Resin composition, method for producing resin composition, molding material, and article

Abstract

The present invention provides a resin composition to which proteins do not adhere easily and, therefore, which is suitable for manufacturing an article that comes in contact with proteins, said resin composition containing a vinyl chloride-based polymer (A1), a plasticizer (A2) and a (meth)acrylic copolymer (B), wherein the (meth)acrylic copolymer (B) is a block copolymer or a graft copolymer containing a monomer unit (b1) represented by formula (1). [Chemical formula 1]

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a method for producing a resin composition, a molding material, and an article. This application claims priority based on Japanese Patent Application No. 2021-173458 filed in Japan on October 22, 2021, and Japanese Patent Application No. 2022-151815 filed in Japan on September 22, 2022, the contents of which are incorporated herein by reference. [Background technology]

[0002] In recent years, in the fields of medical devices, biochemical analysis, and protein separation and purification, various polymer materials (polystyrene, polypropylene, polyethylene, polyurethane, polyvinyl chloride, polymethyl methacrylate, nylon), glass, and metals such as stainless steel have been used for various parts and containers such as various reaction vessels, centrifuge tubes, tubing, syringes, pipettes, filters, and separation columns. However, proteins tend to adhere to any of these materials, resulting in reduced detection sensitivity, reduced reproducibility, and poor purification. Furthermore, catheters, cannulas, stents, plasma separation membranes, artificial organs such as heart-lung machines, and the like come into contact with circulating blood and metabolic substances in the body, and therefore require biocompatibility to inhibit the adhesion of proteins or the formation of thrombi and other conditions caused by the adhesion of plasma proteins.

[0003] Patent Document 1 describes that polymethoxyethyl acrylate (PMEA) has biocompatibility, such as antithrombogenicity and protein adhesion inhibition. Patent Document 2 describes a method for obtaining a film to which platelets do not easily adhere by heat-treating a coating of a blend solution of polymethyl methacrylate (PMMA) and PMEA and exposing it to ultrapure water. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2004-161954 [Patent Document 2] Japanese Patent Application Publication No. 2013-121430 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the PMEA described in Patent Document 1 has a very low glass transition temperature of approximately -50°C. Therefore, it is difficult to handle PMEA, which is a highly viscous liquid at room temperature, when used directly as an additive to a molding material. Furthermore, when a molded article is produced using a molding material containing PMEA as an additive, there is a concern that PMEA may bleed out and / or fall off from the molded article. Furthermore, when used as a paint, it is difficult to obtain a coating film with sufficient strength and hardness, making it difficult to ensure practical use. Furthermore, the method described in Patent Document 2 has the drawback that the manufacturing process is complicated and the processing time is long.

[0006] An object of the present invention is to provide a resin composition to which proteins are less likely to adhere and which is suitable for producing an article that comes into contact with proteins, a method for producing a resin composition, a molding material, and an article. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] A resin composition comprising a vinyl chloride polymer (A1), a (meth)acrylic copolymer (B), and a plasticizer (A2), The resin composition, wherein the (meth)acrylic copolymer (B) is a block copolymer or a graft copolymer containing a monomer unit (b1) represented by the following formula (1): [ka] (In formula (1), R 3 represents a hydrogen atom or a methyl group, and R 4 represents an alkylene group having 1 to 4 carbon atoms, and R 5 represents a hydrocarbon group having 1 to 6 carbon atoms, and p is a natural number from 1 to 10. [2] The resin composition according to [1], wherein the proportion of the (meth)acrylic copolymer (B) in the total of 100% by mass of the resin composition is 20% by mass or less. [3] The resin composition according to [1] or [2], wherein the proportion of the (meth)acrylic copolymer (B) in the total of 100% by mass of the resin composition is 10% by mass or less. [4] The resin composition according to any one of [1] to [3], wherein the (meth)acrylic copolymer (B) is a block copolymer or a graft copolymer containing a polymer (B1) and a polymer (B2). [5] The resin composition according to [4], wherein the proportion of the monomer units (b1) in the total of 100% by mass of the monomer units contained in the polymer (B1) is 70% by mass or more. [6] The resin composition according to [4] or [5], wherein the proportion of the monomer units (b1) in the total of 100% by mass of the monomer units contained in the polymer (B1) is 90% by mass or more. [7] The resin composition according to any one of claims [4] to [6], wherein the monomer unit (b1) is a monomer unit derived from at least one monomer selected from the group consisting of methoxymethyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, methoxybutyl acrylate, methoxypolyethylene glycol acrylate, methoxymethyl methacrylate, methoxyethyl methacrylate, methoxypropyl methacrylate, methoxybutyl methacrylate, and methoxypolyethylene glycol methacrylate. [8] The resin composition according to any one of [4] to [7], wherein the polymer (B2) has a glass transition point (Tg) of 50 to 150°C. [9] The polymer (B2) is composed of monomer units (b2), The resin composition according to any one of [4] to [8], wherein the monomer unit (b2) is a monomer unit derived from at least one monomer selected from the group consisting of hydrocarbon group-containing (meth)acrylates in which the hydrocarbon group has 1 to 12 carbon atoms.

[10] The polymer (B2) is composed of monomer units (b2), The resin composition according to any one of [4] to [9], wherein the monomer units (b2) include monomer units derived from methyl methacrylate.

[11] The resin composition according to any one of [1] to

[10] , wherein the polymer (B2) contains a unit derived from a macromonomer represented by the following formula (2): [ka] (In formula (2), R 0 ~R n each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, or an unsubstituted or substituted non-aromatic heterocyclic group; 0 ~R n may be the same or different, and X 1 ~X n represents a hydrogen atom or a methyl group, and multiple X 1 ~X n may be the same or different, Z is a terminal group, and n is a natural number from 2 to 10,000.

[12] The resin composition according to any one of [1] to

[11] , wherein the plasticizer (A2) is at least one selected from the group consisting of phthalic acid compounds, terephthalic acid compounds, trimellitic acid compounds, cyclohexanedicarboxylic acid ester compounds, phosphoric acid compounds, adipic acid compounds, citric acid compounds, ether compounds, and polyester compounds.

[13] The resin composition according to any one of [1] to

[12] , wherein the plasticizer (A2) is at least one selected from the group consisting of bis(2-ethylhexyl) phthalate, bis(2-ethylhexyl) terephthalate, tris(2-ethylhexyl) trimellitate, and diisononyl cyclohexane-1,2-dicarboxylate.

[14] The resin composition according to any one of [1] to

[13] , wherein the plasticizer (A2) contains diisononyl cyclohexane-1,2-dicarboxylate.

[15] The resin composition further contains a stabilizer (A3), The resin composition according to any one of [1] to

[14] , wherein the stabilizer (A3) is at least one selected from the group consisting of calcium-zinc stabilizers and epoxidized vegetable oils.

[16] The resin composition according to any one of [1] to

[15] , wherein the haze value of a 1 mm thick sheet measured in accordance with Japanese Industrial Standard JIS K 7136:2000 is less than 50%.

[17] The resin composition further contains a (meth)acrylic polymer (P) different from the (meth)acrylic copolymer (B), the ratio of the (meth)acrylic polymer (P) to a total of 100 parts by mass of the vinyl chloride polymer (A1), the (meth)acrylic copolymer (B), and the plasticizer (A2) is 0.1 to 20 parts by mass, The content of methyl methacrylate units in the (meth)acrylic polymer (P) is 50% by mass or more in a total of 100% by mass, and The resin composition according to any one of [1] to

[16] , wherein the (meth)acrylic polymer (P) has a mass average molecular weight of 100,000 or more.

[18] The resin composition further contains anti-blocking particles (Q), the ratio of the anti-blocking particles (Q) to 100 parts by mass of the (meth)acrylic copolymer (B) is 0.1 parts by mass or more and 20 parts by mass or less; The resin composition according to any one of [1] to

[17] , wherein the median diameter of the anti-blocking particles (Q) measured using a particle size distribution analyzer is 35% or less of the median diameter of the (meth)acrylic copolymer (B).

[19] A resin composition comprising a (meth)acrylic copolymer (B) and anti-blocking particles (Q), The (meth)acrylic copolymer (B) is a block copolymer or a graft copolymer containing a polymer (B1) and a polymer (B2), and the polymer (B1) contains a monomer unit (b1) represented by the following formula (1): A resin composition, wherein the proportion of the anti-blocking particles (Q) is 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the (meth)acrylic copolymer (B), and the median diameter of the anti-blocking particles (Q) measured using a particle size distribution analyzer is 35% or less of the median diameter of the (meth)acrylic copolymer (B). [ka] (In formula (1), R 3 represents a hydrogen atom or a methyl group, and R 4 represents an alkylene group having 1 to 4 carbon atoms, and R 5 represents a hydrocarbon group having 1 to 6 carbon atoms, and p is a natural number from 1 to 10.

[20] A method for producing a resin composition containing a vinyl chloride polymer (A1), a plasticizer (A2), and a (meth)acrylic copolymer (B), comprising: the (meth)acrylic copolymer (B) is a block copolymer or a graft copolymer containing a polymer (B1) and a polymer (B2), A method for producing a resin composition, wherein the polymer (B1) contains a monomer unit (b1) represented by the following formula (1): [ka] (In formula (1), R 3 represents a hydrogen atom or a methyl group, and R 4 represents an alkylene group having 1 to 4 carbon atoms, and R 5 represents a hydrocarbon group having 1 to 6 carbon atoms, and p is a natural number from 1 to 10.

[21] A method for producing the resin composition according to

[20] , comprising the following step (I): [Process (I)] a step of mixing the resin composition containing the vinyl chloride polymer (A1) and the (meth)acrylic copolymer (B) at 150°C or higher;

[22] A molding material comprising the resin composition according to any one of [1] to

[19] .

[23] An article molded from the molding material described in

[22] .

[24] The article according to

[23] , which comes into contact with plasma proteins. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a resin composition to which proteins are unlikely to adhere and which is suitable for producing an article that comes into contact with proteins, a method for producing a resin composition, a molding material, and an article. The resin composition of the present invention has a protein adhesion inhibitory effect and is suitable for producing articles that come into contact with proteins. The resin composition of the present invention can be obtained by adding a (meth)acrylic block and / or graft copolymer to a polyvinyl chloride resin. A molding material using the resin composition of the present invention and a molded article produced using the molding material can realize a PVC member that is particularly antithrombogenic. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a diagram showing an apparatus for preparing a sample for evaluating blocking resistance. DETAILED DESCRIPTION OF THE INVENTION

[0010] The following definitions of terms apply throughout the specification and claims. "(Meth)acrylic monomer" means a monomer having a (meth)acryloyl group. "(Meth)acryloyl group" is a general term for acryloyl group and methacryloyl group. "(Meth)acrylate" is a general term for acrylate and methacrylate. "(Meth)acrylic acid" is a general term for acrylic acid and methacrylic acid. The symbol "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

[0011] Hereinafter, embodiments of the present invention will be described. The following embodiments are merely examples for explaining the present invention, and are not intended to limit the present invention to these embodiments. The present invention can be implemented in various forms without departing from the spirit of the present invention.

[0012] [Resin composition] A first embodiment of the resin composition of the present invention is a resin composition containing a vinyl chloride polymer (A1), a plasticizer (A2), and a (meth)acrylic copolymer (B).

[0013] <Vinyl chloride polymer (A1)> The resin composition of the present invention contains a vinyl chloride polymer (A1) as an essential component. The vinyl chloride polymer (A1) is not particularly limited as long as it is a polymer containing a vinyl chloride monomer unit, and non-limiting examples of the vinyl chloride polymer (A1) include a homopolymer of vinyl chloride (polyvinyl chloride), a post-chlorinated vinyl chloride polymer (chlorinated polyvinyl chloride), a partially cross-linked vinyl chloride polymer (cross-linked polyvinyl chloride), and a copolymer of vinyl chloride and a vinyl compound copolymerizable with vinyl chloride (vinyl chloride copolymer).

[0014] The average chlorine content of the vinyl chloride polymer (A1) is not particularly limited, but is preferably 56 to 75% by mass of the total mass of the vinyl chloride polymer (A1). The vinyl chloride polymer (A1) is preferably at least one selected from vinyl chloride polymers having an average chlorine content of 56 to 75% by mass and vinyl chloride copolymers obtained by copolymerizing a vinyl chloride polymer with an elastic material and / or an elastomer.

[0015] In the vinyl chloride copolymer, if the content of structural units other than vinyl chloride monomer units increases, the mechanical properties decrease. Therefore, it is preferable that the vinyl chloride monomer units contained in the vinyl chloride copolymer account for 70 mass % or more of the total mass of the vinyl chloride copolymer. In the vinyl chloride copolymer, the vinyl monomer other than vinyl chloride copolymerizable with vinyl chloride may be a monomer having a reactive double bond in the molecule (excluding vinyl chloride). Non-limiting examples of such vinyl monomers include α-olefins such as ethylene, propylene, and butylene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and phenyl (meth)acrylate; aromatic vinyls such as styrene and α-methylstyrene; vinyl halides (excluding vinyl chloride) such as vinylidene chloride and vinyl fluoride; and N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. In the vinyl chloride copolymer, the vinyl monomer other than vinyl chloride that is copolymerizable with vinyl chloride can be used alone or in combination of two or more.

[0016] The average degree of polymerization of the vinyl chloride polymer (A1) is not particularly limited, but is preferably 300 to 5,000, and more preferably 500 to 3,000. When the average degree of polymerization of the vinyl chloride polymer (A1) is 300 or more, the mechanical properties of an article (molded body) obtained by molding a molding material containing the resin composition of the present invention are improved. Furthermore, when the average degree of polymerization of the vinyl chloride polymer (A1) is 5,000 or less, the processability of the resin composition of the present invention is improved.

[0017] The method for producing the vinyl chloride polymer (A1) is not particularly limited, and it can be produced by any method, such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization.

[0018] In the resin composition of the present invention, the vinyl chloride polymer (A1) can be used either individually or in combination of two or more.

[0019] <Plasticizer (A2)> The resin composition of the present invention contains a plasticizer (A2) as an essential component. The plasticizer (A2) is not particularly limited as long as it has good miscibility and compatibility with the vinyl chloride polymer (A1), and any conventionally known plasticizer can be appropriately selected and used. Non-limiting examples of such plasticizers include phthalic acid compounds, terephthalic acid compounds, trimellitic acid compounds, cyclohexanedicarboxylic acid ester compounds, phosphoric acid compounds, adipic acid compounds, citric acid compounds, ether compounds, and polyester compounds.

