JP5450299B2 - Block copolymer-containing resin composition and sheet or film obtained from the resin composition - Google Patents

Description

  The present invention relates to a block copolymer-containing resin composition and a sheet or film obtained from the resin composition.

  A block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene, which has a relatively high vinyl aromatic hydrocarbon content, is used for injection molding applications, sheets or films by utilizing properties such as transparency and impact resistance. It is used for extrusion molding applications.

  In particular, a sheet using a block copolymer resin composed of a vinyl aromatic hydrocarbon and a conjugated diene is excellent in transparency, impact resistance, and the like, and thus is used for a blister sheet, a beverage container, and the like.

  Properties required for the sheet include transparency, mechanical strength, surface appearance, stackability (sliding property), and absence of burrs when punching holes in the sheet (punching property).

  For example, in Patent Document 1, in order to obtain a composition having excellent mechanical properties, optical properties, stretching properties, crack resistance properties, and the like, the content of the aliphatic unsaturated carboxylic acid derivative is 5 to 80% by weight, and the Vicat softening point. A vinyl aromatic hydrocarbon-aliphatic unsaturated carboxylic acid derivative copolymer component (A) having a temperature not exceeding 90 ° C. and a copolymer component (B) comprising a block of vinyl aromatic hydrocarbon and conjugated diene And disclosed as a constituent of the composition.

  In Patent Document 2, in order to obtain a composition that balances transparency, rigidity, and low-temperature impact, a copolymer composed of a block of vinyl aromatic hydrocarbon and conjugated diene having a specific structure and molecular weight distribution, and vinyl An aromatic hydrocarbon- (meth) acrylic acid ester copolymer resin is disclosed as a constituent of the composition.

  Patent Document 3 discloses a block copolymer having a vinyl aromatic hydrocarbon block having a specific structure and a copolymer block of vinyl aromatic hydrocarbon and conjugated diene in order to obtain a resin composition having excellent transparency and impact resistance. It is disclosed that a combination, a copolymer of a vinyl aromatic hydrocarbon and a (meth) acrylic ester are used as components of the composition.

  In Patent Document 4, in order to obtain a resin composition having improved transparency, color tone, blocking resistance and impact resistance, and friction coefficient, a vinyl aromatic hydrocarbon and conjugated diene block copolymer, and a melting point of 70 are used. It is disclosed that microcrystalline wax at ˜120 ° C. is used as a constituent of the composition.

JP 59-221348 A JP-A-6-220278 Japanese Patent Laid-Open No. 7-216187 JP-A-1-304146

  However, a molded article (for example, a sheet) obtained from a block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene described in Patent Documents 1 to 4 or a composition containing the block copolymer has rigidity and impact resistance. The balance of property, transparency, surface appearance, blocking resistance, etc. is not sufficient.

  For example, in plastic cup applications, slipperiness is required when printing with a printing machine, but molded articles (for example, sheets) obtained from the compositions described in Patent Documents 1 to 4 have slipperiness. This is not sufficient and causes problems when printing with a printing press. Note that the slipping property does not necessarily coincide with the friction coefficient, and a correlation is seen with the slip angle measured under a specific condition.

  In addition, in a molded product (for example, a sheet) obtained from the compositions described in Patent Documents 1 to 4, the temperature condition in which the surface appearance deteriorates and the temperature condition in which the surface appearance does not deteriorate tend to be the same under long-term storage conditions. There is a problem that is not.

  It is difficult to solve such a change in slip angle and surface appearance and punchability, and molded products (for example, sheets) obtained from conventional compositions still have problems in the market.

  The present invention has an excellent balance of physical properties such as rigidity, impact resistance and transparency, and can maintain a stable surface appearance regardless of the surface appearance, particularly storage conditions, and also has excellent stackability and punchability. It aims at providing the composition which can obtain a sheet | seat film.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by using a resin composition containing a specific microcrystalline wax, a specific block copolymer and liquid paraffin. It came to.

  That is, the present invention is as follows.

[1]
Component (I); a block copolymer comprising 60 to 95% by weight of a vinyl aromatic hydrocarbon and 5 to 40% by weight of a conjugated diene or a hydrogenated product thereof;
Component (II); microcrystalline wax;
Component (III); liquid paraffin,
The component (II) comprises normal paraffin and isoparaffin;
The content of isoparaffin having 44 or less carbon atoms in the component (II) is 12.5% by weight or more with respect to a total of 100% by weight of normal paraffin and isoparaffin,
The normal paraffin content of 44 or less carbon atoms in the component (II) is 30 wt% or less with respect to 100 wt% of the total of normal paraffin and isoparaffin,
The content of the component (II) is 0.1 to 1 part by weight and the content of the component (III) is 0.1 to 0.5 part by weight with respect to 100 parts by weight of the component (I). , Resin composition.

[2]
In addition, component (B); containing a vinyl aromatic hydrocarbon polymer,
The component (B) is at least one vinyl aromatic hydrocarbon polymer selected from the group consisting of the following (a) to (c):
The resin composition according to [1], wherein a weight ratio of the component (I) to the component (B) (component (I) / component (B)) is 99/1 to 5/95;
(A) a styrenic polymer,
(B) at least one aliphatic unsaturated carboxylic acid selected from the group consisting of vinyl aromatic hydrocarbons, aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid anhydrides and aliphatic unsaturated carboxylic acid esters Or a copolymer with a derivative thereof,
(C) A block copolymer elastomer of a vinyl aromatic hydrocarbon and a conjugated diene having a vinyl aromatic hydrocarbon content of less than 60% by weight or a hydrogenated product thereof.

[3]
A sheet or film obtained from the resin composition according to [1] or [2].

  The sheet obtained from the resin composition of the present invention is excellent in surface appearance, stacking property, transparency and punching property while maintaining a balance of physical properties such as rigidity and impact resistance, and has a particularly wide surface appearance over time under environmental conditions. Excellent stability in

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following description, and various modifications can be made within the scope of the gist thereof.

[Resin composition]
The resin composition according to this embodiment includes component (I); a specific block copolymer or a hydrogenated product thereof, component (II); a specific microcrystalline wax, and component (III); liquid paraffin. .

<Component (I): Block copolymer or hydrogenated product thereof>
The block copolymer or hydrogenated product thereof used in the present embodiment (hereinafter collectively referred to as “block copolymer etc.” or “component (I)”) is a vinyl aromatic hydrocarbon 60-95. % By weight and 5 to 40% by weight conjugated diene, preferably 65 to 90% by weight vinyl aromatic hydrocarbon and 10 to 35% by weight conjugated diene, more preferably 70 to 90% by weight vinyl aromatic hydrocarbon and Containing 10 to 30% by weight of conjugated diene.

