JP6507611B2 - Surface physical property improving agent composition, acrylic resin composition, and acrylic resin molded article - Google Patents

Description

  The present invention relates to a surface property improver composition applicable to various thermoplastic resins, an acrylic resin composition, and an acrylic resin molded article.

  Thermoplastic resins are widely used in various fields such as automobiles, electric appliances, building materials, sundries, etc. in terms of weight reduction, price reduction, easiness of processing, and recyclability. In recent years, the design properties of these thermoplastic resins are strongly demanded, and improvements in abrasion resistance and abrasion resistance are strongly desired.

  As a method of improving the abrasion resistance and abrasion resistance of a thermoplastic resin, addition of a lubricant such as fatty acid amide is widely known, but there is a problem that the fatty acid amide bleeds out and the surface of the molded article becomes sticky. On the other hand, ethylene / α-olefin copolymer rubber or ethylene / α-olefin / non-conjugated diene copolymer rubber is used as a method of improving the abrasion resistance of the thermoplastic resin while suppressing the bleeding of the lubricant. A composition comprising a copolymer of ethylene and at least one vinyl monomer, and a higher fatty acid amide has been proposed (see Patent Document 1). For the same purpose, a graft copolymer composition containing fatty acid amide has been proposed (see Patent Document 2).

JP, 2006-143938, A JP 2002-338778 A

  However, with the compositions described in Patent Document 1 and Patent Document 2, although the scratch resistance of the thermoplastic resin molded article can be improved, the bleeding suppressing power is insufficient, and bleeding occurs with the passage of time, resulting in the surface of the molded article. There was a glaring problem.

  In view of the above circumstances, an object of the present invention is to provide a surface physical property improving agent composition capable of improving the abrasion resistance and the abrasion resistance of a thermoplastic resin while preventing the occurrence of bleeding on the surface of a molded body. An acrylic resin composition and an acrylic resin molded article.

In order to achieve the above object, the surface property modifier composition according to one aspect of the present invention comprises 10 to 40% by weight of (A) ethylene / α-olefin copolymer rubber, or ethylene / α-olefin / non-conjugated Diene copolymer rubber, 35 to 70% by weight of (B) ethylene / vinyl copolymer, 10 to 30% by weight of (C) fatty acid amide, and 1 to 30% by weight of (D) graft copolymer And.
The (B) ethylene-vinyl copolymer contains ethylene and a vinyl monomer containing an oxygen atom.
The (D) graft copolymer is composed of 50 to 80% by weight of (d1) ethylene / acrylic acid alkyl ester copolymer and 20 to 50% by weight of (d2) vinyl copolymer, (D1) An ethylene / acrylic acid alkyl ester copolymer is used as a main chain, and the above (d2) vinyl copolymer is used as a side chain.
The vinyl monomer constituting the (d2) vinyl copolymer includes (d2-1) an aromatic vinyl monomer, (d2-2) (meth) acrylic acid alkyl ester monomer, and (d2-) 3) (meth) acrylic acid hydroxyalkyl ester monomer.

  According to the above configuration, the (D) graft copolymer contained in the surface physical property modifier composition is (A) an ethylene / α-olefin copolymer rubber, or an ethylene / α-olefin / non-conjugated diene copolymer It functions as a compatibilizer for the combined rubber and (B) ethylene / vinyl copolymer. Thus, the thermoplastic resin can be well mixed with (A) ethylene / α-olefin copolymer rubber or ethylene / α-olefin / non-conjugated diene copolymer rubber and (B) ethylene / vinyl copolymer. It is possible to improve the abrasion resistance and the abrasion resistance of the thermoplastic resin while preventing the generation of the bleeding of the (C) fatty acid amide on the surface of the molded body.

  The acrylic resin composition according to an aspect of the present invention contains 100 parts by weight of an acrylic resin and 1 to 10 parts by weight of the above-mentioned surface physical property improving agent composition.

  According to the above configuration, it is possible to obtain an acrylic resin composition having good abrasion resistance and abrasion resistance without causing bleeding on the surface.

  Moreover, the acrylic resin molding concerning one form of the present invention is obtained by molding the above-mentioned acrylic resin composition.

  According to the above-mentioned configuration, it is possible to obtain an acrylic resin molded article having good scratch resistance and abrasion resistance without causing bleeding on the surface.