[0020] Examples of the phthalic acid compounds include dialkyl phthalates such as bis(2-ethylhexyl) phthalate, dioctyl phthalate, diisononyl phthalate, and diisodecyl phthalate; alkylbenzyl phthalates such as butylbenzyl phthalate; alkylaryl phthalates; dibenzyl phthalate; and diaryl phthalates. An example of the terephthalic acid compound is bis(2-ethylhexyl) terephthalate. Examples of the trimellitic acid-based compounds include trialkyl trimellitates such as tris(2-ethylhexyl) trimellitate. An example of the cyclohexanedicarboxylic acid ester compound is diisononyl cyclohexane-1,2-dicarboxylate. Examples of the phosphoric acid compounds include triaryl phosphates such as tricresyl phosphate; trialkyl phosphates; and alkylaryl phosphates. Examples of the adipic acid compound include adipic acid esters. Examples of the citric acid compounds include citrate esters such as acetyl tributyl citrate. Examples of the ether compounds include polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Examples of the polyester compounds include polyesters of dibasic acids such as adipic acid, sebacic acid, or phthalic acid and glycols such as 1,2-propanediol or butanediol.

[0021] The plasticizer (A2) is preferably at least one selected from the group consisting of phthalic acid compounds, terephthalic acid compounds, trimellitic acid compounds, cyclohexanedicarboxylic acid ester compounds, phosphoric acid compounds, adipic acid compounds, citric acid compounds, ether compounds, and polyester compounds, more preferably at least one selected from the group consisting of bis(2-ethylhexyl)phthalate, bis(2-ethylhexyl)terephthalate, tris(2-ethylhexyl)trimellitate, and diisononyl cyclohexane-1,2-dicarboxylate, and even more preferably diisononyl cyclohexane-1,2-dicarboxylate from the viewpoints of the transparency of an article (molded body) obtained by molding a molding material containing the resin composition of the present invention and low migration to other resins.

[0022] In the resin composition of the present invention, the plasticizer (A2) can be used either individually or in combination of two or more.

[0023] In the resin composition of the present invention, the content of the plasticizer (A2) is not particularly limited. In the resin composition of the present invention, the content of the plasticizer (A2) is preferably 10 to 150 parts by mass, more preferably 30 to 150 parts by mass, per 100 parts by mass of the vinyl chloride polymer (A1). In the resin composition of the present invention, when the content of the plasticizer (A2) is 10 parts by mass or more per 100 parts by mass of the vinyl chloride polymer (A1), the interaction between the polymer chains of the vinyl chloride polymer (A1) is sufficiently inhibited, and the distance between the polymer chains of the vinyl chloride polymer (A1) is sufficiently increased, thereby imparting further flexibility. In addition, in the resin composition of the present invention, when the content of the plasticizer (A2) is 150 parts by mass or less per 100 parts by mass of the vinyl chloride polymer (A1), deterioration of the mechanical properties, flame retardancy, and electrical properties of the resin composition of the present invention can be prevented.

[0024] <Stabilizer (A3)> The resin composition of the present invention may contain a stabilizer (A3) as a component other than the vinyl chloride polymer (A1), the plasticizer (A2), and the (meth)acrylic copolymer (B).

[0025] The stabilizer refers to an auxiliary agent that imparts thermal and chemical stability to the vinyl chloride polymer (A1) contained in the resin composition of the present invention during molding and when used as an article.

[0026] Non-limiting examples of the stabilizer (A3) include lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, and lead silicate; metal soap-based stabilizers derived from a metal such as potassium, magnesium, barium, zinc, cadmium, or lead and a fatty acid such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, or behenic acid; organotin-based stabilizers having an alkyl group, an ester group, a fatty acid group, a maleic acid group, or a sulfide-containing group; complex metal soap-based stabilizers such as Ba-Zn-based, Ca-Zn-based, Ba-Ca-Sn-based, Ca-Mg-Sn-based, Ca-Zn-Sn-based, Pb-Sn-based, and Pb-Ba-Ca-based; and metal soap-based stabilizers derived from a metal group such as barium or zinc and a fatty acid such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, or behenic acid. Examples of metal-based stabilizers include metal salt-based stabilizers typically derived from two or more organic acids such as branched fatty acids such as 2-ethylhexanoic acid, isodecanoic acid, and trialkylacetic acid; unsaturated fatty acids such as oleic acid, ricinoleic acid, and linoleic acid; alicyclic acids such as naphthenic acid; and aromatic acids such as carbolic acid, benzoic acid, salicylic acid, and their substituted derivatives; and metal salt liquid stabilizers obtained by dissolving these stabilizers in organic solvents such as petroleum hydrocarbons, alcohols, and glycerin derivatives and further blending them with stabilizing aids such as phosphites, color development inhibitors, transparency improvers, light stabilizers, antioxidants, bleed-out inhibitors, and lubricants.Other examples include non-metallic stabilizers such as epoxy resins, epoxidized vegetable oils, and epoxy compounds such as epoxidized fatty acid alkyl esters; and organic phosphites. In the resin composition of the present invention, the stabilizer (A3) can be used either individually or in combination of two or more.

[0027] The stabilizer (A3) is preferably a complex metal soap-based stabilizer because of its excellent stabilizing effect, and a Ca-Zn-based stabilizer is preferred as the complex metal soap-based stabilizer because it does not contain harmful heavy metals. The Ca-Zn stabilizer is a mixture of a calcium fatty acid salt and a zinc fatty acid salt. Examples of fatty acids constituting the fatty acid salt include behenic acid, stearic acid, lauric acid, oleic acid, palmitic acid, ricinoleic acid, and benzoic acid. The fatty acids can be used alone or in combination of two or more. In the Ca-Zn stabilizer, the ratio of calcium to zinc is preferably 1:2 to 1:3 by mass of the elements. If the ratio of zinc to calcium in the Ca-Zn stabilizer is less than 2, a reddish tinge specific to calcium salts tends to occur. If the ratio of zinc to calcium in the Ca-Zn stabilizer is more than 3, zinc chloride produced during molding may act as a decomposition catalyst for the vinyl chloride polymer (A1), causing rapid blackening and decomposition, commonly known as "zinc burn." In the resin composition of the present invention, the complex metal soap-based stabilizer may be used alone or in combination of two or more.

[0028] The stabilizer (A3) is preferably an epoxy compound because of its low volatility. Examples of the epoxy compounds include epoxidized vegetable oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, epoxidized peanut oil, epoxidized safflower oil, epoxidized grapeseed oil, and epoxidized olive oil. Of the epoxidized vegetable oils, epoxidized soybean oil is preferred in terms of availability. In the resin composition of the present invention, the epoxy compounds can be used alone or in combination of two or more.

[0029] In the resin composition of the present invention, it is preferable to use the composite metal soap-based stabilizer and the epoxy compound in combination, since this has an excellent effect of improving thermal stability.

[0030] In the resin composition of the present invention, the content of the stabilizer (A3) is not particularly limited, but is preferably 1 to 15 parts by mass, more preferably 1 to 8 parts by mass, per 100 parts by mass of the vinyl chloride polymer (A1). In the resin composition of the present invention, when the content of the stabilizer (A3) is 1 part by mass or more per 100 parts by mass of the vinyl chloride polymer (A1), thermal decomposition during processing can be suppressed. In addition, in the resin composition of the present invention, when the content of the stabilizer (A3) is 15 parts by mass or less per 100 parts by mass of the vinyl chloride polymer (A1), deterioration in the mechanical properties of the molded article can be prevented.

[0031] Furthermore, in the resin composition of the present invention, the content of the complex metal soap-based stabilizer is not particularly limited, but is preferably 1 to 14 parts by mass, more preferably 1 to 7 parts by mass, per 100 parts by mass of the vinyl chloride polymer (A1). In the resin composition of the present invention, when the content of the complex metal soap-based stabilizer is 1 part by mass or more per 100 parts by mass of the vinyl chloride polymer (A1), thermal decomposition during processing can be suppressed. In addition, in the resin composition of the present invention, when the content of the complex metal soap-based stabilizer is 14 parts by mass or less per 100 parts by mass of the vinyl chloride-based polymer (A1), deterioration in the mechanical properties of the molded product can be prevented.

[0032] Furthermore, in the resin composition of the present invention, the content of the epoxy compound is not particularly limited, but is preferably 1 to 14 parts by mass, more preferably 1 to 7 parts by mass, per 100 parts by mass of the vinyl chloride polymer (A1). In the resin composition of the present invention, when the content of the epoxy compound is 1 part by mass or more per 100 parts by mass of the vinyl chloride polymer (A1), thermal decomposition during processing can be suppressed. In addition, in the resin composition of the present invention, when the content of the epoxy compound is 14 parts by mass or less per 100 parts by mass of the vinyl chloride polymer (A1), deterioration in the mechanical properties of the molded article can be prevented.

[0033] <(Meth)acrylic copolymer (B)> The resin composition of the present invention contains the (meth)acrylic copolymer (B) as an essential component.

[0034] The (meth)acrylic copolymer (B) is a block copolymer or a graft copolymer containing a monomer unit (b1) represented by the following formula (1).

[0035] [ka]

[0036] In formula (1), R 3 represents a hydrogen atom or a methyl group, and R 4 represents an alkylene group having 1 to 4 carbon atoms, and R 5 represents a hydrocarbon group having 1 to 6 carbon atoms, and p is a natural number from 1 to 10.

[0037] The block and / or graft structure of the (meth)acrylic copolymer (B) may be any of diblock, triblock, multiblock, graft, cyclic, star, comb, dendritic, ladder, etc., or may be a combination of two or more of these structures. Among these structures, it is preferable to have at least one of the diblock, triblock, and graft structures, since this is expected to impart the ability to inhibit protein adhesion to the surface of a molded article and is relatively easy to produce.

[0038] In the resin composition of the present invention, the (meth)acrylic copolymer (B) can be used either individually or in combination of two or more.

[0039] In the resin composition of the present invention, the content of the (meth)acrylic copolymer (B) is not particularly limited. The content of the (meth)acrylic copolymer (B) in the resin composition of the present invention is preferably 90% by mass or less, more preferably 50% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less, based on 100% by mass of the total resin composition of the present invention. When the content of the (meth)acrylic copolymer (B) is 90% by mass or less, based on 100% by mass of the total resin composition of the present invention, deterioration of the mechanical properties of a molded article using the resin composition of the present invention can be further suppressed. Furthermore, the content of the (meth)acrylic copolymer (B) in the resin composition of the present invention is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and even more preferably 7% by mass or more, based on 100% by mass of the total resin composition of the present invention. When the content of the (meth)acrylic copolymer (B) is 1% by mass or more, based on 100% by mass of the total resin composition of the present invention, an article using the resin composition of the present invention can be imparted with better protein adhesion inhibitory ability.

[0040] The (meth)acrylic copolymer (B) preferably has at least one of the structures of a (meth)acrylic block copolymer and / or a (meth)acrylic graft copolymer. The (meth)acrylic block copolymer and the (meth)acrylic graft copolymer may be referred to as a (meth)acrylic block-graft copolymer or a (meth)acrylic block / graft copolymer.

[0041] The (meth)acrylic copolymer (B) is preferably a block copolymer or a graft copolymer containing a polymer (B1) and a polymer (B2).

[0042] (Polymer (B1)) In the (meth)acrylic copolymer (B), the polymer (B1) mainly has the effect of inhibiting protein adhesion.

[0043] Monomer unit (b1) The polymer (B1) preferably contains, as a monomer unit, a monomer unit (b1) represented by the following formula (1).

[0044] [ka]

[0045] In formula (1), R 3 represents a hydrogen atom or a methyl group, and R 4 represents an alkylene group having 1 to 4 carbon atoms, and R 5 represents a hydrocarbon group having 1 to 6 carbon atoms, and p is a natural number from 1 to 10.

[0046] The monomer unit (b1) is a monomer unit derived from the monomer (b'1). Non-limiting examples of the monomer (b'1) include methoxymethyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, methoxybutyl acrylate, ethoxymethyl acrylate, ethoxyethyl acrylate, ethoxypropyl acrylate, ethoxybutyl acrylate, propoxymethyl acrylate, propoxyethyl acrylate, propoxypropyl acrylate, propoxybutyl acrylate, butoxymethyl acrylate, butoxyethyl acrylate, butoxypropyl acrylate, butoxybutyl acrylate, methoxymethyl methacrylate, methoxyethyl methacrylate, methoxypropyl methacrylate, methoxybutyl methacrylate, ethoxymethyl methacrylate, Examples of such methacrylates include acrylate, ethoxyethyl methacrylate, ethoxypropyl methacrylate, ethoxybutyl methacrylate, propoxymethyl methacrylate, propoxyethyl methacrylate, propoxypropyl methacrylate, propoxybutyl methacrylate, butoxymethyl methacrylate, butoxyethyl methacrylate, butoxypropyl methacrylate, butoxybutyl methacrylate, "Blemmer PME-100" (a methoxypolyethylene glycol methacrylate (having two ethylene glycol chains), manufactured by NOF Corporation, trade name), and "Blemmer PME-200" (a methoxypolyethylene glycol methacrylate (having four ethylene glycol chains), manufactured by NOF Corporation, trade name).

[0047] From the viewpoint of suppressing protein adhesion, the monomer (b'1) is preferably at least one selected from the group consisting of methoxymethyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, methoxybutyl acrylate, methoxypolyethylene glycol acrylate, methoxymethyl methacrylate, methoxyethyl methacrylate, methoxypropyl methacrylate, methoxybutyl methacrylate, and methoxypolyethylene glycol methacrylate, more preferably at least one selected from the group consisting of methoxyethyl acrylate, methoxypropyl acrylate, methoxypolyethylene glycol acrylate, and methoxypolyethylene glycol methacrylate, and even more preferably at least one selected from the group consisting of methoxyethyl acrylate and methoxyethyl methacrylate.

[0048] The monomer (b'1) can be used alone or in combination of two or more.