  In addition, the component (I) used in the present embodiment has a weight ratio of vinyl aromatic hydrocarbon to conjugated diene of 60/40 to 95/5, preferably 65 from the viewpoint of balance between rigidity and impact resistance. / 35 to 90/10, more preferably 70/30 to 90/10.

  When the weight ratio of the vinyl aromatic hydrocarbon to the conjugated diene is in the range of 65/35 to 95/5, a sheet having improved rigidity and impact resistance can be obtained.

  In addition, you may grasp | ascertain the vinyl aromatic hydrocarbon content of the hydrogenated product of a block copolymer by the vinyl aromatic compound content of the block copolymer before hydrogenation.

  The block ratio of the vinyl aromatic hydrocarbon incorporated in the block copolymer or the like used in the present embodiment is preferably 10 to 95% by weight, more preferably 30 to 90% by weight, still more preferably 40 to 85% by weight. Particularly preferred is 45 to 80% by weight. When the block ratio is in the range of 10 to 95% by weight, a sheet having excellent rigidity and impact resistance can be obtained.

  The block ratio in the case of obtaining a block copolymer having good rigidity is preferably more than 50% by weight and 90% by weight or less, more preferably 60 to 85% by weight, still more preferably 65 to 80% by weight. It is recommended.

  The block ratio of the vinyl aromatic hydrocarbon incorporated in the block copolymer used in the present embodiment is determined by oxidative decomposition of the block copolymer before hydrogenation with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst. The vinyl aromatic hydrocarbon polymer block component obtained by the method (however, the average value) can be measured by the following method (method described in IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)). This is a value obtained from the following equation using the weight of a vinyl aromatic hydrocarbon polymer component having a degree of polymerization of about 30 or less.

Block ratio (% by weight) = (weight of vinyl aromatic hydrocarbon polymer block in block copolymer / weight of total vinyl aromatic hydrocarbon in block copolymer) × 100
The block copolymer used in the present embodiment has a number average molecular weight (polystyrene equivalent molecular weight) measured by gel permeation chromatography (GPC), preferably 30,000 to 500,000, more preferably 50,000 to 400,000, and more Preferably, it may be a mixture of a plurality of block copolymers having a number average molecular weight of 60,000 to 300,000, particularly preferably 70,000 to 200,000.

  When the number average molecular weight of the block copolymer or the like used in the present embodiment is in the range of 30,000 to 500,000, a sheet having an excellent balance between mechanical strength such as rigidity and workability can be obtained.

  The melt flow index (measured by ISO1133. Conditions are G condition, temperature 200 ° C., load 5 kg) is preferably 0.1 to 100 g / 10 min from the viewpoint of molding processability. More preferably 0.5 to 50 g / 10 min, and still more preferably 1 to 30 g / 10 min.

  The number average molecular weight and the melt flow index can be arbitrarily adjusted according to the amount of catalyst used for polymerization.

  The block copolymer used in the present embodiment has a molecular weight of 5,000 to 50,000, preferably 10,000 to 50,000, and more preferably 15,000 to 50,000 in order to obtain a sheet having a particularly excellent balance between rigidity and impact resistance. Preferably, at least one vinyl aromatic hydrocarbon polymer block having a peak molecular weight in the range is incorporated.

  In the present embodiment, the number average molecular weight and weight average molecular weight of the block copolymer and the like are measured by gel permeation chromatography (GPC), and a calibration curve obtained from measurement of a commercially available monodisperse polystyrene for GPC. The number average molecular weight and the weight average molecular weight calculated according to a conventional method (for example, “Gel Chromatography <Basics>” published by Kodansha).

  The molecular weight of the vinyl aromatic hydrocarbon polymer block incorporated in the block copolymer or the like is the same vinyl aromatic hydrocarbon polymer as that used for quantification of the block ratio obtained by the oxidative decomposition method described above. In the gel permeation chromatogram of the block component, it is the peak molecular weight determined from the peak count number of the vinyl aromatic hydrocarbon polymer block component and the calibration curve.

  The molecular weight of the vinyl aromatic hydrocarbon polymer block incorporated in the block copolymer or the like is the weight of the vinyl aromatic hydrocarbon, the weight and weight ratio when the vinyl aromatic hydrocarbon and the conjugated diene are copolymerized, It can be controlled by changing the polymerization reactivity ratio, the amount of catalyst, and the like.

  The block copolymer used in the present embodiment is a short chain in which the number of vinyl aromatic hydrocarbon units is in the range of 1 to 3 with respect to the total amount of vinyl aromatic hydrocarbon constituting the block copolymer. It is recommended that the proportion of the vinyl aromatic hydrocarbon polymerized moiety is preferably 1-30% by weight, more preferably 3-25% by weight, and even more preferably 5-20% by weight.

The proportion of short-chain vinyl aromatic hydrocarbon polymerized moieties where the number of vinyl aromatic hydrocarbon units is in the range of 1 to 3 is determined by dissolving the copolymer before hydrogenation in dichloromethane and oxidatively decomposing it with ozone (O ₃ ). After that, the obtained ozonide was reduced with lithium aluminum hydride in diethyl ether and hydrolyzed with pure water, and the gel permeation chromatography (GPC) measurement of the vinyl aromatic hydrocarbon component obtained was performed. This can be quantified by calculating the area ratio of the obtained peaks (see Takayuki Tanaka, Toshiya Sato, Yasunobu Nakafumi, “Proceedings of the Society of Polymer Science,” 29, 2051, 1980).

  The block copolymer or the like used in the present embodiment includes a vinyl aromatic hydrocarbon homopolymer and / or at least one segment composed of a copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene, and a conjugated diene homopolymer. It has at least one segment composed of a polymer and / or a copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene.

  The polymer structure of the block copolymer and the like is not particularly limited, but as a polymer structure before hydrogenation, for example, a linear block copolymer or a radial block copolymer represented by the following formula, or a polymer structure of these polymer structures: Any mixture can be used.

(AB) _n , A- (BA) _n , B- (AB) _{n + 1}
[(AB) _k ] _{m + 1} -X, [(AB) _k -A] _{m + 1} -X
[(BA) _k ] _{m + 1} -X, [(BA) _k -B] _{m + 1} -X
In the above formula, segment A is a vinyl aromatic hydrocarbon homopolymer and / or a copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene, and segment B is a conjugated diene homopolymer and / or a vinyl aromatic hydrocarbon. A copolymer comprising a conjugated diene.