  Provided is a surface physical property improving agent composition, an acrylic resin composition, and an acrylic resin molded article capable of improving the abrasion resistance and abrasion resistance of a thermoplastic resin while preventing the occurrence of bleeding on the surface of the molded article. can do.

  Hereinafter, an embodiment of the present invention will be described. In the present invention, "○ to xx" indicating a numerical range means "○ or more and xx or less" unless otherwise specified. Moreover, "(meth) acrylic acid" is a concept including both methacrylic acid and acrylic acid.

<Surface physical property modifier composition>
The surface property modifier composition according to the present embodiment comprises (A) an ethylene / α-olefin copolymer rubber or an ethylene / α-olefin / nonconjugated diene copolymer rubber, and (B) an ethylene / vinyl copolymer A united body, (C) fatty acid amide, and (D) graft copolymer are contained (hereinafter referred to as components (A) to (D) respectively).

  Hereinafter, components (A) to (D) will be described in detail.

[Component (A)]
Component (A) is an ethylene / α-olefin copolymer rubber or an ethylene / α-olefin / non-conjugated diene copolymer rubber.

  The component (A) is compatible with the component (C) in the surface physical property modifier composition, and has a function of suppressing bleeding out of the component (C).

  Examples of α-olefins copolymerized with ethylene in component (A) include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and the like can be mentioned. These α-olefins may be used alone or in combination of two or more. Further, as non-conjugated dienes, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, 5-ethylidene-2-norbornene, vinyl norbornene and the like can be mentioned.

  Specific examples of the ethylene / α-olefin copolymer rubber include ethylene / propylene copolymer rubber (EPR), ethylene / 1-butene copolymer rubber, ethylene / 1-hexene copolymer rubber, ethylene / 1- An octene copolymer rubber (EOR), a propylene 1-butene copolymer rubber, an ethylene / propylene 1-butene copolymer rubber and the like can be mentioned. In particular, ethylene-propylene copolymer rubber (EPR) or ethylene / 1-octene copolymer rubber (EOR) is preferable. Further, as specific examples of ethylene / α-olefin / non-conjugated diene copolymer rubber, ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (EPDM), ethylene / propylene / dicyclopentadiene copolymer Rubber etc. are mentioned. The ethylene / α-olefin copolymer rubber and the ethylene / α-olefin / non-conjugated diene copolymer rubber may be used alone or in combination of two or more.

  Commercial products can be used as the ethylene / α-olefin copolymer rubber and the ethylene / α-olefin / non-conjugated diene copolymer rubber. Examples of the commercially available products include Sumitomo Chemical Co., Ltd. product names: Esprene SPO V0111, Esprene SPO V0131, Esprene SPO V0132, Esprene SPO V0141, Esprene EPDM 502, Esprene EPDM 512F, Esprene EPDM 552, Esprene EPDM 553, Dow・ Product name of Chemical Japan Co., Ltd .: Engage 7270, Engage 7447, Engage 7467, Engage 8003, Engage 8100, Engage 8200, Engage 8452, Prime Polymer Co., Ltd. Product Name: Prime TPO M142E, Prime TPO R110E, Prime TPO Product name made by R110MP, AS Japan Ltd .: Santo Plain 201-55, Santo Plain 201-64, Santo Plain 201-73, Santo Plain 201-80, Santo Plain 201-87, Santo Plain 203-40, Santo Plain 203-50, product name made by Mitsui Chemicals, Inc. Product name: Mirastomer 5030N, Mirastomer 6030N, Mirastomer 7030N, Mirastomar 8030N, Mirastomar 8032N, Mirastomer 9020N, product name of JSR Corporation: JSR EP21, JSR EP22, JSR EP24, JSR EP25, JSR EP27, JSR EP33, JSR EP35, JSR EP43, JSR EP51, JSR EP57F, JSR EP57F EP57C, JSR EP65, JSR EP93, JSR EP96, JSR EP98, JSR EP103AF and the like can be mentioned.

  Assuming that the total content of the components (A) to (D) is 100% by weight, the content of the component (A) is 10 to 40% by weight. By setting the content of the component (A) to 10% by weight or more, the ability to retain the component (C) in the acrylic resin composition is improved. In addition, by setting the content of the component (A) to 40% by weight or less, the component (C) holding ability can be suppressed to an appropriate range, and the scratch resistance and the abrasion resistance of the acrylic resin molded body are improved. .