[0049] The reason why the polymer (B1) containing the monomer unit (b1) has the ability to inhibit protein adhesion is thought to be as follows: It is known that the water that hydrates the polymer surface includes free water, which interacts weakly with the polymer, intermediate water, which interacts intermediately with the polymer, and unfrozen water, which interacts strongly with the polymer. The presence of intermediate water on the polymer surface makes it difficult for proteins to adhere to the polymer surface, and as a result, it is thought that the ability to inhibit protein adhesion is imparted. In order to have intermediate water present on the polymer surface, it is thought that it is effective to contain the monomer unit (b1) represented by the formula (1), and among these, it is thought that monomer units based on methoxyethyl acrylate and methoxyethyl methacrylate are particularly effective. The degree of polymerization of the monomer unit (b1) in the polymer (B1) is preferably a natural number of 1 to 1,000,000, and from the viewpoint of suppressing protein adhesion, is more preferably a natural number of 2 to 100,000, and even more preferably a natural number of 5 to 50,000. When the degree of polymerization is 1 or more, the protein adhesion suppression effect is more excellent. Furthermore, when the degree of polymerization is 1,000,000 or less, the moldability is more excellent.

[0050] The polymer (B1) may contain a monomer unit other than the monomer unit (b1). The structural units other than the monomer unit (b1) are monomer units derived from monomers other than the monomer (b'1). The monomer other than the monomer (b'1) can be selected from known monomers without any particular limitation, as long as it is copolymerizable with the monomer (b'1). Examples of the monomer other than the monomer (b'1) include various radically polymerizable monomers.

[0051] The proportion of the monomer unit (b1) in the polymer (B1) is not particularly limited, but is preferably 40% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, particularly preferably 99% by mass or more, and may be 100% by mass, based on 100% by mass of the total of the structural units of the polymer (B1). When the content of the monomer unit (b1) is 40% by mass or more, a protein adhesion inhibitory effect is imparted.

[0052] Monomer unit (b4) The polymer (B1) may further contain a monomer unit (b4) as a monomer unit. The monomer unit (b4) is a monomer unit derived from the monomer (b'4). The monomer (b'4) can be selected from known monomers without any particular limitation, as long as it is copolymerizable with the monomer (b'1). Examples of the monomer (b'4) include various radically polymerizable monomers.

[0053] In the resin composition of the present invention, by combining the vinyl chloride polymer (A1), the plasticizer (A2), and the (meth)acrylic copolymer (B), the surface of a molded article is imparted with excellent low protein adsorption properties derived from the polymer (B1). When imparting low protein adsorption properties to the surface of a molded article by utilizing the properties of the polymer (B1), it is generally necessary to employ a method such as applying a coating material made of the polymer (B1) to the surface. In other words, when using the (meth)acrylic copolymer (B) containing both the polymer (B1) and the polymer (B2) as an additive for imparting functionality to the surface of a molded article, it is expected that a large amount will need to be added. However, as a result of extensive investigations, the inventors have found that in the case of a combination of a vinyl chloride polymer (A1), a plasticizer (A2), and a (meth)acrylic copolymer (B), excellent low protein adsorption properties are exhibited even in the range of the amount of (meth)acrylic copolymer (B) added being small, and have thus completed the present invention. That is, it is believed that in the case of a combination of a vinyl chloride polymer (A1), a plasticizer (A2), and a (meth)acrylic copolymer (B), the polymer (B1) segregates specifically to the surface, thereby exhibiting excellent low protein adsorption performance.

[0054] (Polymer (B2)) In the (meth)acrylic copolymer (B), the polymer (B2) has the effect of imparting miscibility and compatibility with the vinyl chloride polymer (A1) and the effect of making the (meth)acrylic copolymer (B) handleable as a solid.

[0055] The polymer (B2) preferably has a glass transition point (Tg) of 50°C or higher, more preferably 65°C or higher, even more preferably 80°C or higher, and even more preferably 95°C or higher. When the Tg is 50°C or higher, the handleability of the resulting copolymer as a solid is improved. Furthermore, the polymer (B2) preferably has a glass transition point (Tg) of 150°C or lower, more preferably 130°C or lower, and even more preferably 110°C or lower. When the Tg is 150°C or lower, the compatibility of the resulting copolymer with the vinyl chloride polymer (A1) and the miscibility when preparing the resin composition of the present invention are improved.

[0056] Tg refers to a value calculated from the glass transition temperature and mass fraction of a homopolymer by the Fox formula described in Polymer Handbook [Polymer Handbook, J. Brandrup, Interscience, 1989]. The Fox formula is as follows: 1 / (273+Tg)=Σ(Wi / (273+Tgi)) In the formula, Wi is the mass fraction of monomer i, and Tgi is the glass transition temperature (°C) of the homopolymer of monomer i. When a monomer whose homopolymer glass transition temperature is not described in the Polymer Handbook is used, the Tg used is a value measured by a differential scanning calorimeter (DSC).

[0057] Monomer unit (b2) The polymer (B2) preferably contains, as a monomer unit, a monomer unit (b2) represented by the following formula (3).

[0058] [ka]

[0059] In equation (3), R 1 represents a hydrogen atom or a methyl group, and R 2 is OR 33 , halogen atoms, COR 34, COOR 35 ,CN,CONR 36 R 37 or R 38 and R 33 ~R 37 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted non-aromatic heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group, or a substituted or unsubstituted organosilyl group; R 38 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and n is a natural number of 2 to 10,000.

[0060] The monomer unit (b2) is preferably a structural unit derived from a (meth)acrylic acid ester. 1 is preferably a hydrogen atom or a methyl group, and R 2 As COOR 35 is preferred.

[0061] R 33 ~R 37 Examples of the unsubstituted alkyl group include branched or linear alkyl groups having 1 to 22 carbon atoms. Specific examples of branched or linear alkyl groups having 1 to 22 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, i-butyl, pentyl (amyl), i-pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, i-octyl, nonyl, i-nonyl, decyl, i-decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl), i-octadecyl, nonadecyl, icosyl, and docosyl groups.

[0062] R 33 ~R 37Examples of the unsubstituted aryl group include aryl groups having a carbon number of 6 to 18. Specific examples of the aryl group having a carbon number of 6 to 18 include a phenyl group and a naphthyl group. R 33 ~R 37 Examples of the unsubstituted heteroaryl group include heteroaryl groups having 4 to 18 carbon atoms. Specific examples of the heteroaryl group having 4 to 18 carbon atoms include a pyridyl group and a carbazolyl group. R 33 ~R 37 Examples of the unsubstituted non-aromatic heterocyclic group include heterocyclic groups having 4 to 18 carbon atoms. Specific examples of the heterocyclic group having 4 to 18 carbon atoms include oxygen atom-containing heterocyclic groups such as a tetrahydrofuryl group and a tetrahydropyranyl group, and nitrogen atom-containing heterocyclic groups such as a γ-butyrolactone group, an ε-caprolactone group, a pyrrolidinyl group, a pyrrolidone group and a morpholino group. R 33 ~R 37 Examples of the unsubstituted aralkyl group include a benzyl group and a phenylethyl group. R 33 ~R 37 Examples of the unsubstituted organosilyl group include -SiR 17 R 18 R 19 (where R 17 ~R 19 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted aryl group.

[0063] R 17 ~R 19 Examples of the substituted or unsubstituted alkyl group in include the same as those described above, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, a stearyl group, a lauryl group, an isopropyl group, an isobutyl group, an s-butyl group, a 2-methylisopropyl group, and a benzyl group. R 17 ~R 19The substituted or unsubstituted alicyclic group in the formula (I) includes the same as those described above, such as a cyclohexyl group. R 17 ~R 19 The substituted or unsubstituted aryl group in the formula (I) includes the same as those described above, such as phenyl group, p-methylphenyl, etc. R 17 ~R 19 may be the same or different.

[0064] R 33 ~R 37 The substituents of the group include, for example, alkyl groups (where R 33 ~R 37 is an alkyl group having a substituent), an aryl group, -COOR 11 , cyano group, -OR 12 , -NR 13 R 14 , -CONR 15 R 16 , a halogen atom, an allyl group, an epoxy group, a siloxy group, and a group exhibiting hydrophilicity or ionicity. where R 11 ~R 16 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted aryl group.

[0065] The alkyl group and aryl group in the above substituents include the same as the unsubstituted alkyl group and unsubstituted aryl group described above, respectively. -COOR in the above substituents 11 R 11 is preferably a hydrogen atom or an unsubstituted alkyl group. 11 is preferably a carboxy group or an alkoxycarbonyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group. -OR in the above substituents 12 R 12is preferably a hydrogen atom or an unsubstituted alkyl group. 12 is preferably a hydroxy group or an alkoxy group. Examples of the alkoxy group include alkoxy groups having 1 to 12 carbon atoms, and a specific example is a methoxy group. -NR in the above substituents 13 R 14 Examples of the amino group include an amino group, a monomethylamino group, and a dimethylamino group. -CONR in the above substituents 15 R 16 Examples of the alkyl group include a carbamoyl group (-CONH2), an N-methylcarbamoyl group (-CONHCH3), and an N,N-dimethylcarbamoyl group (dimethylamide group: -CON(CH3)2). Examples of the halogen atom in the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrophilic or ionic group in the substituent include cationic substituents such as alkali salts of a carboxy group or alkali salts of a sulfo group, poly(alkylene oxide) groups such as polyethylene oxide groups and polypropylene oxide groups, and quaternary ammonium bases.

[0066] The monomer unit (b2) is a monomer unit derived from the monomer (b'2). Non-limiting examples of the monomer (b'2) include the following monomers:

[0067] Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, hexadecyl (meth)acrylate, (meth)acrylate Hydrocarbon group-containing (meth)acrylic acid esters such as stearyl acrylate, isostearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, terpene acrylate and derivatives thereof, hydrogenated rosin acrylate and derivatives thereof, and docosyl (meth)acrylate.

[0068] Hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerol (meth)acrylate.

[0069] (Meth)acrylic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxypropyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acry carboxyl group-containing vinyl monomers such as trimethyloxypropyl succinate, crotonic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monooctyl maleate, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, monooctyl itaconate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, and monoethyl citraconic acid.

[0070] Vinyl monomers containing an acid anhydride group such as maleic anhydride and itaconic anhydride.

[0071] Unsaturated dicarboxylic acid diester monomers such as dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, dibutyl itaconate, and diperfluorocyclohexyl fumarate.

[0072] Epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate, glycidyl α-ethylacrylate, and 3,4-epoxybutyl (meth)acrylate.

[0073] Amino group-containing (meth)acrylic acid ester vinyl monomers such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.

[0074] Vinyl monomers containing an amide group, such as (meth)acrylamide, dimethyl(meth)acrylamide, diethyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-isopropylacrylamide, hydroxyethylacrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetone acrylamide, maleic acid amide, and maleimide.

[0075] Vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, (meth)acrylonitrile, vinyl chloride, vinyl acetate, and vinyl propionate.

[0076] Divinylbenzene, ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol polyfunctional vinyl monomers such as dipentaerythritol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, allyl (meth)acrylate, triallyl cyanurate, diallyl maleate, polypropylene glycol diallyl ether, and N,N'-methylenebis(meth)acrylamide;

[0077] Heterocyclic monomers such as (meth)acryloylmorpholine, vinylpyrrolidone, vinylpyridine, and vinylcarbazole.

[0078] Polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, isobutoxyethyl (meth)acrylate, t-butoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, acetoxyethyl (meth)acrylate, "Placcel FM" (Daicel Chemical) Caprolactone addition monomer, product name), "Blenmer PME-100" (methoxypolyethylene glycol methacrylate (ethylene glycol chain length: 2), product name, manufactured by NOF Corporation), "Blenmer PME-200" (methoxypolyethylene glycol methacrylate (ethylene glycol chain length: 4), product name, manufactured by NOF Corporation), "Blenmer PME-400" (methoxypolyethylene glycol methacrylate (ethylene glycol chain length: 9), product name, manufactured by NOF Corporation), "Blenmer 50POEP-8 00B" (manufactured by NOF Corporation, octoxy polyethylene glycol-polypropylene glycol-methacrylate (having 8 ethylene glycol chains and 6 propylene glycol chains), trade name), "BLEMMER 20ANEP-600" (manufactured by NOF Corporation, nonylphenoxy (ethylene glycol-polypropylene glycol) monoacrylate, trade name), "BLEMMER AME-100" (manufactured by NOF Corporation, trade name), "BLEMMER AME-200" (manufactured by NOF Corporation, trade name), and "BLEMMER 50AOEP-800B" (manufactured by NOF Corporation, trade name), Glycol ester monomers such as (product name), 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and other silane coupling agent-containing monomers, trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, tri-n-propylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate,Tri-n-amylsilyl (meth)acrylate, tri-n-hexylsilyl (meth)acrylate, tri-n-octylsilyl (meth)acrylate, tri-n-dodecylsilyl (meth)acrylate, triphenylsilyl (meth)acrylate, tri-p-methylphenylsilyl (meth)acrylate, tribenzylsilyl (meth)acrylate, triisopropylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-s-butylsilyl (meth)acrylate, tri-2-methylisopropylsilyl (meth)acrylate Acrylate, tri-tert-butylsilyl (meth)acrylate, ethyldimethylsilyl (meth)acrylate, n-butyldimethylsilyl (meth)acrylate, diisopropyl-n-butylsilyl (meth)acrylate, n-octyldi-n-butylsilyl (meth)acrylate, diisopropylstearylsilyl (meth)acrylate, dicyclohexylphenylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, lauryldiphenylsilyl (meth)acrylate, triisopropylsilylmethyl maleate, triisopropylsilyl amyl maleate, tri-n-butylsilyl-n-butyl maleate, tert-butyldiphenylsilyl methyl maleate, tert-butyldiphenylsilyl-n-butyl maleate, triisopropylsilyl methyl fumarate, triisopropylsilyl amyl fumarate, tri-n-butylsilyl-n-butyl fumarate, tert-butyldiphenylsilyl methyl fumarate, tert-butyldiphenylsilyl-n-butyl fumarate, Silaplane FM-0711 (manufactured by JNC Corporation, trade name), Sila Plain FM-0721 (manufactured by JNC Corporation, trade name), Silaplane FM-0725 (manufactured by JNC Corporation, trade name), Silaplane TM-0701 (manufactured by JNC Corporation, trade name), Silaplane TM-0701T (manufactured by JNC Corporation, trade name), X-22-174ASX (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), X-22-174BX (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), KF-2012 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), X-22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), and X-22-2404 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name),An organosilyl group-containing monomer other than a silane coupling agent-containing monomer.