  X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, 1,3 bis (N, N-glycidylaminomethyl) cyclohexane, epoxidized soybean oil, or an initiator such as a polyfunctional organolithium compound. Indicates residue.

  n, k and m are integers of 1 or more, generally 1 to 5 integers.

  Moreover, the structure of the polymer chain bonded to X may be the same or different.

  In the radial block copolymer represented by the above general formula, A and / or B may be further bonded to X.

  In the present embodiment, the vinyl aromatic hydrocarbons in the copolymer of the vinyl aromatic hydrocarbon and the conjugated diene in the segment A and the segment B are uniformly distributed, but are distributed in a tapered shape (gradual decrease). Also good.

  Further, in the copolymer, a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or portions where tapes are distributed may coexist in the segment.

  Vinyl aromatic hydrocarbon content in segment A ({vinyl aromatic hydrocarbon in segment A / (vinyl aromatic hydrocarbon in segment A + conjugated diene)} × 100) and vinyl aromatic carbon in segment B The relationship between the hydrogen content ({vinyl aromatic hydrocarbon in segment B / (vinyl aromatic hydrocarbon in segment B + conjugated diene)} × 100) is equal to the vinyl aromatic hydrocarbon content in segment A. Is greater than the vinyl aromatic hydrocarbon content in segment B.

  The difference in vinyl aromatic hydrocarbon content between segment A and segment B is preferably 5% by weight or more, more preferably 10% by weight or more.

  In this embodiment, the block copolymer before hydrogenation can be obtained by polymerizing vinyl aromatic hydrocarbon and conjugated diene in a hydrocarbon solvent using an organolithium compound as an initiator.

  Examples of the vinyl aromatic hydrocarbon used in the present embodiment include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, and vinyl. Anthracene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, and the like can be mentioned, and styrene is particularly common.

  These may be used alone or in combination of two or more.

  The conjugated diene used in this embodiment is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), and 2,3-dimethyl-1. 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like, with 1,3-butadiene, isoprene and the like being particularly common.

  These may be used alone or in combination of two or more.

  In this embodiment, the block copolymer before hydrogenation is obtained, for example, by anion living polymerization using an initiator such as an organic alkali metal compound in a hydrocarbon solvent.

  Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and cycloheptane. In addition, alicyclic hydrocarbons such as methylcycloheptane, and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene can be used.

  These may be used alone or in combination of two or more.

  As the polymerization initiator, aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, organic amino alkali metal, which are generally known to have anionic polymerization activity for conjugated dienes and vinyl aromatic compounds. A compound or the like can be used.

  Examples of the alkali metal include lithium, sodium, potassium, and the like. Suitable organic alkali metal compounds include aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, one per one molecule. Examples thereof include compounds containing lithium, dilithium compounds containing a plurality of lithium atoms in one molecule, trilithium compounds, and tetralithium compounds.

  Specifically, n-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexamethylene dilithium, butadienyl dilithium, isoprenyl dilithium, diisopropenylbenzene and sec-butyl lithium Examples of the reaction product include a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene.

  Furthermore, organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent 2,241,239, US Pat. No. 5,527,753, etc. are also used. be able to.

  These may be used alone or in combination of two or more.

  In this embodiment, the polymerization temperature for producing the block copolymer is generally -10 ° C to 150 ° C, preferably 40 ° C to 120 ° C.

  The time required for the polymerization varies depending on the conditions, but is usually within 10 hours, particularly preferably 0.5 to 5 hours.

  The polymerization atmosphere is preferably replaced with an inert gas such as nitrogen gas.

  The polymerization pressure is not particularly limited as long as the polymerization pressure is in a range sufficient to maintain the monomer and solvent in the liquid layer within the above polymerization temperature range.

  Furthermore, care must be taken not to mix impurities, such as water, oxygen, carbon dioxide, etc., that inactivate the catalyst and living polymer into the polymerization system.

  The hydrogenated block copolymer used in the present embodiment is obtained by hydrogenating the block copolymer before hydrogenation obtained above.

  The hydrogenation catalyst is not particularly limited and is conventionally known (1) A supported heterogeneous hydrogenation in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. A catalyst, (2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, (3) Ti, Ru, A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Rh or Zr is used.

  Specific examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-39770, Japanese Patent Publication No. 1-53851, The hydrogenation catalyst described in Japanese Patent Publication No. 2-9041 can be used.

  Preferred hydrogenation catalysts include mixtures with titanocene compounds and / or reducing organometallic compounds.

  As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specific examples thereof include (substitution) such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Examples thereof include compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton.

  Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

  The hydrogenation reaction is preferably carried out in a temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C.

  The pressure of hydrogen used for the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and still more preferably 0.3 to 7 MPa.

  The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours.

  The hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof.

  In the hydrogenated block copolymer used in the present embodiment, the hydrogenation rate of the unsaturated double bond based on the conjugated diene can be arbitrarily selected according to the purpose and is not particularly limited.

  When obtaining a hydrogenated block copolymer having good thermal stability and weather resistance, the proportion of hydrogenated unsaturated double bonds based on the conjugated diene compound in the polymer is preferably more than 70%, It is recommended that it is 75% or more, more preferably 85% or more, particularly preferably 90% or more.

  Moreover, when obtaining a hydrogenated block copolymer with good thermal stability, the hydrogenation rate is preferably 3 to 70%, more preferably 5 to 65%, and particularly preferably 10 to 60%.

  The hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the copolymer is not particularly limited, but is preferably 50% or less, more preferably 30% or less, and still more preferably 20% or less. It is.

  In the present embodiment, the hydrogenation rate can be measured with a nuclear magnetic resonance apparatus (NMR).

  In this embodiment, the microstructure (ratio of cis, trans, vinyl) of the conjugated diene moiety in the block copolymer or the like can be arbitrarily changed by using the above-mentioned polar compound or the like, and is not particularly limited.

  In general, the vinyl bond content of the conjugated diene moiety in the block copolymer or the like is preferably 5 to 90%, more preferably 6 to 80%, and even more preferably 7 to 75%.

  In this embodiment, the vinyl bond amount is the total amount of 1,2-vinyl bond and 3,4-vinyl bond (however, when 1,3-butadiene is used as the conjugated diene, -Vinyl bond amount).