[Component (B)]
Component (B) is an ethylene-vinyl copolymer, and contains ethylene and one or more vinyl monomers containing an oxygen atom.

  Similar to the component (A), the component (B) is compatible with the component (C) in the surface physical property modifier composition and has a function of suppressing the bleed out of the component (C).

  As a vinyl monomer containing an oxygen atom copolymerized with ethylene in the component (B), (meth) acrylic acid, (meth) acrylic acid alkyl ester, glycidyl (meth) acrylate, vinyl acetate, anhydride Maleic acid etc. are mentioned. These vinyl monomers may be used alone or in combination of two or more.

  Specific examples of the ethylene-vinyl copolymer containing ethylene and one or more vinyl monomers containing an oxygen atom include ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer (EMA), ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer (EEA), ethylene-acrylic acid n-butyl copolymer, ethylene-isobutyl acrylate copolymer, ethylene-acrylic acid 2 -Ethylhexyl copolymer, ethylene / glycidyl methacrylate copolymer (EGMA), ethylene / vinyl acetate copolymer (EVA), ethylene / ethyl acrylate / glycidyl methacrylate copolymer, ethylene / ethyl acrylate / maleic anhydride Acid copolymers, ethylene / vinyl acetate / glycidyl methacrylate copolymers, etc. That. In particular, ethylene / methyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / n-butyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene -Vinyl acetate copolymer is preferred. In addition, the compound by which the terminal of vinyl acetate was saponified is also contained in these compounds. The ethylene / vinyl copolymer containing these ethylene and one or more vinyl monomers containing an oxygen atom may be used alone or in combination of two or more. Good.

  A commercial item can be used for the said ethylene-based copolymer. Examples of the commercially available products include product names: DPDJ-6169, DPDJ-6182, DPDJ-9169, NUC-6070, NUC-6170, NUC-6220, NUC-6510, NUC-6520, NUC manufactured by Nippon Unicar Co., Ltd. -5670, NUC-6940, DQDJ-1868, DQDJ-3269, NUC-3195, NUC-3461, NUC-3660, NUC-3810, NUC-3830, NUC-3888, product name of Japan Polyethylene Corporation: Rex Pearl EMA EB 050 S, Rex Pearl EMA EB 140 F, Rex Pearl EMA EB 230 X, Rex Pearl EMA EB 240 H, Rex Pearl EMA EB 330 H, Rex Pearl EMA EB 440 H, Rex Pearl EEA A1100, Rek Pearl EEA A1150, Rexpearl EEA A3100, Rexpearl EEA A4200, Rexpearl EEA A4250, Rexpearl EEA A6200, manufactured by Sumitomo Chemical Co., Ltd. Product name: Bondfast 2C, Bondfast E, Bondfast 2B, Bondfast 7B, Bond Fast 7L, Bondfast 7M, product name by Tosoh Corporation: Ultrasen 633, Ultrasen 680, Ultrasen 681, Ultrasen 635, Ultrasen 640, Ultrasen 634, Ultrasen 751, Ultrasen 710, Ultrasen 720 , Ultra Sen 722, Ultra Sen 726, Ultra Sen 750, and the like.

  Assuming that the total content of the components (A) to (D) is 100% by weight, the content of the component (B) is 35 to 70% by weight. By setting the content of the component (B) to 35% by weight or more, the ability to retain the component (C) in the acrylic resin composition is improved. In addition, by setting the content of the component (B) to 70% by weight or less, the component (C) holding ability can be suppressed to an appropriate range, and the abrasion resistance and the abrasion resistance of the acrylic resin molded body are improved. .

[Component (C)]
Component (C) is a fatty acid amide, and has a function of imparting scratch resistance and abrasion resistance to an acrylic resin. The carbon atom number of the fatty acid moiety of the component (C) is not particularly limited, but it is desirable that the carbon atom number of the moiety is 12 to 24. When the carbon atom number of the fatty acid portion is 12 or more, good lubricity can be obtained, and sufficient abrasion resistance and abrasion resistance can be imparted to the acrylic resin molded article. In addition, from the viewpoint of availability, fatty acid amides having 24 or less carbon atoms in the fatty acid moiety are preferable.

  Specific examples of component (C) include lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, ethylenebisstearic acid amide, ethylenebisbehenic acid amide, Ethylene bis oleic acid amide, ethylene bis erucic acid amide, etc. are mentioned. In particular, oleic acid amide, erucic acid amide, ethylenebisstearic acid amide, ethylenebisoleic acid amide and ethylenebiserucic acid amide are preferable. These fatty acid amides may be used alone or in combination of two or more.