[0079] Vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, halogenated olefins such as chlorotrifluoroethylene, 2-isocyanatoethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluorophenyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 3-(perfluorobutyl)-2-hydroxypropyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth)acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate fluorine-containing monomers (excluding halogenated olefins) such as 1H,1H,5H-octafluoropentyl (meth)methacrylate, 1H,1H,2H,2H-tridecafluorooctyl (meth)acrylate, 1H-1-(trifluoromethyl)trifluoroethyl (meth)acrylate, 1H,1H,3H-hexafluorobutyl (meth)acrylate, and 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl (meth)acrylate; monomers having an acetal structure such as 1-butoxyethyl (meth)acrylate, 1-(2-ethylhexyloxy)ethyl (meth)acrylate, 1-(cyclohexyloxy)ethyl methacrylate, and 2-tetrahydropyranyl (meth)acrylate; 4-methacryloyloxybenzophenone; and 2-isocyanatoethyl (meth)acrylate.

[0080] As the monomer (b'2), in terms of copolymerizability and the glass transition temperature (Tg) of the polymer (B2), a (meth)acrylic acid ester is preferred, a hydrocarbon group-containing (meth)acrylic acid ester is more preferred, methyl (meth)acrylate is even more preferred, and methyl methacrylate is even more preferred. In addition, in order to impart compatibility between the polymer (B2) and the vinyl chloride polymer (A1), the monomer (b'2) is preferably a (meth)acrylic acid ester, more preferably a hydrocarbon group-containing (meth)acrylic acid ester, even more preferably methyl (meth)acrylate, and even more preferably methyl methacrylate.

[0081] The monomer (b'2) can be used alone or in combination of two or more.

[0082] When methyl methacrylate is used as the monomer (b'2) that is the raw material of the polymer (B2), the content of methyl methacrylate is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, relative to 100% by mass of the total of the monomers (b'2). By containing 50% by mass or more of methyl methacrylate, it becomes easier to adjust the glass transition temperature (Tg) of the polymer (B2) within a preferred range, and compatibility between the (meth)acrylic copolymer (B) and the vinyl chloride polymer (A1) and miscibility when preparing the resin composition of the present invention become good.

[0083] (Polymer (B3)) The (meth)acrylic copolymer (B) may contain a polymer (B3) in addition to the polymer (B1) and the polymer (B2).

[0084] Monomer unit (b3) The polymer (B3) preferably contains, as a monomer unit, a monomer unit (b3) represented by the following formula (4).

[0085] [ka]

[0086] In equation (4), R 8 represents a hydrogen atom or a methyl group, and R 9 are hydrogen atoms, halogen atoms, OH, OR 35 , C.N., N.R. 20 R 21 or R 22and R 20 , R 21 , R 35 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted non-aromatic heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group, or a substituted or unsubstituted organosilyl group; R 22 represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0087] The monomer unit (b3) is a monomer unit derived from the monomer (b'3). Non-limiting examples of the monomer (b'3) include the following monomers:

[0088] Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, hexadecyl (meth)acrylate, (meth)acrylate Hydrocarbon group-containing (meth)acrylic acid esters such as stearyl acrylate, isostearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, terpene acrylate and derivatives thereof, hydrogenated rosin acrylate and derivatives thereof, and docosyl (meth)acrylate.

[0089] hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerol (meth)acrylate; 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxypropyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxypropyl Carboxyl group-containing vinyl monomers such as succinic acid, (meth)acrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monooctyl maleate, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, monooctyl itaconate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, and monoethyl citraconic acid.

[0090] Vinyl monomers containing an acid anhydride group such as maleic anhydride and itaconic anhydride.

[0091] Unsaturated dicarboxylic acid diester monomers such as dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, dibutyl itaconate, and diperfluorocyclohexyl fumarate.

[0092] Epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate, glycidyl α-ethylacrylate, and 3,4-epoxybutyl (meth)acrylate.

[0093] Amino group-containing (meth)acrylic acid ester vinyl monomers such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.

[0094] Vinyl monomers containing an amide group, such as (meth)acrylamide, N-methyl(meth)acrylamide, N,N'-dimethyl(meth)acrylamide, N-isopropylacrylamide, N-(hydroxymethyl)acrylamide, diethyl(meth)acrylamide, hydroxyethylacrylamide, N-butoxymethyl(meth)acrylamide, diacetone acrylamide, maleic acid amide, and maleimide.

[0095] Ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate ) acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, allyl (meth)acrylate, triallyl cyanurate, diallyl maleate, polypropylene glycol diallyl ether, and polyfunctional vinyl monomers such as N,N'-methylenebis(meth)acrylamide.

[0096] Heterocyclic monomers such as (meth)acryloylmorpholine, vinylpyrrolidone, vinylpyridine, and vinylcarbazole.

[0097] Polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, acetoxyethyl (meth)acrylate, "Placcel FM" (product name of caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.), Monomers containing silane coupling agents such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane, trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, tri-n-propylsilyl (meth)acrylate, tri-n-butyl ... Trimethylsilyl (meth)acrylate, tri-n-amylsilyl (meth)acrylate, tri-n-hexylsilyl (meth)acrylate, tri-n-octylsilyl (meth)acrylate, tri-n-dodecylsilyl (meth)acrylate, triphenylsilyl (meth)acrylate, tri-p-methylphenylsilyl (meth)acrylate, tribenzylsilyl (meth)acrylate, triisopropylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate organosilyl group-containing monomers other than silane coupling agent-containing monomers, such as methyl silyl acrylate, tri-s-butylsilyl(meth)acrylate, tri-2-methylisopropylsilyl(meth)acrylate, tri-tert-butylsilyl(meth)acrylate, ethyldimethylsilyl(meth)acrylate, n-butyldimethylsilyl(meth)acrylate, diisopropyl-n-butylsilyl(meth)acrylate, n-octyldi-n-butylsilyl(meth)acrylate, diisopropylstearylsilyl(meth)acrylate, dicyclohexylphenylsilyl(meth)acrylate, tert-butyldiphenylsilyl(meth)acrylate, lauryldiphenylsilyl(meth)acrylate, triisopropylsilylmethylmaleate, triisopropylsilylamylmaleate, tri-n-butylsilyl-n-butylmaleate, tert-butyldiphenylsilylmethylmaleate, and tert-butyldiphenylsilyl-n-butylmaleate.

[0098] 2-Isocyanatoethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluorophenyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 3-(perfluorobutyl)-2-hydroxypropyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth)acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H Fluorine-containing monomers (excluding halogenated olefins) such as 5H-octafluoropentyl (meth)methacrylate, 1H,1H,2H,2H-tridecafluorooctyl (meth)acrylate, 1H-1-(trifluoromethyl)trifluoroethyl (meth)acrylate, 1H,1H,3H-hexafluorobutyl (meth)acrylate, 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl (meth)acrylate, and monomers with an acetal structure such as 1-butoxyethyl (meth)acrylate, 1-(2-ethylhexyloxy)ethyl (meth)acrylate, 1-(cyclohexyloxy)ethyl methacrylate, and 2-tetrahydropyranyl (meth)acrylate.

[0099] 4-Methacryloyloxybenzophenone and 2-isocyanatoethyl (meth)acrylate.

[0100] The monomer (b'3) is preferably at least one selected from the group consisting of the following monomers, from the viewpoint of ease of handling.

[0101] Hydrocarbon group-containing (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, and terpene acrylates and derivatives thereof.

[0102] Hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0103] Carboxyl group-containing vinyl monomers such as (meth)acrylic acid.

[0104] Epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate and glycidyl α-ethylacrylate.

[0105] Amino group-containing (meth)acrylic acid ester vinyl monomers such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.

[0106] Vinyl monomers containing an amide group, such as (meth)acrylamide, N-methyl(meth)acrylamide, N,N'-dimethyl(meth)acrylamide, N-isopropylacrylamide, and N-(hydroxymethyl)acrylamide.

[0107] Polyfunctional vinyl monomers such as ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, allyl (meth)acrylate, and N,N'-methylenebis(meth)acrylamide.

[0108] Heterocyclic monomers such as (meth)acryloylmorpholine, vinylpyrrolidone, vinylpyridine, and vinylcarbazole.

[0109] Silane coupling agent-containing monomers such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; and organosilyl group-containing monomers other than silane coupling agent-containing monomers, such as trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, tri-n-propylsilyl (meth)acrylate, and tri-n-butylsilyl (meth)acrylate.

[0110] Fluorine-containing monomers (excluding halogenated olefins) such as 2,2,2-trifluoroethyl (meth)acrylate and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and monomers with an acetal structure such as 1-butoxyethyl (meth)acrylate and 1-(2-ethylhexyloxy)ethyl (meth)acrylate.

[0111] (Monomer unit (d)) The (meth)acrylic copolymer (B) may further contain a monomer unit (d) derived from a macromonomer. A macromonomer refers to a polymer having a polymerizable functional group. The monomer unit (d) can be introduced into the (meth)acrylic copolymer (B) as a component consisting of a specific polymer by using the macromonomer (d') as a raw material. The monomer unit (d) may be contained in any of the polymer (B1), the polymer (B2), and the polymer (B3). When the macromonomer (d') is used as a raw material for the polymer (B1), the polymerizable functional group of the macromonomer (d') is preferably copolymerizable with the monomer (b'2) that is a raw material for the polymer (B2). Conversely, when the macromonomer (d') is used as a raw material for the polymer (B2), the polymerizable functional group of the macromonomer (d') is preferably copolymerizable with the monomer (b'1) that is a raw material for the polymer (B1).

[0112] The monomer units constituting the macromonomer (d') can be appropriately selected from the group consisting of the monomer units (b1), (b2), and (b3). The raw materials for the macromonomer (d') can be appropriately selected from the group consisting of the monomer (b'1), the monomer (b'), and the monomer (b'3).

[0113] It is preferable to use the macromonomer (d') as a raw material for the polymer (B2) because the macromonomer (d') can be handled as a solid. By using the macromonomer (d') as a raw material for the polymer (B2) and copolymerizing it with the monomer units that are raw materials for the polymer (B1), a (meth)acrylic copolymer can be efficiently produced.

[0114] The radical polymerizable group contained in the macromonomer (d') is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include CH2=C(COOR 6 )-CH2-, (meth)acryloyl group, 2-(hydroxymethyl)acryloyl group, and vinyl group. where R 6represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, or an unsubstituted or substituted non-aromatic heterocyclic group. R 6 Specific examples of the unsubstituted alkyl group, unsubstituted alicyclic group, unsubstituted aryl group, unsubstituted heteroaryl group, unsubstituted non-aromatic heterocyclic group, and the substituents of each group are R 2 COOR as 35 R 35 The same as R 6 As the alkyl group, an unsubstituted or substituted alkyl group or an unsubstituted or substituted alicyclic group is preferred, and an unsubstituted alkyl group or an unsubstituted or alicyclic group having an alkyl group as a substituent is more preferred.

[0115] R 6 is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, or an unsubstituted or substituted non-aromatic heterocyclic group, and from the viewpoint of availability, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopropyl group, a cyclobutyl group, an isobornyl group, and an adamantyl group are preferred, and at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a cyclopropyl group, a cyclobutyl group, an isobornyl group, and an adamantyl group is preferred.

[0116] The macromonomer (d') preferably has a monomer unit having a radical polymerizable group, and the number of the monomer units having a radical polymerizable group is preferably two or more. The macromonomer (d') preferably has two or more of the monomer units (b2).The macromonomer (d') more preferably has a structure represented by the following formula (2).

[0117] [ka]

[0118] In equation (2), R 0 ~R n each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, or an unsubstituted or substituted non-aromatic heterocyclic group; 0 ~R n may be the same or different, and X 1 ~X n represents a hydrogen atom or a methyl group, and multiple X 1 ~X n may be the same or different, Z is a terminal group, and n is a natural number of 2 to 10,000. Examples of Z include a hydrogen atom, a group derived from a radical polymerization initiator, a radical polymerizable group, and the like, similar to the terminal groups of polymers obtained by known radical polymerization. n is 2 to 10,000, and from the viewpoint of moldability, it is preferably 2 to 1,000, more preferably 5 to 1,000, even more preferably 10 to 500, and even more preferably 20 to 500. Z is a terminal group of the macromonomer (d'). Examples of Z include a hydrogen atom, a group derived from a radical polymerization initiator, a radical polymerizable group, and the like, similar to terminal groups of polymers obtained by known radical polymerization.

[0119] R in equation (2) 0 ~R n is a group having an ethylenically unsaturated bond, CH2=C(COOR 6 )-CH2-R 6 is the same as R in the copolymer 6 is preferably an alkyl group, an alicyclic group, an aryl group, a heteroaryl group, or a non-aromatic heterocyclic group, more preferably an alkyl group or an alicyclic group, and even more preferably an alkyl group, from the viewpoint of maintaining hydrophobicity.

[0120] The number average molecular weight (Mn) of the macromonomer (d') is preferably 200 to 100,000, more preferably 500 to 100,000, even more preferably 1,000 to 50,000, and still more preferably 2,000 to 50,000. When the number average molecular weight of the macromonomer (d') is 200 or more and 100,000 or less, the moldability is more excellent. The number average molecular weight of the macromonomer (d') is calculated by gel permeation chromatography (GPC) as a relative molecular weight using polymethyl methacrylate as a standard resin.

[0121] The proportion of the constituent monomer units (b2) relative to the total of all constituent units constituting the macromonomer (d') (100% by mass) is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 100% by mass.

[0122] (Composition and Molecular Weight of (Meth)acrylic Copolymer (B)) The proportion of the monomer units (b1) in the (meth)acrylic copolymer (B) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the total of all structural units constituting the (meth)acrylic copolymer (B). The proportion of the monomer units (b1) in the (meth)acrylic copolymer (B) is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 60% by mass or less, based on 100% by mass of the total of all structural units constituting the (meth)acrylic copolymer (B). When the proportion of the monomer units (b1) in the (meth)acrylic copolymer (B) exceeds 10% by mass, the protein adhesion inhibitory effect is superior, and when it is 90% by mass or less, the moldability is superior.

[0123] The proportion of the monomer units (b2) in the (meth)acrylic copolymer (B) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the total of all structural units constituting the (meth)acrylic copolymer (B). The proportion of the monomer units (b2) in the (meth)acrylic copolymer (B) is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 60% by mass or less, based on 100% by mass of the total of all structural units constituting the (meth)acrylic copolymer (B). A proportion of the monomer units (b2) greater than 10% by mass provides superior moldability, while a proportion of 90% by mass or less provides superior protein adhesion inhibitory effect.