  In the present embodiment, the vinyl bond amount can be measured by a nuclear magnetic resonance apparatus (NMR).

  In the present embodiment, among the above-mentioned copolymers, those having a block styrene content of 70% or less are likely to exhibit excellent performance in all of the surface appearance, slipperiness, punchability, and mechanical strength. Particularly preferred.

<Ingredient (II); Microcrystalline wax>
The microcrystalline wax (hereinafter also referred to as “component (II)”) used in the present embodiment means a mixture mainly composed of normal paraffin and isoparaffin.

  Normal paraffin and isoparaffin may be either naturally produced or synthesized.

  Examples of the microcrystalline wax used in the present embodiment include ASTROWAX manufactured by Honeywell and HiMic manufactured by Nippon Seiwa Co., Ltd.

  The microcrystalline wax used in the present embodiment includes normal paraffin and isoparaffin.

  The content of isoparaffin having 44 or less carbon atoms in the microcrystalline wax used in the present embodiment is 12.5% by weight or more, preferably 12.5% by weight with respect to 100% by weight of the total of normal paraffin and isoparaffin. The content is 30.0% by weight or less. When the content of the isoparaffin having 44 or less carbon atoms is within the above range, the surface appearance of the obtained sheet is stable over time under long-term storage conditions, particularly at high temperatures, and burrs are generated during punching with a punch or the like. It becomes difficult to do. Furthermore, when the content of the isoparaffin having 44 or less carbon atoms is 12.5 wt% or more and 20 wt% or less, the resulting sheet is excellent in slipperiness and preferable.

  The content of normal paraffin having 44 or less carbon atoms in the microcrystalline wax used in the present embodiment is 30% by weight or less, preferably 10% by weight or more and 30% by weight with respect to 100% by weight of the total of normal paraffin and isoparaffin. % Or less. When the content of normal paraffin having 44 or less carbon atoms is within the above range, the temporal change of the surface appearance of the obtained sheet under long-term storage conditions, particularly under low temperature, is stable. Furthermore, when the content of normal paraffin having 44 or less carbon atoms is 20% by weight or more and 30% by weight or less, it is preferable that the resulting sheet is excellent in slipperiness.

  The weight ratio of normal paraffin and isoparaffin in the microcrystalline wax used in the present embodiment is obtained by performing an extraction operation of normal paraffin and isoparaffin with an appropriate solvent, and the normal paraffin and isoparaffin in the column chromatography (GLC) chart. It can be determined from the area ratio.

  In the present embodiment, the normal paraffin content having 44 or less carbon atoms and the isoparaffin content having 44 or less carbon atoms in the microcrystalline wax can be measured by separating normal paraffin and isoparaffin by the urea addition method. .

  Specifically, first, microcrystalline wax / urea is mixed at 1/25, and mixed in cyclohexane with stirring at 25 ° C. for 2 hours. By this mixing, normal paraffin is adsorbed on urea and isoparaffin remains in cyclohexane without being adsorbed. Thereafter, cyclohexane is distilled off to separate isoparaffin.

  Next, using column chromatography equipped with a capillary column, the molecular weight distribution of normal paraffin in microcrystalline wax and fractionated isoparaffin is measured, so that the normal paraffin content of 44 or less carbon atoms in microcrystalline wax and The content of isoparaffin having 44 or less carbon atoms can be measured.

  In the embodiment of the present invention, the ratio of normal paraffin to isoparaffin in the microcrystalline wax is within a range satisfying the relationship between the normal paraffin content having 44 or less carbon atoms and the isoparaffin content having 44 or less carbon atoms in the microcrystalline wax. If it is in, there will be no limitation in particular.

  In the present embodiment, it is preferable that the melting point of the microcrystalline wax is in the range of 70 to 90 ° C., since there is a tendency that a sheet excellent in the balance between blocking resistance and transparency can be produced. In the present embodiment, the melting point of the microcrystalline wax is a value measured by the method described in Examples described later based on JIS K2235-5.3.2.

  In this embodiment, it is preferable in terms of prevention of sheet blocking that the penetration of the microcrystalline wax is in the range of 10 to 40. In the present embodiment, the penetration of microcrystalline wax is a value measured by the method described in Examples described later based on JIS K2235-5.4 (25 ° C.).

  In this embodiment, content of component (II) with respect to 100 parts by weight of component (I) is 0.1 to 1 part by weight, preferably 0.2 to 0.6 part by weight.

  In addition, when the content of the normal paraffin of the component (II) is in the range of 0.01 to 1 part by weight with respect to 100 parts by weight of the component (I), the resulting sheet has excellent balance between the slipperiness and the surface appearance. .

<Component (III); Liquid paraffin>
In this embodiment, liquid paraffin (hereinafter also referred to as “component (III)”) is also called mineral oil, white oil, etc., and is obtained by distilling petroleum crude oil to remove solid paraffin and refining to high purity. A mixture of liquid saturated hydrocarbons, the main component of which is a mixture of alkyl naphthene hydrocarbons.

  Although there is no restriction | limiting in particular as the property of a preferable liquid paraffin, The thing of SUS viscosity (37.8 degreeC) 40-380 is preferable.

  Content of component (III); liquid paraffin with respect to 100 weight part of component (I) is 0.1-0.5 weight part, More preferably, it is 0.2-0.4 weight part.

  When the content of component (III); liquid paraffin is in the range of 0.1 to 0.5 parts by weight with respect to 100 parts by weight of component (I), component (II); microcrystalline wax has a higher concentration in the composition. Even if it is contained, the change over time of the surface state of the obtained sheet can be suppressed, and the slip angle and punchability tend to be further improved.

<Component (B): Vinyl aromatic hydrocarbon polymer>
The resin composition according to this embodiment may further contain a vinyl aromatic hydrocarbon polymer (hereinafter also referred to as “component (B)”).

  The weight ratio of the component (I) to the component (B) (component (I) / component (B)) is preferably 99/1 to 5/95, more preferably 97/3 to 10/90, especially Preferably it is 95/5-20/80.

By containing the component (B) in the above range, a molded product (for example, a sheet) excellent in rigidity, impact resistance, transparency, blocking resistance and surface appearance can be obtained. Component (B) used in this embodiment ) May be at least one vinyl aromatic hydrocarbon polymer selected from the group consisting of the following (a) to (c).

  (A) Styrenic polymer.