  Assuming that the total content of the components (A) to (D) is 100% by weight, the content of the component (C) is 10 to 30% by weight. By setting the content of the component (C) to 10% by weight or more, sufficient lubricity is obtained, and the abrasion resistance and the abrasion resistance of the acrylic resin molded article are improved. Further, by setting the content of the component (C) to 30% by weight or less, bleeding of the excess component (C) to the surface of the acrylic resin molded product can be suppressed. Furthermore, since the component (C) has an effect of plasticizing the acrylic resin, by setting the content of the component (C) to 30% by weight or less, the decrease in mechanical strength of the acrylic resin molded product can be prevented. it can.

[Component (D)]
Component (D) is a graft copolymer, and has (d1) ethylene / acrylic acid alkyl ester copolymer as the main chain and (d2) vinyl copolymer as the side chain (hereinafter simply referred to as (d1)) , (D2))).

  As described above, although the component (A) and the component (C), or the component (B) and the component (C) are compatible with each other, a sufficient bleeding suppression effect can not be expected by this alone. In addition, when the component (A), the component (B), and the component (C) are simultaneously blended, the compatibility between the component (A) and the component (B) is low, so that a sufficient bleeding suppression effect can not be obtained.

  Then, since the component (D) which comprises a surface physical property modifier composition has (d1) and (d2), it functions as a compatibilizer of component (A) and component (B). Thereby, a component (A) and a component (B) can be mixed favorable, and the bleed of the component (C) to the acrylic resin molded object surface can be suppressed.

  Assuming that the total content of the components (A) to (D) is 100% by weight, the content of the component (D) is 1 to 30% by weight. By adjusting the content of the component (D) to 1% by weight or more, the compatibility between the component (A) and the component (B) is improved, and the component (A) and the component (B) are mixed well. it can. Thereby, a component (C) can be hold | maintained in an acrylic resin composition, and the bleed | breed to the acrylic resin molded object surface of a component (C) can be suppressed. Moreover, the excess holding | maintenance of the component (C) in an acrylic resin composition can be prevented by content of a component (D) being 30 weight% or less.

(1) Main chain (d1)
(D1) is a main chain of the graft copolymer and is a segment compatible with the component (B). (D1) is not limited to a specific type as long as it is an ethylene / acrylic acid alkyl ester copolymer compatible with the component (B), and can be determined appropriately.

(2) Side chain (d2)
(D2) is a side chain of the graft copolymer and is a segment compatible with both component (A) and component (B).

  The vinyl monomers constituting (d2) are (d2-1) aromatic vinyl monomers, (d2-2) (meth) acrylic acid alkyl ester monomers, and (d2-3) (meth) It is an acrylic acid hydroxyalkyl ester monomer (hereinafter, also referred to as vinyl monomers (d2-1) to (d2-3), respectively).

  The vinyl monomers (d2-1) to (d2-3) are not limited to specific types as long as they are the above compounds. By combining these vinyl monomers having different polarities, it becomes possible to exhibit compatibility with both the component (A) and the component (B).

  Assuming that the total content of (d1) and (d2) is 100% by weight, the content of (d1) is 50 to 80% by weight, and the content of (d2) is 20 to 50% by weight.

  There is no restriction | limiting in particular as a method to synthesize | combine (d2), Well-known polymerization methods, such as a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, a block polymerization method, can be used. In particular, suspension polymerization is preferred.

  When synthesizing (d2), only (d2) may be synthesized and then mixed with (d1) at the time of grafting. Also, vinyl monomers (d2-1) to (d2-3) constituting (d1) and (d2) are introduced into the same reaction tank, and (d2) is synthesized in the presence of (d1). May be

  There are no particular limitations on the polymerization initiator that can be used in the synthesis of (d2). For example, using known polymerization initiators such as azo polymerization initiators, organized oxides, persulfates, hydrogen peroxide water, redox polymerization initiators (polymerization initiators combining an oxidizing agent and a reducing agent), etc. Can. In particular, when used in the suspension polymerization method, oil-soluble organic oxide is preferable.