[0124] When the (meth)acrylic copolymer (B) contains the monomer unit (b3), the proportion of the monomer unit (b3) in the (meth)acrylic copolymer (B) is preferably 0 to 33 mass%, more preferably 0 to 25 mass%, and even more preferably 0.5 to 20 mass%, and may be 0 mass%, relative to 100 mass% of the total of all structural units constituting the (meth)acrylic copolymer (B). When the proportion of the monomer unit (b3) in the (meth)acrylic copolymer (B) is 0 to 33 mass%, relative to 100 mass% of the total of all structural units constituting the (meth)acrylic copolymer (B), the functions of the polymers (B1) and (B2) are not impaired.

[0125] The weight-average molecular weight of the (meth)acrylic copolymer (B) is preferably 75,000 or more, more preferably 75,000 to 1,000,000, and even more preferably 80,000 to 500,000. A weight-average molecular weight of 75,000 to 1,000,000 provides excellent moldability. The weight-average molecular weight of the copolymer is calculated by gel permeation chromatography (GPC) as a relative molecular weight using polymethyl methacrylate as a standard resin.

[0126] (Method for producing (meth)acrylic copolymer (B)) Examples of methods for producing the (meth)acrylic copolymer (B) include living polymerization and methods using macromonomers. Examples of living polymerization include living radical polymerization and living anionic polymerization. Examples of living radical polymerization include reversible addition-fragmentation chain transfer polymerization (RAFT), atom transfer radical polymerization (ATRP), nitroxide-mediated polymerization (NMP), and living radical polymerization with organotellurium as a growing terminal (TERP). Methods using macromonomers are advantageous in that they allow the (meth)acrylic copolymer (B) to be produced relatively easily, and are preferred because they do not require the steps of removing catalyst and auxiliary residues and terminal treatment, which are required in living polymerization.

[0127] (Method for producing (meth)acrylic copolymer (B) using macromonomer) In the method for producing the (meth)acrylic copolymer (B) using the macromonomer (d'), the macromonomer (d') may be used as a raw material for any of the polymer (B1), the polymer (B2), and the polymer (B3). Here, as an example, a method for using the macromonomer (d') as a raw material for the polymer (B2) will be described.

[0128] For example, there is a method in which a monomer mixture containing the monomer (b'1) and the macromonomer (d') which is the raw material of the polymer (B2) is subjected to bulk polymerization, suspension polymerization or solution polymerization. A preferred method is to carry out suspension polymerization of a polymerizable composition containing 0.001 to 5 parts by mass of a non-metallic chain transfer agent relative to 100 parts by mass of a monomer mixture. The polymerizable composition preferably contains a dispersant. Suspension polymerization produces copolymers with excellent moldability and ease of processing. Solution polymerization produces copolymers with narrow molecular weight distributions. For example, bead-like copolymers may be recovered from the suspension obtained by suspension polymerization and used to produce molded articles, or the bead-like copolymers may be formed into pellets and used to produce molded articles. For example, the polymer solution obtained by solution polymerization may be dropped into a poor solvent to cause reprecipitation, or the solvent may be removed by degassing extrusion or the like to recover powdered copolymers and use them to produce molded articles, or the powdered copolymers may be formed into pellets and used to produce molded articles.

[0129] Preferred methods for producing the copolymer by suspension polymerization include, for example, the following methods (A), (B) and (C).

[0130] In method (A), macromonomer (d') is dissolved in a monomer other than macromonomer (d') to prepare a monomer mixture, and then a radical polymerization initiator and, if necessary, a non-metallic chain transfer agent are added to the monomer mixture to prepare a polymerizable composition. The polymerizable composition is then dispersed in an aqueous solution containing, if necessary, a dispersant to prepare a syrup dispersion of the polymerizable composition, and the resulting syrup dispersion of the polymerizable composition is subjected to suspension polymerization. In method (A), a syrup is prepared in which the macromonomer particles are completely dissolved in the monomer, which makes it easy to obtain particles with a uniform composition. Therefore, the copolymer obtained by method (A) has excellent mechanical strength when molded.

[0131] In method (B), a syrup dispersion of a monomer mixture is prepared by adding a monomer other than macromonomer (d') to an aqueous suspension in which macromonomer (d') and, if necessary, a dispersant are dispersed. A radical polymerization initiator and, if necessary, a non-metallic chain transfer agent are added to this syrup dispersion of the monomer mixture to prepare a syrup dispersion of a polymerizable composition. The syrup dispersion of the polymerizable composition is then subjected to suspension polymerization. In method (B), the step of recovering the macromonomer (d') can be omitted, thereby shortening the production process. That is, in method (B), a suspension obtained by synthesizing the macromonomer (d') by suspension polymerization is used as the aqueous suspension, and a monomer () can be added to this suspension for copolymerization, thereby omitting the step of recovering the macromonomer (d'). A known method can be used to synthesize the macromonomer (d') by suspension polymerization. In contrast, in method (A), the macromonomer (d') synthesized by suspension polymerization is recovered as particles and used.

[0132] In method (C), macromonomer (d') is dissolved in a monomer other than macromonomer (d') to prepare a monomer mixture, and then a radical polymerization initiator and, if necessary, a non-metallic chain transfer agent are added to the monomer mixture to prepare a polymerizable composition. The polymerizable composition is then dispersed in water to prepare a syrup dispersion of the polymerizable composition. A dispersant is added immediately before polymerization, and the syrup dispersion of the polymerizable composition is then subjected to suspension polymerization. Here, the term "aqueous suspension" means a state in which the monomer and / or syrup is dispersed in water. In method (C), the state of dispersion of the monomer in the system can be stabilized, and therefore particles having a more uniform composition can be more easily obtained than in method (A).

[0133] In any of the above methods (A), (B), and (C), it is preferable to heat the mixture when dissolving the macromonomer (d') in the monomer other than the macromonomer (d'). The heating temperature when dissolving the macromonomer (d') in the monomer other than the macromonomer (d') is preferably 30 to 90°C. A heating temperature of 30°C or higher tends to improve the solubility of the macromonomer (d') in the monomer other than the macromonomer (d'), while a heating temperature of 90°C or lower tends to suppress volatilization of the monomer mixture. The lower limit of the heating temperature is more preferably 35°C or higher. The upper limit of the heating temperature is more preferably 75°C or lower. That is, when dissolving the macromonomer (d') in the monomer other than the macromonomer (d'), the monomer mixture is preferably heated to 30 to 90°C, more preferably 35 to 75°C.

[0134] When a radical polymerization initiator is used in polymerizing a monomer mixture containing macromonomer (d'), the radical polymerization initiator is preferably added after dissolving macromonomer (d') in monomers other than macromonomer (d'). That is, it is preferable to dissolve macromonomer (d') in monomers other than macromonomer (d') to prepare a monomer mixture, and then add the radical polymerization initiator to the monomer mixture.

[0135] The temperature of the monomer mixture when the radical polymerization initiator is added is preferably 0°C or higher and not higher than the temperature obtained by subtracting 15°C from the 10-hour half-life temperature of the radical polymerization initiator used. When the temperature when the radical polymerization initiator is added is 0°C or higher, the solubility of the radical polymerization initiator in monomers other than the macromonomer (d') tends to be good. Furthermore, when the temperature when the radical polymerization initiator is added is not higher than the temperature obtained by subtracting 15°C from the 10-hour half-life temperature of the radical polymerization initiator, polymerization tends to be stable.

[0136] Examples of the radical polymerization initiator include organic peroxides and azo compounds.

[0137] Non-limiting examples of the organic peroxide include 2,4-dichlorobenzoyl peroxide, tert-butyl peroxypivalate, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, tert-butylperoxy-2-ethylhexanoate, cyclohexanone peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, and di-tert-butyl peroxide.

[0138] Non-limiting examples of the azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), and dimethyl 2,2'-azobis(2-methylpropionate).

[0139] As the radical polymerization initiator, in terms of availability, at least one selected from the group consisting of benzoyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), and dimethyl 2,2'-azobis(2-methylpropionate) is preferred.

[0140] The radical polymerization initiators can be used alone or in combination of two or more.

[0141] In terms of controlling heat generated by polymerization, the amount of the radical polymerization initiator added is preferably 0.0001 parts by mass or more and 10 parts by mass or less, and more preferably 0.0005 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the total amount of the macromonomer (d') and the monomers other than the macromonomer (d').

[0142] In the above-mentioned method (A) or method (B), the polymerization temperature when the polymerizable composition is suspension polymerized is not particularly limited, and is generally preferably 50 to 120°C, more preferably 70 to 100°C. The polymerization time is preferably 1 to 6 hours, more preferably 1.5 to 4 hours. The stirring conditions are preferably 100 to 800 rpm, and more preferably 150 to 600 rpm.

[0143] Examples of dispersants used in suspension polymerization include alkali metal salts of poly(meth)acrylic acid, copolymers of alkali metal salts of (meth)acrylic acid and (meth)acrylic acid esters, copolymers of alkali metal salts of (meth)acrylic acid sulfoalkyl and (meth)acrylic acid esters, alkali metal salts of polystyrene sulfonic acid, copolymers of alkali metal salts of styrene sulfonic acid and (meth)acrylic acid esters, and copolymers of alkali metal salts of (meth)acrylic acid, alkali metal salts of (meth)acrylic acid sulfoalkyl, alkali metal salts of styrene sulfonates and (meth)acrylic acid. Examples of suitable copolymers include copolymers of an alkali metal salt of (meth)acrylic acid, an alkali metal salt of a sulfoalkyl (meth)acrylate, and a (meth)acrylic acid ester; copolymers of an alkali metal salt of (meth)acrylic acid, an alkali metal salt of styrenesulfonic acid, and a (meth)acrylic acid ester; copolymers of an alkali metal salt of a sulfoalkyl (meth)acrylate, an alkali metal salt of styrenesulfonic acid, and a (meth)acrylic acid ester; polyvinyl alcohol with a saponification degree of 70 to 100%; methylcellulose; starch; and hydroxyapatite. These may be used alone or in combination. Among these, copolymers of an alkali metal salt of a sulfoalkyl (meth)acrylate and a (meth)acrylic acid ester are preferred because of their excellent dispersion stability during suspension polymerization.

[0144] The dispersant content is preferably 0.005 to 5% by mass, more preferably 0.01 to 1% by mass, based on the total mass of the aqueous suspension. When the content of the dispersant in the aqueous suspension is 0.005% by mass or more, the dispersion stability of the suspension polymerization liquid tends to be good, and the washability, dewaterability, drying ability, and flowability of the resulting polymer tend to be good. Furthermore, when the content of the dispersant is 5% by mass or less, foaming during polymerization tends to be small, and polymerization stability tends to be good.

[0145] To improve the dispersion stability of the aqueous suspension, an electrolyte such as sodium carbonate, sodium sulfate, or manganese sulfate may be added to the aqueous suspension. In this case, the proportion of the electrolyte is preferably 0.01 to 0.5% by mass relative to the total mass of the aqueous suspension in the case of method (A). In addition, the proportion of the electrolyte in the aqueous suspension is preferably 0.01 to 10% by mass in the case of method (B).

[0146] It is preferable to obtain a copolymer by polymerizing a polymerizable composition containing a monomer mixture and a non-metallic chain transfer agent, which will be described later.

[0147] The non-metallic chain transfer agent is added to a monomer mixture when a polymer is obtained, and is preferably added when a polymer is obtained by suspension polymerization. By using the non-metallic chain transfer agent as a chain transfer agent during polymer production, the amount of unreacted macromonomer contained in the polymer can be reduced.

[0148] Examples of the non-metallic chain transfer agent include sulfur-containing chain transfer agents such as t-dodecyl mercaptan and n-octyl mercaptan, α-methylstyrene dimer, carbon tetrachloride, and terpenoids, and sulfur-containing chain transfer agents are preferred because of their easy availability and high chain transfer ability. The content of the non-metallic chain transfer agent is preferably 0.01 to 0.5 parts by mass relative to 100 parts by mass of the total monomer mixture. When the content of the non-metallic chain transfer agent is 0.01 parts by mass or more, the effect of adding the agent is sufficient, and when the content is 0.5 parts by mass or less, the mechanical strength after curing is excellent. The content of the non-metallic chain transfer agent is more preferably 0.03 to 0.3 parts by mass, and even more preferably 0.05 to 0.2 parts by mass.

[0149] Method for producing macromonomer (d') The macromonomer (d') can be produced by a known method. Examples of methods for producing the macromonomer include a method using a cobalt chain transfer agent (U.S. Patent No. 4,680,352), a method using an α-substituted unsaturated compound such as α-bromomethylstyrene as a chain transfer agent (WO 88 / 04304), a method of chemically bonding a polymerizable group (JP-A No. 60-133007, U.S. Patent No. 5,147,952, and JP-A No. 06-298921), and a method using thermal decomposition (JP-A No. 11-240854). Among these, the method for producing the macromonomer (d') is preferably a method using a cobalt chain transfer agent, since it requires fewer production steps and uses a catalyst with a high chain transfer constant.

[0150] Examples of methods for producing the macromonomer (d') using a cobalt chain transfer agent include bulk polymerization, solution polymerization, and aqueous dispersion polymerization methods such as suspension polymerization and emulsion polymerization. Among these, the aqueous dispersion polymerization method is preferred from the viewpoint of simplifying the recovery process of the macromonomer (d').

[0151] As the cobalt chain transfer agent, a cobalt chain transfer agent represented by the following formula (5) can be used. For example, those described in Japanese Patent No. 3587530, JP-A-6-23209, JP-A-7-35411, U.S. Pat. Nos. 45269945, 4694054, 4834326, 4886861, 5324879, WO 95 / 17435, and JP-T-9-510499 can be used.

[0152] [ka]

[0153] In formula (5), R1 to R4 each independently represent an alkyl group, a cycloalkyl group, or an aryl group, and X each independently represent an F atom, a Cl atom, a Br atom, an OH group, an alkoxy group, an aryloxy group, an alkyl group, or an aryl group.

