JPS61185546A - Olefin polymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent paintability, printability and adhesivity, and high rigidity, and suitable for automobile parts, etc., by compounding a crystalline propylene polymer with specific amounts of a styrene polymer, an ethylene copolymer and slag wool. CONSTITUTION:The objective composition can be produced by compounding 100pts.(wt.) of a crystalline propylene polymer having a melt flow index of 0.01-100g/10min with (A) 0.5-20pts. of a styrene polymer having a molecular weight of 22,000-400,000 and composed mainly of styrene, (B) 3-28pts. of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 5-50(wt)% and/or an ethylene-(meth)acrylic acid ester copolymer having a (meth)-acrylate content of 5-40%, (C) 5-40pts. of artificial slag wool having a fiber thickness of 3-10mu and length of 50-500mu, and if necessary (D) <=30pts. of an ethylene polymer. The sum of the components A, B and D is 10-45pts.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Object of the Invention The present invention relates to an olefin polymer composition having excellent paintability, printability and adhesiveness. More specifically, (A
) crystalline propylene polymer, (B) styrene polymer with a molecular weight of 220,000 to 400,000, (C) ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, and ethylene-methacrylic acid At least one ethylene copolymer selected from the group consisting of ester copolymers and (D) slag wool or these and (
E) This relates to an olefin polymer composition made of an ethylene polymer, and the purpose is to provide an olefin polymer composition that has improved paintability, printability, and adhesion, and has high rigidity. It is.

(II) Background of the Invention As is well known, olefin polymers (ethylene polymers, propylene polymers, and copolymers containing ethylene or propylene as a main component with other olefins) are widely produced industrially. It is used in many ways as a general-purpose resin. However, olefin polymers are so-called non-polar, chemically extremely inert polymeric substances that do not have polar groups in their molecules. Furthermore, they have high crystallinity and extremely low solubility in solvents, so they cannot be used for coating. When used in fields such as printing or adhesion, they are very poor, and when used in fields where high rigidity is required, the rigidity is not sufficient.

In order to solve these problems, various methods such as those described below have been proposed for quite some time.

(a) A method in which an olefin polymer or a molded product thereof is surface-treated from the outside and modified by a physical or chemical method.

(b) A method of adding other polymeric substances or additives to the olefin polymer [hereinafter referred to as "addition method"].

Among these methods, the addition method will be explained in more detail below, and the problems will be described.

This method includes a so-called resin blending method in which a rubber substance and/or a resin containing a polar group is added to an olefin polymer [hereinafter referred to as "addition method (a)"].
] and "fillers (e.g. calcium carbonate,
A method of adding additives such as barium sulfate, talc, clay, wood flour) (hereinafter referred to as "addition method (b)") is mentioned.

In addition method (a), when adding a rubber substance to an olefin polymer, the rubber substance is generally in the form of a lump, so when blending (kneading) the resin with the olefin polymer, a continuous mixer ( For example, it is not only almost impossible to perform continuous kneading using extrusion, but also the mechanical properties of the resulting mixture, such as stiffness, hardness, and heat resistance, are significantly reduced. There are drawbacks.

On the other hand, when a resin containing a polar group is added to an olefin polymer, the compatibility between the resin and the olefin polymer is generally poor, so the physical properties of the molded product of the resulting composition (
For example, strength, impact resistance) are not only reduced;
In extreme cases, there are drawbacks such as delamination.

In addition, in the case of addition method (b), when coating polyurethane etc. using the propylene prefecture East combined brammer, there is a drawback that the coating adhesion is very poor and the range of its use is limited.

Cl11) Structure of the Invention From the above, the present inventors aimed to obtain an olefin polymer composition that does not have these drawbacks, has extremely excellent paintability, printability, and adhesiveness, and has high rigidity. As a result of various searches, (A) Melt flow index (JIS K-8
According to 758, the temperature is 230 °C and the load is 2.1
Measured under the condition of 8 kg, hereinafter referred to as rMFI J) was 0.
100 parts by weight of a crystalline propylene polymer having a molecular weight of 01 to 100 g/10 minutes, (B) 0.5 to 20.0 parts by weight of a styrenic polymer whose main component is styrene with a molecular weight of 22,000 to 400,000. .