  (B) at least one aliphatic unsaturated carboxylic acid selected from the group consisting of vinyl aromatic hydrocarbons, aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid anhydrides and aliphatic unsaturated carboxylic acid esters Or a copolymer thereof.

  (C) A block copolymer elastomer of a vinyl aromatic hydrocarbon and a conjugated diene or a hydrogenated product thereof having a vinyl aromatic hydrocarbon content of less than 60%.

  The (a) styrenic polymer used in this embodiment is obtained by polymerizing the above-mentioned vinyl aromatic hydrocarbon or a monomer copolymerizable therewith (except for (b)).

  Examples of the monomer copolymerizable with the vinyl aromatic hydrocarbon include acrylonitrile and methacrylonitrile.

  (A) Examples of the styrenic polymer include polystyrene, styrene-α-methylstyrene copolymer, acrylonitrile-styrene copolymer, methacrylonitrile-styrene copolymer, and the like.

  In addition, among (a) styrene-based polymers, polystyrene obtained by polymerizing styrene includes polystyrene having a syndiotactic structure and polystyrene having an isotactic structure.

  These (a) styrene polymers preferably have a weight average molecular weight of 50,000 to 500,000.

  These (a) styrenic polymers can be used alone or as a mixture of two or more, and can be used as a rigidity improving agent.

  Component (b) vinyl aromatic hydrocarbon used in the present embodiment and at least one fat selected from aliphatic unsaturated carboxylic acid, aliphatic unsaturated carboxylic acid anhydride, and aliphatic unsaturated carboxylic acid ester A copolymer with a group unsaturated carboxylic acid or a derivative thereof will be described.

  Examples of the aliphatic unsaturated carboxylic acid used for the synthesis of the component (b) include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, and the like, and aliphatic unsaturated carboxylic acid anhydrides. Examples thereof include fumaric anhydride, itaconic anhydride, maleic anhydride and the like, and examples of the aliphatic unsaturated carboxylic acid ester include, for example, the above aliphatic unsaturated carboxylic acid, C1 to C12, Preferred are mono- or diesters with C2 to C12 alcohols.

  Examples of the vinyl aromatic hydrocarbon include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, 1,1. -Diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and the like can be mentioned, and styrene is particularly common.

  These may be used alone or in combination of two or more.

  The content of the aliphatic unsaturated carboxylic acid and / or aliphatic unsaturated carboxylic acid derivative in the component (b) is preferably 5 to 50% by weight, more preferably 8 to 30% by weight, still more preferably 10 to 25% by weight. %.

  Examples of the aliphatic unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, and hexyl acrylate.

  When a vinyl aromatic hydrocarbon polymer having a relatively low Vicat softening point is used as component (b), the Vicat softening point is preferably 50 to 95 ° C, more preferably 60 to 90 ° C, still more preferably 65 to 85. Aliphatic unsaturated carboxylic acid ester-styrene copolymers at ℃ are recommended.

  The Vicat softening temperature is a value measured according to ASTM D-1525 (load: 1 kg, temperature increase rate: 2 ° C./min) using a test piece compression-molded to a thickness of 3 mm.

  A preferred aliphatic unsaturated carboxylic acid ester-styrene copolymer is a copolymer mainly composed of n-butyl acrylate and styrene, and the total amount of n-butyl acrylate and styrene is 50% by weight or more, More preferred is an aliphatic unsaturated carboxylic acid ester-styrene copolymer in which the total amount of n-butyl acrylate and styrene is 60% by weight or more.

  A sheet using an aliphatic unsaturated carboxylic acid ester-styrene copolymer mainly composed of n-butyl acrylate and styrene has good transparency and rigidity.

  In addition, the manufacturing method of a component (b) can use the well-known method of manufacturing a styrene resin, for example, a block polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method etc.

  The weight average molecular weight of component (b) is preferably 50,000 to 500,000.

  The component (c) vinyl aromatic hydrocarbon and conjugated diene block copolymer elastomer or hydrogenated product thereof used in the present embodiment has a vinyl aromatic hydrocarbon content of less than 60% by weight, preferably 10 to 10%. The component having the same structure as the component (I); block copolymer used in the present embodiment can be used at 50% by weight, and impact resistance, elongation, etc. can be improved.

  In the hydrogenated block copolymer elastomer, the hydrogenation rate of the unsaturated double bond based on the conjugated diene can be arbitrarily selected according to the purpose and is not particularly limited.

  Preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more of the unsaturated double bonds based on the conjugated diene in the block copolymer elastomer may be hydrogenated, or only partly. May be hydrogenated.

  When only a part is hydrogenated, the hydrogenation rate is preferably 10% or more and less than 70%, more preferably 15% or more and less than 65%, and more preferably 20% or more and less than 60%. Particularly preferred.

  In particular, the component (B) vinyl aromatic hydrocarbon polymer used in this embodiment preferably has a melt flow index (MI) (temperature of 200 ° C. under G condition, load of 5 kg) from the viewpoint of molding. 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min, and still more preferably 1 to 30 g / 10 min.

<Additive>
Various additives can be added to the resin composition of the present embodiment depending on the purpose.

(Lubricant)
A lubricant may be added to the resin composition of the present embodiment.

  As the lubricant, for example, at least one selected from the group consisting of fatty acid amides, paraffins and hydrocarbon resins, and fatty acids can be used.

  The amount of the lubricant added is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight, and still more preferably 0.1 to 100 parts by weight of the component (I) block copolymer and the like. ~ 3 parts by weight. By adding a lubricant within the above range, the blocking resistance can be further improved.

  Examples of fatty acid amides include stearoamide, oleyl amide, erucyl amide, behen amide, mono- or bisamide of higher fatty acids, ethylene bis stearoamide, stearyl oleylamide, N-stearyl erucamide, etc. May be used alone or in combination of two or more.

  Examples of the paraffin and hydrocarbon resin include paraffin wax, paraffin synthetic wax, polyethylene wax, composite wax, montan wax, hydrocarbon wax, silicone oil, and the like in addition to the above-mentioned microscriptarin wax. These can be used alone or in admixture of two or more.

  Examples of fatty acids include saturated fatty acids, unsaturated fatty acids, N-substituted fatty acids and the like.