[0154] Specific examples of cobalt chain transfer agents include bis(borondifluorodimethyldioximinocyclohexane)cobalt(II), bis(borondifluorodimethylglyoximate)cobalt(II), bis(borondifluorodiphenylglyoximate)cobalt(II), cobalt(II) complexes of vicinaliminohydroxyimino compounds, cobalt(II) complexes of tetraazatetraalkylcyclotetradecatetraenes, N,N'-bis(salicylidene)ethylenediaminocobalt(II) complexes, cobalt(II) complexes of dialkyldiazadioxodialkyldodecadienes, and cobalt(II) porphyrin complexes. Among these, bis(borondifluorodiphenylglyoximate)cobalt(II) (R 1 ~R 4 X: a phenyl group, and X: a F atom) are preferred. One or more of these can be appropriately selected and used. The amount of the cobalt chain transfer agent used is preferably 5 ppm to 350 ppm relative to 100 parts by mass of the total of the monomers used to obtain macromonomer (d'). If the amount of the cobalt chain transfer agent used is 5 ppm or more, the molecular weight is likely to be sufficiently reduced, and if it is 350 ppm or less, the obtained macromonomer (d') is less likely to be discolored. Examples of solvents used when obtaining macromonomer (d') by solution polymerization include hydrocarbons such as toluene, ethers such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and chloroform, ketones such as acetone, alcohols such as methanol, nitriles such as acetonitrile, vinyl esters such as ethyl acetate, carbonates such as ethylene carbonate, and supercritical carbon dioxide. These can be used alone or in combination of two or more.

[0155] <(Meth)acrylic polymer (P)> The resin composition of the present invention may contain a (meth)acrylic polymer (P) different from the (meth)acrylic copolymer (B). The (meth)acrylic polymer (P) can be used as a processing aid for the vinyl chloride polymer (A1). This processing aid helps to increase the melt viscosity of the vinyl chloride polymer (A1) by loosening the polymer chains during melt-kneading (promoting gelation), and has the effect of facilitating mixing with the plasticizer (A2) and the (meth)acrylic copolymer (B). The proportion of the (meth)acrylic polymer (P) in a total of 100 parts by mass of the vinyl chloride polymer (A1), the (meth)acrylic copolymer (B), and the plasticizer (A2) is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and even more preferably 1 part by mass or more and 5 parts by mass or less.

[0156] The proportion of methyl methacrylate units in 100% by mass of the (meth)acrylic polymer (P) is preferably 30 to 100% by mass, more preferably 50 to 80% by mass. When the proportion of methyl methacrylate units in the (meth)acrylic polymer (P) is 30% by mass or more, the compatibility between the vinyl chloride polymer (A1) and the (meth)acrylic polymer (P) is improved, which helps loosen the polymer chains of the vinyl chloride polymer (A1) and increase the melt viscosity, thereby enabling the (meth)acrylic polymer (P) to function as a processing aid. When the proportion of methyl methacrylate units in 100% by mass of the (meth)acrylic polymer (P) is 100% by mass or less, it is possible to adjust the softening temperature and improve thermal decomposition resistance. In other words, by copolymerizing a monomer unit other than methyl methacrylate with the (meth)acrylic polymer (P), it is possible to balance various performances. For example, copolymerization with an alkyl acrylate such as methyl acrylate, ethyl acrylate, propyl acrylate, or n-butyl acrylate can improve the thermal decomposition resistance of the (meth)acrylic polymer (P) during melt processing, and can adjust the temperature at which the (meth)acrylic copolymer melts.

[0157] Commercially available (meth)acrylic polymers (P) include acrylic polymer processing aids, such as Metablen P type manufactured by Mitsubishi Chemical Corp. Examples of Metablen P type include P-531A, P-530A, P-551A, P-550A, P-501A, and P-570A.

[0158] The amount of the (meth)acrylic polymer (P) added is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, relative to the vinyl chloride polymer (A1). By adding 0.1 part by mass or more, a gelation-promoting effect during processing can be obtained, and by adding 20 parts by mass or less, changes in mechanical properties can be suppressed.

[0159] The (meth)acrylic polymer (P) may be added when preparing the polyvinyl chloride resin (A) by kneading a mixture containing the vinyl chloride polymer (A1) and the plasticizer (A2), or when preparing the resin composition of the present invention by kneading the polyvinyl chloride resin (A) and the (meth)acrylic copolymer (B). Alternatively, the processing aid may be added when preparing the resin composition of the present invention by kneading a mixture containing the vinyl chloride polymer (A1), the plasticizer (A2), and the (meth)acrylic copolymer (B). Furthermore, the processing aid may be added when kneading the mixture containing the vinyl chloride polymer (A1) and the (meth)acrylic copolymer (B), or when mixing the precursor obtained by kneading the vinyl chloride polymer (A1) and the (meth)acrylic copolymer (B) with the plasticizer (A2). That is, the order in which the vinyl chloride polymer (A1), the plasticizer (A2), and the (meth)acrylic copolymer (B) are kneaded can be freely selected depending on the equipment used, miscibility, compatibility, etc., and the processing aid may be added in any step.

[0160] <Anti-blocking particles (Q)> The resin composition of the present invention may contain anti-blocking particles (Q) as needed. A part or all of the anti-blocking particles (Q) may be the above-mentioned (meth)acrylic polymer (P). The anti-blocking particles (Q) are used to impart anti-blocking properties to the raw materials used in the resin composition of the present invention, the resin composition of the present invention, molding materials comprising the resin composition of the present invention, and molded articles thereof. In particular, they are preferably used to prevent blocking of pellets, beads, powder, etc. In particular, the anti-blocking particles (Q) can be used to prevent the particles of the (meth)acrylic copolymer (B) from blocking. That is, it is preferable to add the anti-blocking particles (Q) when the (meth)acrylic copolymer (B) is produced by suspension polymerization and recovered as beads. The anti-blocking particles (Q) may be added in the form of a polymer slurry obtained by suspension polymerization, or in the process of dehydrating the polymer slurry or the process of recovering the beads after dehydration.

[0161] The anti-blocking particles (Q) adsorb to the surface of the (meth)acrylic copolymer (B) and have the effect of preventing blocking. The proportion of the anti-blocking particles (Q) per 100 parts by mass of the (meth)acrylic copolymer (B) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more. Furthermore, the amount of the anti-blocking particles (Q) added per 100 parts by mass of the (meth)acrylic copolymer (B) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less. When the amount of the anti-blocking particles (Q) added is 0.01 parts by mass or more, the powder has excellent fluidity and is easy to handle, while when it is 50 parts by mass or less, the performance of the (meth)acrylic copolymer (B) is not impaired.

[0162] The particle size of the anti-blocking particles (Q), as measured using a particle size distribution analyzer, is preferably 35% or less, more preferably 20% or less, even more preferably 10% or less, and particularly preferably 5% or less, of the median diameter of the (meth)acrylic copolymer (B). The particle size of the anti-blocking particles (Q), as measured using a particle size distribution analyzer, is preferably 0.1% or more, more preferably 0.2% or more, even more preferably 0.3% or more, and particularly preferably 0.5% or more, of the median diameter of the (meth)acrylic copolymer (B). If the particle size of the anti-blocking particles (Q), as measured using a particle size distribution analyzer, is 35% or less, or 0.1% or more, of the median diameter of the (meth)acrylic copolymer (B), the powder has excellent fluidity and is easy to handle. The median diameter refers to the median value when particle size data are arranged in order from minimum to maximum.

[0163] Examples of the anti-blocking particles (Q) include powders of (meth)acrylic polymers such as the (meth)acrylic polymer (P), particles made of vinyl chloride polymers, inorganic fine particles such as silica, etc. Among these, powders of (meth)acrylic polymers such as the (meth)acrylic polymer (P) or particles made of vinyl chloride polymers are preferably used. Examples of vinyl chloride polymers include fine particles produced by suspension polymerization or emulsion polymerization. Among these, fine particles produced by emulsion polymerization are particularly suitable as anti-blocking particles (Q) because they have a small particle size of 1 to 200 μm.

[0164] <Other ingredients> The resin composition of the present invention may contain other components as needed, such as a mold release agent, an antioxidant, an impact modifier, a flexibility modifier, a weather resistance modifier, a colorant, an inorganic pigment, an organic pigment, carbon black, ferrite, an electrical conductivity modifier, an ultraviolet absorber, an infrared absorber, a lubricant, an inorganic filler, a reinforcing agent, an antiplasticizer, a neutralizing agent, a crosslinking agent, a flame retardant, an antiseptic, an insect repellent, an aromatic, a radical scavenger, a sound absorbing material, a core-shell rubber, and other polymers.

[0165] Examples of lubricants include pure hydrocarbon-based lubricants such as liquid paraffin, natural paraffin, microwax, synthetic paraffin, and low-molecular-weight polyethylene; halogenated hydrocarbon-based lubricants; fatty acid-based lubricants such as higher fatty acids and oxyfatty acids; fatty acid amide-based lubricants such as fatty acid amides and bisfatty acid amides; ester-based lubricants such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, and fatty alcohol esters of fatty acids (ester waxes); as well as metal soaps, fatty alcohols, polyhydric alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, partial esters of fatty acids and polyglycols and polyglycerols, and silicone oils, and these can be used alone or in combination of two or more.

[0166] Among these, the lubricants are preferably used because they are effective in improving moldability. In terms of availability, pure hydrocarbon lubricants, fatty acid amide lubricants, and silicone oils are preferred.

[0167] The amount of lubricant added is not particularly limited, but is preferably 0.1 to 15 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the vinyl chloride polymer (A1). By adding 0.1 part by mass or more, adhesion of the resin composition to the molding machine can be reduced, and by adding 15 parts by mass or less, deterioration of processability can be prevented.

[0168] Examples of other polymers include (meth)acrylic resins such as PMMA, polyolefins, polystyrene, polyamides, polyurethanes, unsaturated polyesters, saturated polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonates, silicone resins, epoxy resins, polyether ether ketone, and polyvinylidene fluoride. As other polymers, thermoplastic resins are preferred.

[0169] <Method of manufacturing resin composition> The resin composition of the present invention, which contains a vinyl chloride polymer (A1), a plasticizer (A2), and a (meth)acrylic copolymer (B) that is a block copolymer or a graft copolymer containing a polymer (B1) and a polymer (B2), can be produced, for example, by a production method including the following step (I): [Step (I)] A step of mixing a resin composition containing the vinyl chloride polymer (A1) and the (meth)acrylic copolymer (B) at 150°C or higher.

[0170] The resin composition of the present invention can also be produced using, for example, a polyvinyl chloride resin (A) containing a vinyl chloride polymer (A1) and a plasticizer (A2). This polyvinyl chloride resin (A) is a resin composition containing a vinyl chloride polymer (A1) and a plasticizer (A2) but not a (meth)acrylic copolymer (B). The resin composition of the present invention can be produced by first preparing the polyvinyl chloride resin (A) and then mixing it with the (meth)acrylic copolymer (B). As an alternative method, the resin composition of the present invention can be prepared from a mixture containing the vinyl chloride polymer (A1), the plasticizer (A2), and the (meth)acrylic copolymer (B) without using the polyvinyl chloride resin (A).

[0171] <Another embodiment> Another embodiment of the resin composition of the present invention is a resin composition containing the (meth)acrylic copolymer (B) and the anti-blocking particles (Q).

[0172] In this embodiment, the (meth)acrylic copolymer (B) is a block copolymer or a graft copolymer containing the polymer (B1) and the polymer (B2), and the polymer (B1) contains a monomer unit (b1) represented by the following formula (1):

[0173] [ka]

[0174] In formula (1), R 3 represents a hydrogen atom or a methyl group, and R4 represents an alkylene group having 1 to 4 carbon atoms, and R 5 represents a hydrocarbon group having 1 to 6 carbon atoms, and p is a natural number from 1 to 10.

[0175] In this embodiment, the proportion of the anti-blocking particles (Q) is 0.1 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the (meth)acrylic copolymer (B), and the median diameter of the anti-blocking particles (Q) measured using a particle size distribution analyzer is 35% or less of the median diameter of the (meth)acrylic copolymer (B).

[0176] [Molding material] The resin composition of the present invention can be used as a molding material. As a molding method, in addition to extrusion molding using a kneading extruder such as a single-screw extruder or a twin-screw extruder, it can also be applied to conventional molding methods such as injection molding, blow molding, and roll processing to obtain various desired molded articles.

[0177] There are no particular restrictions on the shape of the molding material, but when it is envisaged that the molding material will be used to melt-mold a molded body, it is preferable to melt-knead the copolymer, other polymers, and other components to be blended as needed in advance and process them into pellets or beads.

[0178] The content of the (meth)acrylic copolymer (B) relative to the total mass of the molding material is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and even more preferably 7% by mass or more. The content of the (meth)acrylic copolymer (B) relative to the total mass of the molding material is preferably 90% by mass or less, more preferably 50% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less. When the content is 1% by mass or more and 90% by mass or less, excellent protein adhesion inhibitory ability is achieved.

[0179] From the viewpoint of transparency of the molded article, the haze value of a 1 mm thick test piece obtained by molding the resin composition of the present invention, measured in accordance with Japanese Industrial Standard JIS K 7136: 2000, is preferably 0% to 90% or less, more preferably 0% to 70% or less, even more preferably 0% to 50% or less, and even more preferably 0% to 30% or less. When the haze value is 90% or less, sufficient transparency is obtained.

[0180] The molding material of the present invention can be used by appropriately selecting a general method for producing polyvinyl chloride molding materials. Furthermore, the production of the molding material and the production of the molded article described below may be carried out in separate steps or may be carried out continuously. In the method for producing the molding material of the present invention, the production process for the molding material can be assembled by combining production equipment such as a Henschel mixer, Banbury mixer, V-type mixer, ribbon blender, planetary mixer, super mixer, tumbler, single-screw extruder, twin-screw extruder, multi-screw extruder, co-kneader, planetary gear extruder, plasticator, and roll kneader. Various packaging methods can be used for molding materials to prevent the inclusion or adsorption of foreign matter, or the absorption of unnecessary gases. For example, various clean packaging methods can be used to prevent the inclusion of foreign matter. Various coatings can be applied to packaging materials to impart gas barrier properties. When producing a molding material, the order in which the vinyl chloride polymer (A1), plasticizer (A2), and acrylic copolymer (B) contained in the resin composition of the present invention are mixed is not particularly limited. Furthermore, the stabilizer (A3), (meth)acrylic polymer (P), anti-blocking particles (Q), and other components, which are used as needed, may also be added in any step. Each component can be added in portions at each step and / or the temperature conditions during mixing can be adjusted. Regarding the order of mixing, it is preferable to knead the vinyl chloride polymer (A1) and the plasticizer (A2) first from the viewpoint of workability. The (meth)acrylic copolymer (B) used in the resin composition of the present invention may be kneaded in advance in a separate process and then pelletized. For this pelletization, an extruder such as a single-screw extruder, a twin-screw extruder, or a multi-screw extruder is preferably used. When pelletizing the (meth)acrylic copolymer (B) using an extruder, it is preferable to perform devolatilization. For the purpose of removing impurities by devolatilization, water or alcohol can be added to the (meth)acrylic copolymer (B) to be fed into the extruder to increase the efficiency of devolatilization. When producing a molding material using the resin composition of the present invention, the raw materials—vinyl chloride polymer (A1), plasticizer (A2), stabilizer (A3), polyvinyl chloride resin (A), (meth)acrylic copolymer (B), and other components—must be kept optimally dry. For example, they may contain water and / or organic solvents to remove impurities during melt-kneading. Conversely, thorough pre-drying may be beneficial to prevent deterioration during kneading. The moisture content of the raw materials is preferably 0.01 to 5%, more preferably 0.5 to 3%, and particularly preferably 1 to 2%. A moisture content of 0.1% or more is expected to reduce the impurity concentration during kneading, while a moisture content of 5% or less can suppress deterioration of the resin composition.