  There is no restriction | limiting in particular as a method of grafting (d1) and (d2), Well-known grafting methods, such as a chain transfer method and ionizing radiation irradiation method, are employable. In particular, a method using a radically polymerizable organic peroxide represented by Formula (1) or Formula (2) is preferable.

…（１）

... (1)

In formula (1), R ₁ is a hydrogen atom, a methyl group or an ethyl group, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are each an alkyl group having 1 to 4 carbon atoms, and R ₅ is a carbon atom This represents an alkyl group having 1 to 12 atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. The value of m is 1 or 2.

…（２）

... (2)

In the formula, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₇ is a hydrogen atom or a methyl group, R ₈ and R ₉ are each an alkyl group having 1 to 4 carbon atoms, and R ₁₀ is It shows a C1-C12 alkyl group, a phenyl group, an alkyl substituted phenyl group, or a C3-C12 cycloalkyl group. The value of n is 0, 1 or 2.

  The grafting precursor (d2) is obtained by polymerizing the vinyl monomers (d2-1) to (d2-3) using the radically polymerizable organic peroxide. The graft precursor (d2) and (d1) are mixed and melt-kneaded using a single screw extruder or the like, so that the organic peroxide site is bonded to (d1) to form a graft copolymer. You can get it.

  The amount of the radically polymerizable organic peroxide used is usually 0.5 to 5% by weight based on the total amount of the vinyl monomers (d2-1) to (d2-3). Can.

<Acrylic resin composition>
The acrylic resin composition according to the present embodiment contains 1 to 10 parts by weight of the surface physical property improving agent composition with respect to 100 parts by weight of the acrylic resin. By setting the content of the surface physical property improving agent composition to 1 part by weight or more, the abrasion resistance and the abrasion resistance of the acrylic resin molded article can be improved. In addition, by setting the content of the surface physical property improving agent composition to 10 parts by weight or less, bleeding out of the component (C) to the surface of the acrylic resin molded body, reduction in mechanical strength of the acrylic resin molded body and appearance defect You can prevent.

  The above-mentioned acrylic resin is not limited to a specific type. For example, a homopolymer of methyl methacrylate monomer, a copolymer of methyl methacrylate monomer and a monomer other than methyl methacrylate (PMMA), and the like can be mentioned.

  In the above acrylic resin composition, known heat stabilizers, antioxidants, weathering stabilizers, ultraviolet light absorbers, antistatic agents, colorants, lubricants, dispersants, foaming agents, as long as the object of the present invention is not impaired. A plasticizer, an impact modifier, etc. may be blended.

<Method of producing acrylic resin composition>
The acrylic resin composition is obtained by heating and melting an acrylic resin and a surface physical property improving agent composition at 100 to 300 ° C. and kneading. By setting the heating temperature to 100 ° C. or more, each component can be favorably melted and the melt viscosity can be sufficiently kneaded. This can prevent phase separation and delamination. Moreover, decomposition | disassembly of each component can be prevented by heating temperature being 300 degrees C or less.

  The melting and kneading methods are not particularly limited. For example, known kneading methods such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, and a roll can be used.

<Acrylic resin molding>
The acrylic resin molded product according to the present embodiment is obtained by molding the above acrylic resin composition. It does not specifically limit as a form of an acrylic resin molding. For example, a sheet | seat, a film, a hollow body, a block body, a plate-like body, a cylinder, a complex shape body, a foam etc. are mentioned.

<Molding method of acrylic resin molding>
It will not be specifically limited if it is a shaping | molding method of an acrylic resin as a shaping | molding method of an acrylic resin molded object. For example, a calendar molding method, a compression molding method, a blow molding method, a foam molding method, an extrusion molding method, an injection molding method, a vacuum molding method, a powder slush molding method and the like can be mentioned.

  The resulting acrylic resin molded article can be used for various products and semi-finished products in a wide range of fields such as automobile parts, electrical appliances, construction materials, general goods, etc., by the excellent abrasion resistance and abrasion resistance.

  EXAMPLES Hereinafter, the embodiments of the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited to the scope of these examples. Unless otherwise indicated, "part" and "%" in each example show a "weight part" and "weight%." In addition, abbreviations of substances used in the following Examples, Comparative Examples and Tables, substance names, components containing the substances, product names and manufacturers are shown in Table 1.