(r',) Ethylene-vinyl acetate copolymer whose vinyl acetate content is 5.0 to 50% by weight and/or the content of acrylic ester or methacrylic ester is 5.0 to 40% by weight Ethylene-acrylic acid ester copolymer or ethylene-methacrylic acid ester copolymer 3, Q ~ 28.0 parts by weight, and (D) tan thickness is 3.0 ~ lO microns,
and 5.0 to 40 parts by weight of artificial amorphous slag wool having a length of 50 to 500 microns, or (E) a density of o, 900 to 0.975 g/cr.
n”-c and melt index (JIS K-
According to 8780, the temperature is 190°C and the load is 2.
Measured under the condition of 18Kg, hereinafter rM, 1. 3. Ethylene-based polymers having an average temperature of at least 0.1 g/10 min.
It was discovered that 0 to 30.0 parts by weight does not have the above-mentioned drawbacks and has excellent paintability, printability, adhesiveness, and rigidity, and the present invention was achieved based on this finding.

(TV) Detailed Description of the Invention (A) Propylene Polymer The propylene polymer used in the present invention is crystalline, including propylene homopolymer, propylene and ethylene, and/or having 4 to 12 carbon atoms. Random or block copolymers of α-olefins (eg, butene-1°hexene-1,4-methylpentene-1, octene) and Among these propylene-based polymers, the copolymerization proportion of ethylene and α-olefin in random and block copolymers is usually at most 25% by weight (preferably 20% by weight).
below). In addition, MFI is 0.01 to 100 g/
10 minutes and 0. O1 to 50g/10 minutes is desirable,
Particularly suitable is 0.1 to 50 g/10 minutes. M
If a propylene polymer having an FI of less than 0.01 g/10 minutes is used, it is difficult to knead the composition and obtain a uniform composition.

On the other hand, even if a uniform composition is obtained, it may not be possible to produce molded articles. On the other hand, MFI is 100
If a propylene-based polymer having a ratio exceeding g/10 min is used, crosstalk properties and moldability are good, but on the other hand, a composition having excellent mechanical strength cannot be obtained.

(B) Styrenic polymer The molecular weight of the styrenic polymer used in the present invention is 22,000 to 400,000, and 22,000 to 400,000.
350,000 to 350,000 is preferred, and 22,000 to 300,000 is particularly preferred. If the molecular weight exceeds 400,000, the miscibility with the propylene polymer will be poor and dispersion during kneading will be difficult.

On the other hand, if the molecular weight is less than 22,000, the resulting composition will have poor impact resistance. The styrenic polymer used in the present invention may be a styrene homopolymer or a copolymer of styrene and another monomer (copolymerization ratio is 40 mol% or less). Other monomers include monoolefins (at most 8 carbons), diolefins (at most 8 carbons) and (meth)acrylic esters (at most 8 carbons) and acrylonitrile. Examples include polar group-containing vinyl compounds such as. The styrenic polymers may be used alone or in combination of two or more.

(C) Ethylene-vinyl acetate copolymer Furthermore, the content of vinyl acetate in the ethylene-vinyl acetate copolymer used in the present invention is 5 to 50% by weight.
and particularly preferably 10 to 40% by weight. If an unmixed ethylene-vinyl acetate copolymer with a vinyl acetate content of 5% by weight is used, the modification effect will not be satisfactory, which is not desirable.

On the other hand, when an ethylene/vinyl acetate copolymer with a vinyl acetate content exceeding 50% by weight is used, it has poor compatibility with the propylene polymer, which not only deteriorates the physical properties of the composition but also This is not preferable as it may cause peeling.