[0181] [Uses of resin composition] As will be shown in the examples below, the resin composition of the present invention has excellent moldability and has a protein adhesion inhibitory effect, making it suitable for producing articles that come into contact with proteins. It is particularly suitable for producing articles that come into contact with plasma proteins. The resin composition of the present invention is suitable as a molding material. When a molding material containing the resin composition is molded, an article (molded body) that has a protein adhesion inhibitory effect is obtained.

[0182] The molding material of the present invention has a protein adhesion inhibiting function, and in the following protein adhesion test (2), 2 The fibrinogen adsorption amount per particle is preferably 1.25 μg or less, and more preferably 1.10 μg or less.

[0183] (Protein adhesion test: μBCA method) The test material was immersed in a 1 mg / mL fibrinogen (FB) solution dissolved in phosphate-buffered saline (PBS) at 37°C for 2 hours. After immersion for 2 hours, the material was washed with PBS, then immersed in 6 mL of sodium dodecyl sulfate aqueous solution and ultrasonically cleaned for 5 minutes. 150 μL of the ultrasonically cleaned solution was placed in a 96-well plate, and 150 μL of protein quantification reagent from a commercially available BCA kit was added to the same well. The plate was then incubated at 37°C for 2 hours. After 2 hours, the absorbance at 562 nm was measured using a plate reader, and the amount of FB adsorption was calculated by applying the result to a calibration curve obtained from an FB solution of known concentration.

[0184] [Molded body] Examples of the shape of the article (molded body) include a sheet, a film, a tube, and a three-dimensional shape. Furthermore, the surface of the molded body may be a mirror finish, or one or both sides may be textured with a textured or matte finish. A protective film or separator may be placed on the surface of the molded body. Various powders may be attached to the surface to prevent blocking.

[0185] <Method of manufacturing molded body> The method for producing an article (molded body) by molding the molding material is preferably a melt molding method, such as injection molding, compression molding, blow molding, extrusion molding, rotational molding, casting, and solvent casting. Of these, injection molding and extrusion molding are preferred from the viewpoint of productivity. There are no particular limitations on the mold, resin temperature, molding conditions, etc., used when molding using the molding machine. When producing a molded body, as with the production of the molding material described above, it is preferable to pre-dry the molding material at an appropriate temperature and time to ensure that the moisture content of the molding material is within an appropriate range. If the temperature is too low or the time is too short, problems such as foaming and / or poor appearance may occur when melt-molding a molding material containing volatile components. Conversely, if the pre-drying temperature is too high or the time is too long, thermal degradation of the molding material may occur, resulting in a decrease in the physical properties and / or discoloration of the molded body.

[0186] <Processing using molded bodies> The molded article can be bonded or welded to other parts, or sheets, films, or tubes can be bonded or fused together to produce various products. Methods for welding molded articles using the resin composition of the present invention include ultrasonic welding, vibration welding, high-frequency welding, hot plate welding, laser welding, and spin welding. The molded article can be bonded using various adhesives, such as epoxy resins, vinyl acetates, acrylic resins, phenolic resins, chloroprene rubbers, nitrile rubbers, silicone rubbers, styrene butadiene rubbers, and cyanoacrylates. Solvent bonding can also be used. Tape bonding, such as double-sided tape, can also be used. When bonding different materials together, it is possible to combine a plurality of bonding methods depending on the materials to be bonded.

[0187] The article (molded body) is preferably an article that comes into contact with protein-containing body fluids (blood, digestive fluid, exudate, etc.), and is preferably used as the inner layer of a multilayer film that comes into contact with plasma proteins, antibody drugs, or biopharmaceuticals. Examples of articles that come into contact with plasma proteins include medical instruments such as scalpels, tweezers, contact lenses, cannulas, catheters, syringes, intravenous lines, intravenous bags, infusion bags, blood bags, stents, and endoscopes; biochemical instruments such as pipette tips, petri dishes, cells, microplates, storage bags, plates, reagent storage containers, tubes, and flasks; and cell therapy devices such as mixers, bioreactors, and jar fermenters. Examples of articles that come into contact with proteins other than plasma proteins include cell culture dishes, cell culture cells, cell culture microplates, cell culture bags, cell culture plates, cell culture tubes, cell culture flasks, biopharmaceutical dishes, biopharmaceutical cells, biopharmaceutical microplates, biopharmaceutical plates, biopharmaceutical tubes, biopharmaceutical bags, biopharmaceutical containers, biopharmaceutical syringes, biopharmaceutical flasks, antibody pharmaceutical dishes, antibody pharmaceutical cells, antibody pharmaceutical microplates, antibody pharmaceutical plates, antibody pharmaceutical tubes, antibody pharmaceutical bags, antibody pharmaceutical containers, antibody pharmaceutical syringes, antibody pharmaceutical flasks, blood bags (whole blood, plasma, platelets, red blood cells), blood product vials, blood product bags, shunt tubes, indwelling needles, drains, etc. [Example]

[0188] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples, "parts" means "parts by mass."

[0189] [GPC measurement] Mw and Mn were determined using gel permeation chromatography (GPC) under the following measurement conditions: Device: HLC-8220 (Tosoh Corporation) Column: TSK GUARD COLUMN SUPER HH (4.6 x 35 mm, Tosoh Corporation) and two TSK-GEL SUPER HM-H (6.0 x 150 mm, Tosoh Corporation) connected in series Eluent: tetrahydrofuran Measurement temperature: 40℃ Flow rate: 0.6mL / min Mw (mass average molecular weight) and Mn (number average molecular weight) were calculated using a calibration curve prepared using four types of polymethyl methacrylate (Mp (peak molecular weight) = 141,500, 55,600, 11,100, and 1,590) manufactured by Polymer Laboratories. The molecular weight distribution was calculated using the formula "molecular weight distribution = (mass average molecular weight) / (number average molecular weight)".

[0190] [Transparency Assessment] The haze value of a 1 mm thick test piece was measured in accordance with Japanese Industrial Standard JIS K7136.

[0191] [Blocking resistance] Figure 1 shows the equipment used to prepare samples for evaluating blocking resistance. 20 g of sample was placed in a cylindrical case 2 with a bottom lid 1, and a top lid 3 was placed on top of the sample. A 5 kg weight 5 was placed on top of the case 2 with a weight stand 4, and the load (pressure: 20 kPa / cm) of the weight 5 was applied to the sample. 2 The sample preparation equipment was placed in a gear oven at 50°C and heated for 6 hours while applying a pressure of 1.4 mm to create a block-shaped sample. After the sample was prepared, it was cooled to room temperature and then placed on a #12 mesh (1.4 mm opening) sieve using a shaker and shaken at regular intervals. The sample block was broken down by shaking, and the time and amount of broken block (amount of powder in the tray) were measured at regular intervals. The time until 50% of the block (10 g) broke was defined as the 50% crushing time, and blocking resistance was evaluated.

[0192] <Production Example 1: Synthesis of Dispersant (1)> A reactor equipped with a stirrer, a condenser, and a thermometer was charged with 61.6 parts of a 17% by mass aqueous solution of potassium hydroxide, 19.1 parts of methyl methacrylate, and 19.3 parts of deionized water. The liquid in the reactor was then stirred at room temperature, and after confirming the exothermic peak, the mixture was stirred for 4 hours. The reaction liquid in the reactor was then cooled to room temperature to obtain an aqueous solution of potassium methacrylate. Next, 900 parts of deionized water, 70 parts of a 42% by weight aqueous solution of sodium 2-sulfoethyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester SEM-Na), 16 parts of the above potassium methacrylate aqueous solution, and 7 parts of methyl methacrylate were added to a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, and the mixture was stirred. While the atmosphere inside the polymerization apparatus was replaced with nitrogen, the temperature of the liquid in the reaction apparatus was raised to 50°C. 0.053 parts of V-50 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: 2,2'-azobis(2-methylpropionamidine) dihydrochloride) was added as a polymerization initiator to the polymerization apparatus, and the temperature of the liquid in the reaction apparatus was raised to 60°C. After adding the polymerization initiator, 1.4 parts of methyl methacrylate was added in five increments (total amount of methyl methacrylate: 7 parts) every 15 minutes. Thereafter, the liquid in the polymerization apparatus was kept at 60° C. for 6 hours while being stirred, and then cooled to room temperature to obtain a dispersant (1) in the form of a transparent aqueous solution with a solid content of 8% by mass.

[0193] <Production Example 2: Synthesis of Chain Transfer Agent (1)> In a synthesis apparatus equipped with a stirrer, 2.00 g (8.03 mmol) of cobalt(II) acetate tetrahydrate (Fujifilm Wako Pure Chemical Industries, Ltd., special grade), 3.86 g (16.1 mmol) of diphenylglyoxime (Tokyo Chemical Industry Co., Ltd., EP grade), and 100 ml of diethyl ether previously deoxygenated by nitrogen bubbling were placed under a nitrogen atmosphere and stirred at room temperature for 2 hours. Next, 20 ml of boron trifluoride diethyl ether complex (Tokyo Chemical Industry Co., Ltd., EP grade) was added and stirred for an additional 6 hours. The resulting mixture was filtered, the solid was washed with diethyl ether, and dried at 100 MPa or less at 20°C for 12 hours to obtain a brown solid chain transfer agent (1). 5.02 g (7.93 mmol, yield 99% by mass) was obtained.

[0194] <Production Example 3: Synthesis of Macromonomer (d'-1)> A polymerization apparatus equipped with a stirrer, a condenser, and a thermometer was charged with 135 parts of deionized water, 0.1 parts of sodium sulfate (Na2SO4), and 0.26 parts by mass of the dispersant (1) (solid content 10% by mass) produced in Production Example 1, and the mixture was stirred to prepare a uniform aqueous solution. Next, 95 parts of methyl methacrylate, 5 parts of methyl acrylate, 0.0010 parts by mass of the chain transfer agent (1) produced in Production Example 2, and 0.1 parts by mass of Perocta O (manufactured by NOF Corporation, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, trade name) as a polymerization initiator were added to prepare an aqueous dispersion. The atmosphere inside the polymerization reactor was then thoroughly purged with nitrogen, and the aqueous dispersion was heated to 80°C and maintained there for 3 hours, then heated to 90°C and maintained there for 2 hours. The reaction solution was then cooled to 40°C to obtain an aqueous suspension of a macromonomer. This aqueous suspension was filtered through a filter cloth, and the filtrate was washed with deionized water and dried at 40°C for 16 hours to obtain macromonomer (d'-1). The Mw of macromonomer (d'-1) was 36,000, and the Mn was 15,000.

[0195] <Production Example 4: (Meth)acrylic copolymer (B-1)> A reactor equipped with a stirrer, a condenser, and a thermometer was charged with 145 parts of deionized water, 0.36 parts of sodium sulfate, 1.25 parts of the dispersant (1) produced in Production Example 1, 40 parts of the macromonomer (d'-1) produced in Production Example 3, 60 parts of methoxyethyl acrylate (Osaka Organic Chemical Industry Co., Ltd.), and 0.2 parts of n-octyl mercaptan (Kanto Chemical Co., Ltd., trade name), and the mixture was heated to 55°C with stirring to obtain a composition in a syrup dispersion state. After cooling the composition to below 40°C, 0.12 parts of V601 (Fujifilm Wako Pure Chemical Industries, Ltd., dimethyl 2,2'-azobis(2-methylpropionate), trade name) was dissolved in the composition, and the syrup dispersion state was polymerized. A sexual composition was obtained.

[0196] Next, the temperature of the syrup dispersion was raised to 75°C and maintained at that temperature for 2 hours, and then raised to 85°C and maintained at that temperature for 90 minutes.

[0197] The suspension was cooled to below 40°C, filtered, and the residue was washed with deionized water and dried at 70°C for 12 hours to obtain (meth)acrylic copolymer (B-1). The resulting copolymer had an Mn of 56,000 and an Mw of 300,000.

[0198] <Production Example 5: Polyvinyl chloride resin (A-1)> 100 parts of TK-1300 (manufactured by Shin-Etsu Chemical Co., Ltd., average degree of polymerization 1300, average chlorine content 57% by mass) as a vinyl chloride polymer (A1), 50 parts of DOP (bis(2-ethylhexyl) phthalate, manufactured by J-Plus Corporation) as a plasticizer (A2), 2.0 parts of epoxidized vegetable oil (ADK STAB O-130P, manufactured by ADEKA Corporation) as a stabilizer (A3), 3.0 parts of a Ca-Zn stabilizer (ADK STAB 37, manufactured by ADEKA Corporation) as a stabilizer (A3), and 1.0 part of a lubricant (LOXIOL VPN233, manufactured by Emery Oleochemicals Japan Co., Ltd.) were supplied to a Henschel mixer and uniformly mixed to obtain a polyvinyl chloride resin (A-1).

[0199] Example 1 A resin composition prepared by mixing 90 parts of the polyvinyl chloride resin (A-1) obtained in Production Example 5 and 10 parts of the (meth)acrylic copolymer (B-1) obtained in Production Example 4 was fed into a 25 mm diameter single-screw extruder (manufactured by Thermo Plastics Industries Co., Ltd., screw rotation speed: 60 rpm) equipped with a T-die (width 10 cm, gap 1.0 mm), and extrusion and film formation were carried out at a resin temperature of 170°C. The obtained molded article was subjected to a fibrinogen (FB) adhesion test using the protein adhesion test (μBCA method) described above. The test results are shown in Table 1.

[0200] <Example 2> The same procedure as in Example 1 was repeated, except that the amount of polyvinyl chloride resin (A-1) obtained in Production Example 5 was changed to 80 parts, and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 20 parts. The results are shown in Table 1.