<Production of (D) graft copolymer>
Production Example 1-1
In a 5 L reaction tank, 2000 g of water was placed, and 2.0 g of polyvinyl alcohol was dissolved therein as a suspending agent, and 20 g of calcium phosphate tribasic was dispersed as a dispersing agent. Among them, 700 g of EEA as (d1), 100 g of St as a vinyl monomer (d2-1), 100 g of BA as a vinyl monomer (d2-2), 100 g of HPMA as a vinyl monomer (d2-3) Then, 3 g of t-butylperoxymethacryloyloxyethyl carbonate as a radically polymerizable organic peroxide was added, and the temperature was raised to 70 ° C. while stirring. Stirring is continued after the temperature in the reaction tank reaches 70 ° C. for 1 hour, and then 4.5 g of di-3,5,5-trimethylhexanoyl peroxide is introduced as a radical polymerization initiator. The polymerization reaction was carried out for 5 hours. Thereafter, it was cooled to room temperature, washed with water, filtered and dried to obtain a grafted precursor (d2). The obtained grafting precursor (d2) is extruded at 180 ° C. using a Labo Plastomill single screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to produce a grafting reaction with (d1). The graft copolymer (D) of Example 1-1 was obtained.

[Production Examples 1-2 to 1-6 and Comparative Production Examples 1-1 to 1-10]
The same operation as in Production Example 1-1 is performed, except that the used resin (d1) and the vinyl monomers (d2-1) to (d2-3) are changed to the components and the blending amounts shown in Table 2. Thus, graft copolymers (D) of Production Examples 1-2 to 1-6 and Comparative Production Examples 1-1 to 1-10 were obtained.

<Production of Surface Physical Property Modifier Composition>
Example 1-1-1
170 g of EPR as component (A), 390 g of EEA as component (B), 200 g of OA as component (C), and 240 g of the graft copolymer of Production Example 1-1 as component (D) were dry-blended. Thereafter, the mixture is melt-kneaded and pelletized by a coaxial twin screw extruder (Ikegai Co., Ltd.) with a screw diameter of 30 mm set to a cylinder temperature of 180 ° C., and the surface physical property improver according to Example 1-1-1 The composition was obtained.

[Examples 1-1-2 to 1-1-8, Comparative Examples 1-1-1 to 1-1-21 and 1-2-1 to 1-2-12]
Examples 1-1-2 to 1-1-2 are carried out by the same operation as Example 1-1-1, except that the components (A) to (D) used are changed to the components and the blending amounts shown in Table 3. The surface physical property improving agent composition which concerns on -1-8, comparative example 1-1-1 to 1-121, and 1-2-1 to 1-2-12 was obtained.

<Production of Acrylic Resin Composition and Evaluation of Acrylic Resin Molding>
Example 2-1-1
1000 g of PMMA as an acrylic resin and 100 g of the surface physical property improving agent composition according to Example 1-1-1 were dry-blended. Thereafter, the acrylic resin composition according to Example 2-1-1 is melt-kneaded and pelletized by a coaxial twin screw extruder (Ikegai Co., Ltd.) with a screw diameter of 30 mm set to a cylinder temperature of 250 ° C. I got Each specimen is molded at a mold temperature of 50 ° C. using an injection molding machine set to a cylinder temperature of 250 ° C., and the obtained acrylic resin composition is used to determine the presence or absence of bleed, abrasion resistance, and abrasion resistance. evaluated.

[Examples 2-1-2 to 2-1-8 and Comparative Examples 2-1-1 to 1-2-40]
Examples 2-1-2 to 2-1 are carried out by the same operation as Example 2-1-1, except that the used surface physical property improving agent composition is changed to the components and blending amounts shown in Table 4. The acrylic resin composition concerning -8 and comparative example 2-1-1-2-40 was obtained. The obtained acrylic resin composition was molded by performing the same operation as in Example 2-1-1, and the presence or absence of bleed, the abrasion resistance, and the abrasion resistance were evaluated.

<Evaluation method>
[Bleed evaluation]
Using an injection molding machine (manufactured by Nissei Resin Industry Co., Ltd.), plate specimens of 80 mm × 55 mm and a thickness of 2 mm were molded from the pellets. The plate test piece was left in an oven at 70 ° C. for 120 hours, the amount of fatty acid amide bleeding on the surface of the plate test piece was visually observed, and the appearance was evaluated based on the following criteria.
○: There is no bleed ×: There is bleed

[Abrasion resistance test]
Using a scratch tester (manufactured by Kato Tech Co., Ltd., KK-01) and scratching under the conditions of load 1 to 30 N, scratch speed 100 mm / s, scratch distance 100 mm, chip φ = 1 mm (stainless steel) by a method according to ISO19252 A test was conducted to measure the load at which whitening scratches begin to appear, and the average value measured three times with different specimens of the same type was taken as the evaluation point. The test piece used and shape | molded the test piece of ISO3167 (multipurpose test piece A type, thickness 4 mm) from the pellet using the injection molding machine (made by Nissei resin Kogyo Co., Ltd.).

