全てを満たす、請求項6~8のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)の製造方法。
(i')GPCで測定した重量平均分子量(Mw)が50,000~1,000,000の範囲にある
(ii')DSCで測定した融点(Tm)が60~120℃の範囲にある
(iii')DSCで測定した結晶融点ピークの半値幅が1~20℃の範囲にある - 請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)と、他の樹脂(B1)とを含み、
前記変性プロピレン・α-オレフィン共重合体(A)と前記他の樹脂(B1)の重量比が、1/99~90/10である、樹脂組成物。 - 水または有機溶媒100重量部と、前記水または有機溶媒に溶解または分散された請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)0.1~100重量部とを含む、コーティング材。
- 水または有機溶媒100重量部と、前記水または有機溶媒に溶解または分散された請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)および他の樹脂(B1)を合計0.1~100重量部とを含み、
前記変性プロピレン・α-オレフィン共重合体(A)と前記他の樹脂(B1)の重量比は、1/99~90/10である、コーティング材。 - 前記有機溶媒のSP値が7~12である、請求項11または12に記載のコーティング材。
- 前記有機溶媒が、炭化水素系溶媒、アルコール系溶媒、エステル系溶媒から少なくとも一種を含む、請求項11~13のいずれか一項に記載のコーティング材。
- 前記変性プロピレン・α-オレフィン共重合体(A)が、50℃以上の温度で前記有機溶媒に完全に溶解する、請求項11~14のいずれか一項に記載のコーティング材。
- 熱可塑性樹脂および熱硬化性樹脂からなる群から選択される少なくとも1種の樹脂(B2)100~50重量部と、
無機強化材(C)0~50重量部(ただし、成分(B2)と成分(C)との合計を100重量部とする)と、
請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)を0.01~10重量部と、を含む、成形用樹脂組成物。 - ベースポリマー(B3)100重量部と、
粘着付与剤(D)10~300重量部と、
請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)1~100重量部と、を含む、ホットメルト組成物。 - 請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)、もしくは、請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)および他の樹脂(B1)を含む、塗料。
- 請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)、もしくは、請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)および他の樹脂(B1)を含む、プライマー。
- 請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)、もしくは、請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)および他の樹脂(B1)を含む、接着剤。
- 請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)、もしくは、請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)および他の樹脂(B1)を含む、粘着剤。
- 請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)、もしくは、請求項1~5のいずれか一項に記載の変性プロピレン・α-オレフィン共重合体(A)および他の樹脂(B1)を含む、焼結助剤。
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EP14860398.8A EP3067372A4 (en) | 2013-11-05 | 2014-11-05 | Modified propylene-(alpha-olefin) copolymer, method for producing same, coating material comprising same, resin composition for molding use, and hot-melt composition |
KR1020167011751A KR101800567B1 (ko) | 2013-11-05 | 2014-11-05 | 변성 프로필렌·α-올레핀 공중합체와 그의 제조 방법, 그것을 포함하는 코팅재, 성형용 수지 조성물 및 핫 멜트 조성물 |
US15/034,136 US10072116B2 (en) | 2013-11-05 | 2014-11-05 | Modified propylene-(α-olefin) copolymer, method for producing same, coating material comprising same, resin composition for molding use, and hot-melt composition |
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EP3067372A4 (en) | 2017-06-21 |
EP3067372A1 (en) | 2016-09-14 |
TWI635100B (zh) | 2018-09-11 |
JP6293778B2 (ja) | 2018-03-14 |
US20160280828A1 (en) | 2016-09-29 |
JPWO2015068385A1 (ja) | 2017-03-09 |
KR101800567B1 (ko) | 2017-11-22 |
KR20160067919A (ko) | 2016-06-14 |
US10072116B2 (en) | 2018-09-11 |
TW201522386A (zh) | 2015-06-16 |
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