  That is, saturated fatty acids such as lauric acid, palmitic acid, stearic acid, behenic acid, hydroxystearic acid, unsaturated fatty acids such as oleic acid, erucic acid, ricinoleic acid, N-stearyl stearic acid, N-oleyl oleic acid, N- Stearyl oleic acid, N-oleyl stearic acid, N-stearyl erucic acid, N-oleyl palmitic acid, substituted fatty acids such as methylol stearic acid, methylol behenic acid, methylene bis stearic acid, ethylene biscapric acid, ethylene bis lauric acid, ethylene Saturated fatty acids such as bis-stearic acid, ethylene bisisostearic acid, ethylene bishydroxystearic acid, ethylene bisbehenic acid, hexamethylene bishydroxystearic acid, N, N′-distearyl adipic acid, N, N′-distearyl sebacic acid , D Unsaturated fatty acids such as lenbis oleic acid, hexamethylene bis oleic acid, N, N′-dioleyl adipic acid, N, N′-dioleyl sebacic acid, m-xylylene bis stearic acid, N, N′-di Although stearyl isophthalic acid etc. are mentioned, these can be used individually or in mixture of 2 or more types.

(UV absorber and light stabilizer)
An ultraviolet absorber and a light stabilizer may be added to the resin composition of this embodiment.

  As the ultraviolet absorber and the light stabilizer, for example, at least one selected from the group consisting of a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber and a hindered amine light stabilizer can be used.

  The added amount of the ultraviolet absorber and the light stabilizer is preferably 0.05 to 3 parts by weight, more preferably 0.05 to 2.5 parts by weight with respect to 100 parts by weight of the component (I) block copolymer and the like. More preferably, it is 0.1 to 2 parts by weight. Light resistance is improved by adding an ultraviolet absorber and a light stabilizer in the above range.

(Stabilizer)
You may add a stabilizer to the resin composition of this embodiment.

  As a stabilizer, for example, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 2-t-butyl-6- Use at least one selected from the group consisting of (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and 2,4-bis [(octylthio) methyl] -o-cresol Can do.

  The added amount of the stabilizer is preferably 0.05 to 3 parts by weight, and more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the component (I) block copolymer and the like. By adding a stabilizer in the above range, a gel suppressing effect can be obtained.

  If the addition amount of the stabilizer is less than 0.05 parts by weight, there is a tendency that the effect of suppressing the gel does not exist, and even if the stabilizer is added in excess of 3 parts by weight, it may not contribute to the gel suppression effect required in this embodiment. is there.

  The resin composition of this embodiment includes n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,4-bis- (n -Octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and other phenolic stabilizers are added to the components (I) and (II) Preferably 0.05-3 weight part can be added with respect to a total of 100 weight part.

  Further, the resin composition of this embodiment includes tris- (nonylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2-[[2,4, 8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] -N, N-bis [2-[[2 , 4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] -ethyl] -ethanamine, tris (2 , 4-di-t-butylphenyl) phosphite, etc., at least one of organic phosphate-based and organic phosphite-based stabilizers is added in an amount of 0.05 to 3 parts by weight can be added.

(Other)
Various polymers and additives can be further added to the resin composition of the present embodiment according to the purpose.

  A suitable polymer is a rubber-modified styrene polymer.

  A rubber-modified styrenic polymer is obtained by polymerizing a mixture of a vinyl aromatic hydrocarbon, a monomer copolymerizable with the vinyl aromatic hydrocarbon, and an elastomer copolymerizable with the vinyl aromatic hydrocarbon. As polymerization methods, suspension polymerization, emulsion polymerization, bulk polymerization, bulk-suspension polymerization and the like are generally performed.

  Examples of the vinyl aromatic hydrocarbon include styrene, α-methylstyrene, vinyl naphthalene and the like, and monomers copolymerizable with the vinyl aromatic hydrocarbon include acrylonitrile, methacrylonitrile, acrylic acid ester, Examples include methacrylic acid esters and maleic anhydride.

  As the elastomer copolymerizable with the vinyl aromatic hydrocarbon, natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, high styrene rubber and the like are used.

  These elastomers are added to the vinyl aromatic hydrocarbon or the total amount of vinyl aromatic hydrocarbon and a monomer copolymerizable therewith, preferably 3 to 50 parts by weight with respect to 100 parts by weight. Or in the form of latex, which is used in emulsion polymerization, bulk polymerization, bulk-suspension polymerization, and the like.

  A particularly preferable rubber-modified styrene polymer is an impact-resistant rubber-modified styrene polymer (HIPS).

  The rubber-modified styrenic polymer can be used as an agent for improving rigidity, impact resistance and slipperiness.

  These rubber-modified styrene polymers preferably have a weight average molecular weight of 50,000 to 500,000.

  The addition amount of the rubber-modified styrenic polymer is 0.1 to 10 with respect to 100 parts by weight of component (I) or 100 parts by weight of component (I) and component (B) in consideration of maintaining transparency. Part by weight is preferred.

  Other suitable additives include softeners such as coumarone-indene resins, terpene resins, oils, and plasticizers.

  Various stabilizers, pigments, antiblocking agents, antistatic agents, lubricants and the like can also be added.

  Examples of the antiblocking agent, antistatic agent, and lubricant include fatty acid amide, ethylene bisstearamide, sorbitan monostearate, saturated fatty acid ester of fatty acid alcohol, pentaerythritol fatty acid ester, etc. -t-Butylphenyl salicylate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzo Triazole, 2,5-bis- [5′-t-butylbenzoxazolyl- (2)] thiophene, and the like, compounds described in “Practical Handbook for Additives for Plastics and Rubber” (Chemical Industry Co., Ltd.) can be used. .

  These are generally used in the range of 0.01 to 5% by weight, preferably 0.05 to 3% by weight.

[Sheet or film]
The sheet or film of the present embodiment is obtained from the above resin composition.

  The sheet or film of the present embodiment can be produced by molding the above-described resin composition by a method such as T-die extrusion molding, inflation molding, tenter or stretcher stretching.

  The sheet obtained from the resin composition of the present embodiment preferably has a thickness exceeding 0.3 mm and 5 mm or less, and more preferably 0.5 to 3 mm.

  Moreover, it is preferable that the film obtained from the resin composition of this embodiment is 10-300 micrometers in thickness, It is more preferable that it is 20-200 micrometers, It is still more preferable that it is 30-100 micrometers.

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples, but the present embodiment is not limited to these examples.

(Raw material ingredients)
Table 1 shows component (I); block copolymer, Table 2 shows component (II); microcrystalline wax, and Table 3 shows component (B); general use as vinyl aromatic hydrocarbon polymer. Polystyrene (GPPS), styrene-n-butyl acrylate copolymer and styrene-butadiene block copolymer were shown.