[Abrasion resistance test]
A load of 6.9 N (700 g · f) was applied to the same plate test piece as the test piece used in the bleed evaluation using a Gakushin-type fastness friction and abrasion tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The surface of the test piece after 100 times of reciprocating abrasion according to No. (cotton cloth) was visually observed and evaluated according to the following evaluation criteria.
4: No scar is found 3: Scars are found on less than 25% of the test surface 2: Scars are found on 25% to 50% of the test surface 1: Scars are found on 50% or more of the test surface

<Evaluation criteria>
It is good that the bleeding evaluation is ○, the abrasion resistance evaluation is 5 N or more, and the abrasion resistance evaluation is all 4 to 3 in all the cases.

<Evaluation result>
The evaluation result about the acrylic resin molded object which concerns on Example 2-1 to 1-2-8, and comparative example 2-1-1 to 1-2-40 is shown in Table 4. From Table 4, it can be seen that no bleeding occurs in Examples 2-1-1 to 1-2-8, and the abrasion resistance and the abrasion resistance are excellent results.

  On the other hand, Comparative Example 2-1-1 not containing the surface physical property modifier composition, Comparative Example 2-1-2 containing EPR instead of the surface physical property modifier composition, and the surface physical property modifier composition In each of Comparative Examples 2-1 to 1-3 containing EA, the abrasion resistance and the abrasion resistance decreased. In Comparative Example 2-1-4 where OA was kneaded instead of the surface physical property improving agent composition, OA could not be held in the acrylic resin composition, and bleeding occurred. The abrasion resistance and abrasion resistance of Comparative Example 2-1-5, in which the component (D) was kneaded instead of the surface physical property improving agent composition, were lowered.

  Bleeding occurred in Comparative Example 2-1-6 containing the surface physical property improving agent composition exceeding 10 parts by weight. The abrasion resistance and the abrasion resistance of Comparative Example 2-1-7 containing less than 1 part by weight of the surface physical property improving agent composition decreased.

  The abrasion resistance and abrasion resistance of Comparative Example 2-1-8 using the surface physical property improving agent composition not containing the component (C) were reduced. In Comparative Example 2-1-9 using the surface physical property improving agent composition not containing the component (B), bleeding occurred, and the abrasion resistance and the abrasion resistance decreased. The abrasion resistance and abrasion resistance of Comparative Example 2-1-10 using the surface physical property improving agent composition in which the content of the component (A) is less than 10% by weight decreased. In Comparative Example 2-1-11 using the surface property improver composition in which the content of the component (C) exceeds 30% by weight, bleeding occurred.

  In Comparative Example 2-1-12 using the surface property improver composition containing the component (D) in which (d1) is PE, bleeding occurred and the abrasion resistance and the abrasion resistance decreased. In Comparative Example 2-1-13 using the surface physical property improving agent composition containing the component (D) in which (d1) is PP, bleeding occurred and the abrasion resistance and the abrasion resistance decreased.

  Comparative Examples 2-1-14, 2-1-15, and 2-1-16 using a surface property modifier composition containing a component (D) in which (d2) consists of a single vinyl monomer In all cases, bleeding occurred, and the abrasion resistance and the abrasion resistance decreased.

  Comparative Example 2-1-17 using a surface property improver composition containing the component (D) in which the content of (d1) exceeds 80% by weight, and the content of (d1) is less than 50% by weight In Comparative Example 2-1-18 using the surface property improver composition containing the component (D), bleeding occurred and the abrasion resistance and the abrasion resistance were reduced.