(D) Ethylene-acrylic ester copolymer and ethylene-methacrylic ester copolymer Also, acrylic ester and ethylene-methacrylic ester copolymer in the ethylene-acrylic ester copolymer used in the present invention The content of methacrylic acid ester is 5 to 40% by weight, preferably 10 to 30% by weight. When using an unlayered ethylene-acrylic ester copolymer or ethylene-methacrylic ester copolymer containing 5% by weight of acrylic ester or methacrylic ester, it is preferable because the modification effect is not satisfactory. do not have. On the other hand, if an ethylene-acrylic ester copolymer or ethylene-methacrylic ester copolymer with an acrylic ester or methacrylic ester content exceeding 40% by weight is used, it will have poor compatibility with the propylene polymer. Therefore, not only the physical properties of the composition deteriorate, but also the layer ilI#
, which is undesirable.

The monomers of the copolymer, acrylic ester and methacrylic ester, are obtained from acrylic acid or methacrylic acid and an alcohol having 1 to 8 carbon atoms.

In carrying out the present invention, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, and ethylene-methacrylic acid ester copolymer may be used alone or in combination of two or more types. .

(E) Slug wool 1; The slag wool used in the Sara Umaki invention is made by melting raw materials such as blast furnace slag and ore containing silicic acid in a cupola (approximately 1500°C), and then using centrifugal force to melt the melted material. It is an artificial amorphous mineral fiber. The thickness of this slug wool is 3.0 to 10 microns. The length is 50 to 500 microns, preferably 50 to 400 microns, and particularly preferably 50 to 300 microns. If slug wool with a length exceeding 500 microns is used, the appearance of the resulting molded composition will be poor. On the other hand, if the diameter is less than 30 microns, the effect of improving the stiffness of the composition will not be sufficient.

In producing the olefin polymer composition of the present invention, the above-mentioned crystalline propylene polymer, styrene polymer, slag wool, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, and ethylene- Although it is obtained by uniformly blending (mixing) at least one type of ethylene copolymer selected from the group consisting of methacrylic acid ester copolymers in the composition ratio described below, it is further blended with the ethylene-based polymer described below. By this process, a composition with further improved coating adhesion can be obtained.

(F) Ethylene polymer The ethylene polymer used in the present invention is selected from ethylene homopolymers and copolymers of ethylene and α-olefins having at most 12 carbon atoms. Among the ethylene polymers, the copolymerization ratio of α-olefin in the copolymer of ethylene and α-olefin is generally at most 20% by weight (preferably.

15% by weight or less). Further, typical examples of the α-olefin include propylene, butene-1, hexene-1
, 4-methylpentene-1 and octene-1. The density of this ethylene polymer is 0.900 to 0.900.
975 g/c, especially between 0.900 and 0.9
70 g/cm" is preferable. Furthermore, ■,
is at least 0.1/10 minutes, and 0.1 to 50
g/10 minutes is desirable, especially 0.5 to 20 g/10 minutes.
10 minutes is preferred.

M, 1. When using an ethylene polymer with a weight of less than 0.1 g 710 min, it is difficult to obtain a uniform composition, and even if a molded product is obtained, the paintability and appearance of the molded product are poor.

The propylene polymer, ethylene polymer, styrene polymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer and ethylene-methacrylic ester copolymer of the present invention can all be used industrially. It is produced and used in many ways.

(C) Composition ratio Styrenic polymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, and ethylene polymer based on 100 parts by weight of the propylene polymer of the present invention The composition ratio of the styrene polymer is 0.5 to 20.0 parts by weight, preferably 1.0 to 20.0 parts by weight, and especially 1.0 to 20.0 parts by weight.
．． 0 to 15.0 parts by weight is suitable. If the composition ratio of the styrene polymer to 100 parts by weight of the styrene polymer is less than 0.5 parts by weight, there is almost no modification effect.