[Component (I); Preparation of Block Copolymer]
Component (I): As a block copolymer, n-butyllithium in a cyclohexane solvent as a catalyst, tetramethylethylenediamine as a randomizing agent, styrene content (% by weight) and block rate (% by weight) shown in Table 1 And block copolymers I-1 to I-4 having a number average molecular weight were prepared.

  In the preparation of the block copolymers I-1 to I-4, the monomer diluted with cyclohexane to a concentration of 20% by weight was used.

  Hereinafter, the method for preparing the block copolymers I-1 to I-4 will be described in detail.

1) Block copolymer I-1
Using an autoclave equipped with a stirrer, 0.080 parts by mass of n-butyllithium was added to a cyclohexane solution containing 25 parts by mass of styrene under a nitrogen gas atmosphere, and polymerization was performed at 80 ° C. for 20 minutes.
Next, ii) a cyclohexane solution containing 17 parts by mass of styrene and 24 parts by mass of 1,3-butadiene was continuously added for 60 minutes and polymerized at 80 ° C.
Next, iii) A cyclohexane solution containing 35 parts by mass of styrene was continuously added for 25 minutes and polymerized at 80 ° C., and then kept at 80 ° C. for 10 minutes. Thereafter, the polymerization was stopped by adding methanol to the polymerization vessel at a 0.9-fold molar ratio with respect to n-butyllithium, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) was used as a stabilizer. ) Ethyl] -4,6-di-t-pentylphenyl acrylate is added in an amount of 0.5 parts by mass to 100 parts by mass of the block copolymer, and then the solvent is removed to obtain the block copolymer (I-1). Obtained.

2) Block copolymer I-2
In ii) of the above 1), the blending amount of styrene is changed to 22 parts by mass, the blending amount of 1,3-butadiene is changed to 30 parts by mass, and in iii) of 1), the blending amount of styrene is changed to 23 parts by mass. A block copolymer (I-2) was produced in the same manner as the block copolymer (I-1) except that.

3) Block copolymer I-3
In i) of 1), the amount of n-butyllithium is changed to 0.100 parts by mass. In ii) of 1), the amount of styrene is 12 parts by mass and the amount of 1,3-butadiene is changed. The block copolymer (I-3) was prepared in the same manner as the block copolymer (I-1) except that the amount of styrene was changed to 39 parts by mass in iii) of 1) above. ) Was produced.

4) Block copolymer I-4
In ii) of the above 3), the blending amount of styrene is changed to 28 parts by mass, the blending amount of 1,3-butadiene is changed to 25 parts by mass, and in iii) of the above 3), the blending amount of styrene is changed to 22 parts by mass. A block copolymer (I-4) was produced in the same manner as the block copolymer (I-3) except that.

  In addition, when the addition amount of n-butyllithium is decreased, the molecular weight tends to increase. Further, when the amount of styrene added in ii) is increased with respect to the amount of styrene added in i) and iii), the styrene block rate tends to decrease.

  Table 1 below shows the styrene content, styrene block ratio, and melt flow index (MI) of the block copolymers (I-1) to (I-4) produced as described above.

[Component (II); microcrystalline wax]
Component (II): As the microcrystalline wax, the melting point, normal / isoparaffin content ratio, normal paraffin content with 44 or less carbon atoms, isoparaffin content with 44 or less carbon atoms, penetration, etc., shown in Table 2 Microcrystalline waxes II-1 to II-4 exhibiting properties were used.

  The penetration and melting point were measured by the following methods.

(Penetration)
Based on JIS K2235-5.4, a load of 100 g was applied to a predetermined needle at 25 ° C. to determine how many mm it would enter the sample in 5 seconds, and it was expressed as a value 10 times the calculated value. Things were taken as penetration.

(Melting point)
Based on JIS K2235-5.3.2, a thermometer cooled to 5 ° C. was put in a melting sample and quickly pulled up. At that time, a thermometer to which the sample was fixed and adhered was placed in an air jacket, and the temperature was raised at 1 ° C./min. The temperature at which the adhered sample dropped was taken as the melting point.

[Component (B): Vinyl aromatic hydrocarbon polymer]
Component (B): As the vinyl aromatic hydrocarbon polymer, the following B-1 to B-3 were used.

  B-1: General-purpose polystyrene (GPPS) (PS Japan, polystyrene 685).

  B-2: Styrene-n-butyl acrylate copolymer (PS Japan Co., Ltd., SC004) was used.

  B-3: Styrene-butadiene block copolymer (Asahi Kasei Chemicals Corporation, Toughprene 126).

  The characteristics of B-1 to B-3 are shown in Table 3.

[Component (III); liquid paraffin]
Component (III): As liquid paraffin, Sanko Chemical Co., Ltd. (No. 380S: SUS viscosity = 380) was used.

(Measurement and evaluation method)
Measurement and evaluation in Examples and Comparative Examples were performed by the following methods.

1) Styrene content The styrene content of the block copolymer or the like was measured using an ultraviolet spectrophotometer (device name: UV-2450; manufactured by Shimadzu Corporation).

2) Block ratio The block copolymer before hydrogenation is oxidatively decomposed with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429). (Method described in (1946)), and the block styrene content was measured.

  Further, the block ratio is calculated by the following formula using the vinyl aromatic hydrocarbon polymer block component obtained by the same method (however, the vinyl aromatic hydrocarbon polymer component having an average degree of polymerization of about 30 or less is excluded). I asked for it.

Block ratio (% by weight) = (weight of vinyl aromatic hydrocarbon polymer block in block copolymer / weight of total vinyl aromatic hydrocarbon in block copolymer) × 100
3) Number average molecular weight The number average molecular weight of the block copolymer and the like was measured using a GPC apparatus (manufactured by Waters, USA). Tetrahydrofuran was used as a solvent, and measurement was performed at 35 ° C.

  The number average molecular weight was calculated | required using the analytical curve created using the commercially available standard polystyrene whose weight average molecular weight and number average molecular weight are known.

4) MI
MI of the block copolymer or the like was measured at 200 ° C. and a load of 5 kg in accordance with ISO1133.

5) Normal paraffin content having 44 or less carbon atoms and isoparaffin content having 44 or less carbon atoms First, microcrystalline wax / urea was mixed at 1/25, and the mixture was stirred and mixed in cyclohexane at 25 ° C. for 2 hours. By this mixing, normal paraffin was adsorbed on urea and isoparaffin was not adsorbed and remained in cyclohexane. Thereafter, cyclohexane was distilled off to separate isoparaffin.