  The abrasion resistance and abrasion resistance of Comparative Example 2-1-19 using the surface physical property improving agent composition not containing the component (C) and the component (D) decreased. Bleeding occurred in Comparative Example 2-1-20 using the surface property improver composition that did not contain Component (A) and Component (D). Bleeding occurs in all of Comparative Examples 2-1 to 2-1-30 using the surface physical property improving agent composition not containing the component (D), and also Comparative Examples 2-1 to 21-1 The abrasion resistance and the abrasion resistance decreased at -24 and 2-1-26 to 1-2-1-29. The comparative example 2-1-31 using the surface physical property improving agent composition which does not contain a component (A) generate | occur | produced a bleed, and abrasion resistance and abrasion resistance fell.

  The abrasion resistance and the abrasion resistance of Comparative Example 2-12 using the surface physical property improving agent composition in which the content of the component (A) exceeds 40% by weight were lowered. The abrasion resistance and abrasion resistance of Comparative Example 2-13 using the surface physical property improving agent composition in which the content of the component (B) exceeds 70% by weight were lowered. In Comparative Example 2-1-34 using the surface physical property improving agent composition in which the content of the component (B) is less than 35% by weight, bleeding occurred and the abrasion resistance decreased. The abrasion resistance and abrasion resistance of Comparative Example 2-1-35 using the surface physical property improving agent composition in which the content of the component (C) is less than 10% by weight decreased. The abrasion resistance and abrasion resistance of Comparative Example 2-13 using the surface physical property improving agent composition in which the content of the component (D) exceeds 30% by weight were lowered. In Comparative Example 2-1-37 using the surface property improver composition containing neither the component (A) nor the component (C), bleeding occurred and the abrasion resistance and the abrasion resistance decreased.

  Comparative Example 2-1-38 using a surface property improver composition containing a component (D) containing no vinyl monomer (d2-3), a component containing no vinyl monomer (d2-2) Comparative Example 2-1-39 using the surface property improver composition containing D) and the surface property improver composition containing the component (D) not containing the vinyl monomer (d2-1) In each of Comparative Examples 2-1 to 40, bleeding occurred, and the abrasion resistance and the abrasion resistance decreased.

  As mentioned above, although embodiment of this invention was described, this invention is not limited only to the above-mentioned embodiment, Of course in the range which does not deviate from the summary of this invention, a various change can be added.

  For example, in the above embodiment, an example in which the surface physical property improving agent composition is applied to an acrylic resin has been described, but the surface physical property improving agent composition has the same effect as the acrylic resin by applying to a thermoplastic resin other than acrylic resin. Is obtained.

  Specifically, as the resin to which the surface physical property improving agent composition can be applied, for example, olefin resins such as polyolefin resins such as polyethylene and polypropylene, ethylene / propylene copolymer rubber, ethylene / propylene / conjugated diene copolymer rubber and the like Styrenic thermoplastic elastomers such as thermoplastic elastomer (TPO), styrene butadiene copolymer rubber, styrene isoprene copolymer rubber, hydrogenated styrene butadiene copolymer rubber, hydrogenated styrene isoprene copolymer rubber TPS), polyesters such as styrene-butadiene-acrylonitrile copolymer (ABS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyamides such as 6-nylon, 6,6-nylon, 6,12-nylon PA), polyoxime Ren (POM), polycarbonate (PC), polylactic acid (PLA), PC / ABS alloy, PC / PLA alloy, and the like.

Claims (2)

100 parts by weight of acrylic resin,
10 to 40% by weight of (A) ethylene / α-olefin copolymer rubber or ethylene / α-olefin / nonconjugated diene copolymer rubber and 35 to 70% by weight (B) ethylene / vinyl copolymer And 10 to 30% by weight of (C) fatty acid amide and 1 to 30% by weight of (D) graft copolymer,
The (B) ethylene-vinyl copolymer contains ethylene and a vinyl monomer containing an oxygen atom,
The (D) graft copolymer is composed of 50 to 80% by weight of (d1) ethylene (meth) acrylic acid alkyl ester copolymer, and 20 to 50% by weight of (d2) vinyl copolymer. And (d1) an ethylene / (meth) acrylic acid alkyl ester copolymer as a main chain, and the (d2) vinyl copolymer as a side chain,
The vinyl monomer constituting the (d2) vinyl copolymer is a (d2-1) aromatic vinyl monomer, a (d2-2) (meth) acrylic acid alkyl ester monomer, and (d2- 3) 1 to 10 parts by weight of a surface physical property modifier composition containing (meth) acrylic acid hydroxyalkyl ester monomer;
An acrylic resin composition containing   The acrylic resin molded object obtained by shape | molding the acrylic resin composition of Claim 1.