On the other hand, if the amount exceeds 20.0 parts by weight, physical properties such as impact resistance, elongation, and cold resistance of the resulting composition will decrease, and no effect of increasing the amount will be observed in terms of paintability, printability, and adhesion. . In addition, the composition ratio of ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-methacrylic acid ester copolymer is 3.0 as a total amount.
~28.0 parts by weight, preferably 5.0 to 28.0 parts by weight, particularly preferably 5.0 to 25.0 parts by weight. If the total composition ratio of ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, and ethylene-methacrylic acid copolymer to 100 parts by weight of propylene-based polymer is less than 3.0 parts by weight, modification is not possible. has almost no effect. On the other hand, if it exceeds 28.0 parts by weight,
This is not preferred because it does not have a weight increasing effect and the resulting composition has unsatisfactory stiffness, strength and heat resistance. Furthermore, the composition ratio of the ethylene polymer is at most 30.0 parts by weight, preferably 28.0 parts by weight or less,
Particularly suitable is 3.0 to 25.0 parts by weight.

If the composition ratio of the ethylene polymer to 100 parts by weight of the propylene polymer exceeds 30.0 parts by weight, no effect of increasing the amount of the resulting composition will be observed in terms of paintability, printability and adhesiveness. The composition ratio of the slag wool is 5.0 to 40 parts by weight, preferably 5.0 to 35 parts by weight, and particularly preferably 5.0 to 30 parts by weight.

If the composition ratio of slug wool to 100 parts by weight of propylene polymer is less than 5.0 parts by weight, the effect of adding slug wool will be poor, whereas if it exceeds 40 parts by weight, the paintability of the resulting composition will be poor. Regarding printability and adhesion, no effect of increasing the amount is observed.

Other polymers (styrene polymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, and ethylene polymer) relative to 100 parts by weight of propylene polymer The composition ratio of these polymers is generally 10 to 45 parts by weight as a total amount of these polymers. If the total amount of other polymers is less than 10 parts by weight based on 100 parts by weight of the propylene polymer, the coating properties of the resulting composition will be poor. On the other hand, if it exceeds 45 parts by weight, the mechanical strength (especially rigidity) of the propylene polymer is poor.

(H) Mixing method, molding method, etc. In producing the composition of the present invention, propylene polymers, styrene polymers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, and ethylene-methacrylic Although the purpose can be achieved simply by mixing at least one ethylene copolymer selected from the group consisting of acid ester copolymers and slag wool or these and an ethylene polymer, propylene polymers are Other resins and rubbers may be added within a range (usually 30% by weight or less based on the propylene polymer) that does not essentially impair the physical properties.

In addition, if necessary, oxygen, light or heat stabilizers, flame retardants, fillers, reinforcing agents, processability modifiers, lubricants, antistatic agents and pigments commonly used in propylene polymers. Of course, additives such as the following may be added.

The composition may also be triblended using mixers such as tumblers, ribbon blenders, and Hensel mixers, or mixed using bulk kneaders (e.g., Banbury mixers). It can be kneaded, but it can also be kneaded continuously using a continuous mixer as described above. Further, by using these methods in combination (for example, triblending and then continuously kneading), more uniform mixing can be achieved.

Since the resulting mixture (composition) does not change the physical properties of the propylene polymer, injection molding, extrusion molding, and blow molding methods, which are commonly used in molding propylene polymers, are applied. By doing so, a desired molded product can be created.

Although the theoretical background of the present invention is not necessarily clear, the styrene polymer uniformly dispersed in the propylene polymer is dissolved in the solvent of paint, printing ink, and adhesive, and the surface of the molded product is physically roughened. Faced. On the other hand, the ethylene-vinyl acetate copolymer or ethylene-acrylic acid ester copolymer uniformly dispersed in the propylene polymer is compatible with components such as paint on the surface of the molded article. on the other hand,
Slug wool uniformly dispersed in a propylene polymer can significantly improve rigidity without impeding the aforementioned effects. Furthermore, it is thought that the ethylene polymer dispersed in the propylene polymer acts to capture the paint components that have penetrated the surface of the molded article, thereby exerting a synergistic effect.

The molded product obtained in the above manner has excellent adhesion to polypropylene brimers whose main components are chlorinated polypropylene, cyclized rubber, hydrochloric acid rubber, etc., and also has good adhesion to modified acrylic paints. has.