  Next, using column chromatography equipped with a capillary column, the molecular weight distribution of normal paraffin in microcrystalline wax and fractionated isoparaffin is measured, so that the normal paraffin content of 44 or less carbon atoms in microcrystalline wax and The content of isoparaffin having 44 or less carbon atoms was measured.

6) Penetration Degree of penetration of the microcrystalline wax was measured at 25 ° C. in accordance with JIS K223.5.4.

7) Dirt impact strength Measured according to ASTM D1709.

8) Tensile properties Measured in the sheet extrusion direction according to JIS K7113.

9) Transparency Haze value was measured according to ISO14782.

10) Surface appearance After leaving the sheet at 23 ° C. and 50% relative humidity or at 60 ° C. and 80% relative humidity for 3 months, the surface appearance of the sheet was visually evaluated.

<Criteria>
○: Wax blooming is hardly noticeable.

    Δ: A level where no wax blooming is observed but is a problem.

    X: Wax blooming is conspicuous.

11) Sliding angle A sheet of 5 cm × 10 cm is placed on a smooth glass plate, and a load of 6.5 g is placed on the sheet, and the glass plate is slowly tilted so as to incline in the longitudinal direction of the sheet, and the sheet starts to slide. The angle was measured.

  The slip angle obtained by this measurement has a good correlation with the mounting property when a plastic cup immediately after molding is mounted on a printing press. When the sliding angle exceeds 40 degrees, mounting failure occurs, and mounting properties are good when the angle is 40 degrees or less. When the sliding angle is 35 degrees or less, a high-speed printing speed can be handled.

12) Punching property A 6 mm diameter circular punch (punching machine) was used to make a hole in the sheet, and burrs generated around the punched circular hole were observed, and the following evaluation was performed.

    ○: No burr is generated.

    Δ: Burr having a width of less than 0.3 mm is generated.

    X: Burr having a width of 0.3 mm or more is generated.

13) Wax melting point The melting point of microcrystalline wax was measured according to JIS K2235-5.3.2.

[Examples 1-8 and Comparative Examples 1-8]
Component (I); block copolymer I-1, component (II); any of microcrystalline waxes II-1 to II-4, component (III); liquid paraffin, and the composition (A The pellets were obtained by adding to a 30 mm single screw extruder and pelletizing so that the composition shown in FIG.

  Next, the obtained pellets and component (B); vinyl aromatic hydrocarbon polymers B-2 and B-3 were placed in a 40 mm single screw extruder so as to have the blending composition shown in Table 4. By adding and molding at 210 ° C., a sheet having a thickness of 0.6 mm was obtained. The physical properties of the obtained sheet were measured by the above method. The measurement results are shown in Table 4.

  From this result, the balance of physical properties such as rigidity and impact resistance was maintained by using the resin composition containing the microcrystalline wax specified in this embodiment and the block copolymer and liquid paraffin specified in this embodiment. It was found that a sheet having excellent surface appearance, stackability, transparency and punchability can be obtained.

  In particular, from the comparison between Example 1 and Comparative Example 5 and the comparison between Example 6 and Comparative Example 8, even if the microcrystalline wax has the same melting point and penetration, the number of carbon atoms in the microcrystalline wax is 44 or less. When using microcrystalline wax whose isoparaffin content and normal paraffin content having 44 or less carbon atoms are outside the range specified in this embodiment, the resulting sheet is inferior in physical properties such as surface appearance and punchability. I understood.

[Examples 9 to 20 and Comparative Examples 9 to 14]
Component (I); any of block copolymers I-1 to I-4; Component (II); any of microcrystalline wax II-1, II-2, II-4; and component (III); liquid paraffin Were added to a 30 mm-shaft extruder so as to have the composition shown in the composition (A) of Table 5 and Table 6, and pelletized by pelletizing.

  Next, the obtained pellets and component (B); vinyl aromatic hydrocarbon B-1 were added to a 40 mm single screw extruder so as to have the compounding composition shown in Table 5 and Table 6. By molding at 210 ° C., a sheet having a thickness of 0.6 mm was obtained. The physical properties of the obtained sheet were measured by the above method. The measurement results are shown in Tables 5 and 6.

  From this result, the balance of physical properties such as rigidity and impact resistance was maintained by using the resin composition containing the microcrystalline wax specified in this embodiment and the block copolymer and liquid paraffin specified in this embodiment. It was found that a sheet having excellent surface appearance, stackability, transparency and punchability can be obtained.

  The sheet obtained from the resin composition of the present invention is excellent in physical property balance such as rigidity and impact resistance, and is further excellent in surface appearance, stackability, transparency and punching workability. Therefore, the sheet can be suitably used for beverage containers, trays, blister containers and the like.

Claims (3)

Component (I); a block copolymer comprising 60 to 95% by weight of a vinyl aromatic hydrocarbon and 5 to 40% by weight of a conjugated diene or a hydrogenated product thereof;
Component (II); microcrystalline wax;
Component (III); liquid paraffin,
The component (II) comprises normal paraffin and isoparaffin;
The content of isoparaffin having 44 or less carbon atoms in the component (II) is 12.5% by weight or more with respect to a total of 100% by weight of normal paraffin and isoparaffin,
The normal paraffin content of 44 or less carbon atoms in the component (II) is 30 wt% or less with respect to 100 wt% of the total of normal paraffin and isoparaffin,
The content of the component (II) is 0.1 to 1 part by weight and the content of the component (III) is 0.1 to 0.5 part by weight with respect to 100 parts by weight of the component (I). , Resin composition. In addition, component (B); containing a vinyl aromatic hydrocarbon polymer,
The component (B) is at least one vinyl aromatic hydrocarbon polymer selected from the group consisting of the following (a) to (c):
The resin composition according to claim 1, wherein a weight ratio (component (I) / component (B)) between the component (I) and the component (B) is 99/1 to 5/95;
(A) a styrenic polymer,
(B) at least one aliphatic unsaturated carboxylic acid selected from the group consisting of vinyl aromatic hydrocarbons, aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid anhydrides and aliphatic unsaturated carboxylic acid esters Or a copolymer with a derivative thereof,
(C) A block copolymer elastomer of a vinyl aromatic hydrocarbon and a conjugated diene having a vinyl aromatic hydrocarbon content of less than 60% by weight or a hydrogenated product thereof.   A sheet or film obtained from the resin composition according to claim 1.