(V) Examples and Comparative Examples The present invention will now be explained in more detail with reference to Examples.

In addition, in the Examples and Comparative Examples, the paint film peeling strength test was performed by cutting out a test piece on a strip with a width of 10 mm from the test piece.
After forcibly peeling off a portion of the coating film from one end of the specimen, it was tested using a tensile tester used in plastic tensile tests at a tensile speed of 50 mm/min, a peeling angle of 180 degrees, and a temperature of 20 degrees. The coating film was peeled off under the conditions of C, and the strength at that time was the coating peeling strength (g/10mz). In addition, Izot impact strength was measured with a notch according to ASTM D-258. Furthermore, the flexural modulus is A
Measured according to STM D-747.

In addition, the propylene polymer, styrene polymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, ethylene-methacrylic ester copolymer, which are the compounding components used in the examples and comparative examples,
The physical properties of slag wool and ethylene polymer are shown below.

[(A) Propylene polymer]

As a propylene polymer, the density is 0.900g/Cm
' is a propylene-ethylene block copolymer (M
F I 10.0g710min, ethylene content 18
weight, hereinafter referred to as rPP(A)J] and propylene homopolymer (MFI 10.0 g/10 min, hereinafter referred to as [PP
(B)J] was used.

[(B) Styrenic polymer]

The styrene polymers include a styrene homopolymer with an average molecular weight of approximately 300,000 [hereinafter referred to as rPs (I) J] and a styrene polymer with an average molecular weight of approximately 15,000 [hereinafter referred to as rPs (II) J]. I used

[(C) Ethylene-vinyl acetate copolymer] As the ethylene-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer (M, 1.30 g) with a vinyl acetate content of 33% by weight.
/10 minutes, hereinafter referred to as rEVA(1)J] and an ethylene-vinyl acetate copolymer with a vinyl acetate content of 55% by weight, 1. 15g/10 minutes, hereinafter referred to as rEVA (2)
J] was used.

[(D) Ethylene-acrylic acid ester copolymer] As the ethylene-acrylic acid ester copolymer, an ethylene-ethyl acrylate copolymer CM having an ethyl acrylate content of 18% by weight, 1. a/10 minutes, hereinafter referred to as rEEA
(I)J] and the content of ethyl acrylate is 5
0% by weight of ethylene-ethyl acrylate copolymer CM,
1. 2.5 g/10 minutes, hereinafter referred to as rEEA(II)J] was used.

[(E) Ethylene-methacrylic acid ester copolymer]

As an ethylene-methacrylate ester copolymer, ethylene-methacrylate containing 10% by weight is used.
Methyl methacrylate copolymer [to, ■.

3.0 g/10 min, hereinafter referred to as "EMMA" and the content of methyl methacrylate was 50 rTE-m.
1% ethylene-methyl methacrylate copolymer [River 1.
'3.0g/10 minutes, hereinafter rEMMA (ii)
J) was used.

[(F) Slug wool]

Slug wool with an average length of 150 microns [hereinafter referred to as r'5W(a)J, average thickness 5.0 microns] and slag wool with an average length of 30 microns [hereinafter referred to as r'5W(a)J] r<Wrh”
l + 1-, - TameII +i÷-k Fill;
/;lff1] was used.

[(C) Other inorganic fillers]

For comparison, other inorganic fillers include chopped glass fiber with an average particle size of 13 microns (average length 3 mm, hereinafter referred to as rGFJ), and talc with an average particle size of 3 microns (aspect ratio 7). and mica having an average particle size of 7 microns (aspect ratio approximately 30).

[(H) Ethylene polymer]

As an ethylene polymer, the density is 0.950g/cm''
Ethylene polymer CM of 1. 1. Of/10 minutes, hereinafter referred to as rPE(a)J], with a density of 0.920 g/cm
'no low density polyethylene (M, 1.3.0g/10
minute, hereinafter referred to as "rPE(b)"] and density is 0.92
0 g/cm' linear low density ethylene-butene-1 copolymer [butene content 7.0% by weight,
1. 2.0 g/10 minutes, hereinafter referred to as rPE(c)J] was used.

Examples 1 to 11, Comparative Examples 1 to 14 100 parts by weight of propylene polymers whose types are shown in Table 1 and styrenic polymers whose types are shown in Table 1,
Ethylene polymers, slag wool or ethylene polymers selected from the group consisting of ethylene-vinyl acetate copolymers, ethylene-acrylic ester copolymers and ethylene-methacrylic ester copolymers, and ethylene polymers (The blending amounts of each are shown in Table 1) were tri-blended for 10 minutes using a ribbon blender. Each of the obtained mixtures was melted and mixed using a vented extruder (diameter 50 mm) at a resin temperature of 230°C to produce pellets (compositions). Each of the obtained pellets was injection molded using a 5-ounce injection molding machine at a resin temperature of 230°C, and a flat specimen (150X 150, Primer for Lens (manufactured by Yodo Toyo Co., Ltd., trade name: High Plus 150HB) was formed. was sprayed using a spray gun to a thickness of 5 to 10 microns for a paint film peeling test.Next, two-component urethane paint (manufactured by Nippon B Chemical Co., Ltd., trade name R-2) was sprayed to a thickness of 5 to 10 microns.
64) with a thickness of 35 to 40 for the paint film peeling test.
I used a spray gun to spray it down to micron size. Subsequently, heat drying was performed at a temperature of 90°C for 30 minutes. Then, each sample was subjected to a coating peel strength test after being left at room temperature for two days and nights. The results are shown in Table 2. In addition, the MFI of each pellet, the flexural modulus and Izont impact strength of each specimen (
(notched) are shown in Table 2.

In Table 1, component (I) represents a propylene polymer, and component (II) represents a styrene polymer. Furthermore, component (III) represents an ethylene copolymer, and component (IV) represents slag wool or other inorganic filler.

Further, composition component (V) represents an ethylene polymer.

(Left below) From the results of the following Examples and Comparative Examples, it is clear that the composition obtained by the present invention has good adhesion and excellent processability and fluidity (kneadability). However, since it has high rigidity, it is clear that it can be used in a wide variety of ways as described later.

(Vl) Effects and Applications of the Invention The composition obtained by the present invention not only has the above-mentioned properties, but also exhibits the following effects (characteristics).

(1) It has excellent moldability and can be kneaded continuously using a continuous R kneading machine such as an extruder.
Manufacturing costs can also be reduced.

(2) Good compatibility between olefin polymers, styrene polymers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, or ethylene-methacrylic acid ester copolymers; No delamination occurs.

(3) Mechanical strength (eg, rigidity, impact resistance) is good.

Since the olefin polymer composition obtained by the present invention exhibits the excellent effects (characteristics) mentioned above, it can be applied in a wide variety of ways by being painted or printed. Typical uses are shown below.

(1) Auto parts such as rear quarter grills and front grills (2) Motorcycle parts such as fenders, leg shields and side covers (3) Parts of home appliances such as audio equipment, televisions, electric fans and radio cassettes (4) Ships Outer unit cover (5) Containers (6) Furniture (7) Daily necessities (8) Building materials, etc.

Claims (1)

[Claims] (A) Melt flow index is 0.01 to 100g
/10 minutes, 100 parts by weight of a crystalline propylene polymer, (B) 0.5 to 20.0 parts by weight of a styrenic polymer whose main component is styrene with a molecular weight of 22,000 to 400,000, (
C) Ethylene-vinyl acetate copolymer with a vinyl acetate content of 5.0 to 50% by weight and/or an acrylic ester or methacrylic ester content of 5.0
3.0 to 28.0 parts by weight of an ethylene-acrylic acid ester copolymer or an ethylene-methacrylic acid ester copolymer which is ~40% by weight, and (b) the thickness of the fiber is 3.0 to 10 microns, An olefinic polymer composition comprising 5.0 to 40 parts by weight of artificial amorphous slag wool having a length of 50 to 500 microns.