[0201] <Comparative Example 1> The same procedure as in Example 1 was repeated, except that the amount of polyvinyl chloride resin (A-1) obtained in Production Example 5 was changed to 100 parts, and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 0 parts. The results are shown in Table 1.

[0202] <Production Example 6: Polyvinyl chloride resin (A-2)> 100 parts of TH-2500 (manufactured by Taiyo Vinyl Corporation) as a vinyl chloride polymer (A1), 50 parts of DOP (bis(2-ethylhexyl) phthalate, manufactured by J-Plus Corporation) as a plasticizer (A2), 10.0 parts of epoxidized vegetable oil (ADK STAB O-130P, manufactured by ADEKA Corporation) as a stabilizer (A3), 2.5 parts of a Ca-Zn stabilizer (ADK STAB 37, manufactured by ADEKA Corporation) as a stabilizer (A3), and 1.0 part of ADK STAB SC-2966 (manufactured by ADEKA Corporation) as an additional additive were fed into a Super Mixer (manufactured by Kawata Corporation, a high-speed fluid mixer) and mixed uniformly to obtain polyvinyl chloride resin (A-2).

[0203] <Production Example 7: Polyvinyl chloride resin (A-3)> The same procedure as in Production Example 6 was carried out, except that 54 parts of DOTP (bis(2-ethylhexyl) terephthalate, manufactured by J-Plus Co., Ltd.) was used as the plasticizer (A2), to obtain a polyvinyl chloride resin (A-3).

[0204] <Production Example 8: Polyvinyl chloride resin (A-4)> A polyvinyl chloride resin (A-4) was obtained in the same manner as in Production Example 6, except that 54 parts of DINCH (manufactured by BASF) was used as the plasticizer (A2).

[0205] Example 3 97 parts of the polyvinyl chloride resin (A-2) obtained in Production Example 6 and 3 parts of the (meth)acrylic copolymer (B-1) obtained in Production Example 4 were hand-blended at room temperature, charged into a Banbury mixer, and discharged at 155°C to obtain a resin composition. The obtained resin composition was rolled into a sheet using a mill roll set at 150°C, and then pelletized using a sheet pelletizer (manufactured by Horai Co., Ltd.). The obtained pellets were treated in the same manner as in Example 1 to obtain a film-like molded product. The obtained molded product was subjected to a fibrinogen (FB) adhesion test and transparency evaluation using the protein adhesion test (μBCA method) described above. The test results are shown in Table 2.

[0206] Example 4 The same procedure as in Example 3 was repeated, except that the amount of polyvinyl chloride resin (A-2) obtained in Production Example 6 was changed to 95 parts, and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 5 parts. The results are shown in Table 2.

[0207] <Example 5> The same procedure as in Example 3 was repeated, except that the amount of polyvinyl chloride resin (A-2) obtained in Production Example 6 was changed to 93 parts, and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 7 parts. The results are shown in Table 2.

[0208] Example 6 The same procedure as in Example 3 was repeated, except that the amount of polyvinyl chloride resin (A-2) obtained in Production Example 6 was changed to 90 parts, and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 10 parts. The results are shown in Table 2.

[0209] Example 7 The same procedure as in Example 3 was repeated, except that the polyvinyl chloride resin (A-2) obtained in Production Example 6 was replaced with the polyvinyl chloride resin (A-3) obtained in Production Example 7, and the results are shown in Table 2.

[0210] Example 8 The same procedure as in Example 7 was repeated, except that the amount of polyvinyl chloride resin (A-3) obtained in Production Example 7 was changed to 95 parts, and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 5 parts. The results are shown in Table 3.

[0211] Example 9 The same procedure as in Example 7 was repeated, except that the amount of polyvinyl chloride resin (A-3) obtained in Production Example 7 was changed to 93 parts, and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 7 parts. The results are shown in Table 3.

[0212] Example 10 The same procedure as in Example 7 was repeated, except that the amount of polyvinyl chloride resin (A-3) obtained in Production Example 7 was changed to 90 parts, and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 10 parts. The results are shown in Table 3.

[0213] Example 11 The same procedure as in Example 3 was repeated, except that the polyvinyl chloride resin (A-2) obtained in Production Example 6 was replaced with the polyvinyl chloride resin (A-4) obtained in Production Example 8, and the results are shown in Table 4.

[0214] Example 12 The same procedure as in Example 11 was repeated, except that the amount of polyvinyl chloride resin (A-4) obtained in Production Example 8 was changed to 95 parts, and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 5 parts. The results are shown in Table 4.

[0215] Example 13 The same procedure as in Example 11 was repeated, except that the amount of polyvinyl chloride resin (A-4) obtained in Production Example 8 was changed to 93 parts, and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 7 parts. The results are shown in Table 4.

[0216] Example 14 The same procedure as in Example 11 was repeated, except that the amount of polyvinyl chloride resin (A-4) obtained in Production Example 8 was changed to 90 parts, and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 10 parts. The results are shown in Table 4.

[0217] <Comparative Example 2> The same procedure as in Example 3 was repeated, except that the amount of polyvinyl chloride resin (A-2) obtained in Production Example 6 was changed to 100 parts, and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 0 parts. The results are shown in Table 2.

[0218] <Comparative Example 3> The same procedure as in Comparative Example 2 was repeated, except that the polyvinyl chloride resin (A-2) obtained in Production Example 6 was replaced with the polyvinyl chloride resin (A-3) obtained in Production Example 7, and the results are shown in Table 3.

[0219] <Comparative Example 4> The same procedure as in Comparative Example 2 was repeated, except that the polyvinyl chloride resin (A-2) obtained in Production Example 6 was replaced with the polyvinyl chloride resin (A-4) obtained in Production Example 8, and the results are shown in Table 4.

[0220] <Comparative Example 5> A molding material was prepared by kneading 95 parts of olefin resin MC638 (trade name, manufactured by Mitsubishi Chemical Corporation) and 5 parts of the (meth)acrylic copolymer (B-1) obtained in Production Example 4 in a Labo Plastomill at 250°C and 30 rpm for 5 minutes. The resulting molding material was molded in a press molding machine manufactured by Shoji Iron Works Co., Ltd. The molding conditions were 200°C, 18 MPa, and holding for 5 minutes to produce a molded body with a thickness of 1 mm. The resulting molded body was subjected to a fibrinogen (FB) adhesion test and transparency evaluation using the protein adhesion test (μBCA method) described above. The test results are shown in Table 5.

[0221] <Comparative Example 6> The same procedure as in Comparative Example 5 was repeated, except that the amount of olefin resin MC638 used was changed to 90 parts and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 used was changed to 10 parts. The results are shown in Table 5.

[0222] <Comparative Example 7> The same procedure as in Comparative Example 5 was repeated, except that the amount of olefin resin MC638 used was changed to 80 parts and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 used was changed to 20 parts. The results are shown in Table 5.

[0223] <Comparative Example 8> The same procedure as in Comparative Example 5 was repeated, except that the amount of olefin resin MC638 used was changed to 100 parts, and the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 used was changed to 0 parts. The results are shown in Table 5.

[0224] [Table 1]

[0225] [Table 2]

[0226] [Table 3]

[0227] [Table 4]

[0228] [Table 5]

[0229] As shown in the results in Tables 1 to 5, the molded articles obtained from the molding materials of Examples 1 to 14 containing the resin composition of the present invention have a superior protein adhesion inhibitory effect to the molded articles obtained from the molding materials of Comparative Examples 1 to 8 which do not contain the resin composition of the present invention. Furthermore, Examples 11 to 14, which used DINCH as the plasticizer (A2), have lower haze values ​​and also have excellent transparency compared to Examples 1 to 10, which used other plasticizers (A2).

[0230] <Production Example 10: Anti-blocking resin composition (Q-1)> 99.5 parts of the (meth)acrylic copolymer (B-1) obtained in Production Example 4 and 0.5 parts of Ryuron Paste 860 (manufactured by Tosoh Corporation) as anti-blocking particles were supplied to a Henschel mixer and mixed uniformly to obtain an anti-blocking resin composition (Q-1).

[0231] <Production Example 11: Anti-blocking resin composition (Q-2)> An anti-blocking resin composition (Q-2) was obtained in the same manner as in Production Example 10, except that the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 99 parts and the amount of Leuron Paste 860 was changed to 1 part.

[0232] <Production Example 12: Anti-blocking resin composition (Q-3)> An anti-blocking resin composition (Q-3) was obtained in the same manner as in Production Example 10, except that the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 98 parts and the amount of Leuron Paste 860 was changed to 2 parts.

[0233] <Production Example 13: Anti-blocking resin composition (Q-4)> An anti-blocking resin composition (Q-4) was obtained in the same manner as in Production Example 10, except that the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 90 parts and the amount of anti-blocking particles was changed to 10 parts of Metablen P530A (manufactured by Mitsubishi Chemical Corporation).

[0234] <Production Example 14: Anti-blocking resin composition (Q-5)> An anti-blocking resin composition (Q-5) was obtained in the same manner as in Production Example 10, except that the amount of (meth)acrylic copolymer (B-1) obtained in Production Example 4 was changed to 80 parts and the amount of anti-blocking particles was changed to 20 parts of Metablen P530A (manufactured by Mitsubishi Chemical Corporation).

[0235] Example 15 The anti-blocking resin composition (Q-1) obtained in Production Example 10 was used to evaluate the blocking properties. The results are shown in Table 6.

[0236] Example 16 The anti-blocking resin composition (Q-2) obtained in Production Example 11 was used to evaluate the blocking properties. The results are shown in Table 6.

[0237] Example 17 The anti-blocking resin composition (Q-3) obtained in Production Example 12 was used to evaluate the blocking properties. The results are shown in Table 6.

[0238] Example 18 The anti-blocking resin composition (Q-4) obtained in Production Example 13 was used to evaluate the blocking properties. The results are shown in Table 6.

[0239] Example 19 The anti-blocking resin composition (Q-5) obtained in Production Example 14 was used to evaluate the blocking properties. The results are shown in Table 6.

[0240] <Comparative Example 9> The (meth)acrylic copolymer (B-1) obtained in Production Example 4 was used to evaluate blocking properties. The results are shown in Table 6.

[0241] [Table 6]

[0242] As shown in the results in Table 6, the resin compositions obtained in Examples 15 to 19 containing the anti-blocking particles of the present invention have better anti-blocking properties than the resin composition of Comparative Example 9 which does not contain the resin composition of the present invention. [Industrial Applicability]

[0243] The resin composition of the present invention can impart a protein adhesion inhibitory effect to a molded article. The resin composition of the present invention is suitable for producing articles that come into contact with protein-containing body fluids (blood, digestive fluids, exudates, etc.). For example, the present invention is suitable for the production of medical instruments such as scalpels, tweezers, contact lenses, cannulas, catheters, syringes, syringe needles, intravenous lines, intravenous needles, intravenous bags, blood bags, gauze, stents, and endoscopes; and articles that come into contact with body fluids, plasma proteins, or blood, such as pipette tips, petri dishes, cells, microplates, storage bags, plates, reagent storage containers, tubes, shunt tubes, indwelling needles, and drains.

[0244] 1...Bottom lid 2. Case 3...Top lid 4...weight stand 5...weight

Claims

1. A resin composition comprising a vinyl chloride polymer (A1), a plasticizer (A2), and a (meth)acrylic copolymer (B), The (meth)acrylic copolymer (B) is a block copolymer or a graft copolymer containing a monomer unit (b1) represented by the following formula (1): the proportion of the (meth)acrylic copolymer (B) in the total of 100% by mass of the resin composition is 10% by mass or less, the (meth)acrylic copolymer (B) is a block copolymer or a graft copolymer containing a polymer (B1) and a polymer (B2), the proportion of the monomer units (b1) in the total 100% by mass of the monomer units contained in the polymer (B1) is 70% by mass or more, The resin composition has a content of the plasticizer (A2) of 10 to 150 parts by mass per 100 parts by mass of the vinyl chloride polymer (A1). 【Chemical 1】 (In formula (1), R ３ represents a hydrogen atom or a methyl group, R ４ represents an alkylene group having 1 to 4 carbon atoms, and R ５ represents a hydrocarbon group having 1 to 6 carbon atoms, and p is a natural number from 1 to 10.

2. The resin composition according to claim 1, wherein the proportion of the (meth)acrylic copolymer (B) in the total of 100% by mass of the resin composition is 20% by mass or less.

3. The resin composition according to claim 1, wherein the proportion of the monomer units (b1) in a total of 100% by mass of the monomer units contained in the polymer (B1) is 90% by mass or more.

4. 2. The resin composition according to claim 1, wherein the monomer unit (b1) is a monomer unit derived from at least one monomer selected from the group consisting of methoxymethyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, methoxybutyl acrylate, methoxypolyethylene glycol acrylate, methoxymethyl methacrylate, methoxyethyl methacrylate, methoxypropyl methacrylate, methoxybutyl methacrylate, and methoxypolyethylene glycol methacrylate.

5. The resin composition according to claim 1, wherein the polymer (B2) has a glass transition point (Tg) of 50 to 150°C.

6. the polymer (B2) is composed of a monomer unit (b2), The resin composition according to claim 1, wherein the monomer unit (b2) is a monomer unit derived from at least one monomer selected from the group consisting of hydrocarbon group-containing (meth)acrylates having a hydrocarbon group with 1 to 12 carbon atoms.

7. the polymer (B2) is composed of a monomer unit (b2), The resin composition according to claim 1 , wherein the monomer unit (b2) includes a monomer unit derived from methyl methacrylate.

8. The resin composition according to claim 1, wherein the polymer (B2) contains a unit derived from a macromonomer represented by the following formula (2): 【Chemistry 2】 (In formula (2), R ０ ~R ｎ each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, or an unsubstituted or substituted non-aromatic heterocyclic group; ０ ~R ｎ may be the same or different, and X １ ~X ｎ represents a hydrogen atom or a methyl group, and a plurality of X １ ~X ｎ may be the same or different, Z is a terminal group, and n is a natural number from 2 to 10,000.

9. 2. The resin composition according to claim 1, wherein the plasticizer (A2) is at least one selected from the group consisting of phthalic acid compounds, terephthalic acid compounds, trimellitic acid compounds, cyclohexanedicarboxylic acid ester compounds, phosphoric acid compounds, adipic acid compounds, citric acid compounds, ether compounds, and polyester compounds.

10. The resin composition according to claim 1, wherein the plasticizer (A2) is at least one selected from the group consisting of bis(2-ethylhexyl) phthalate, bis(2-ethylhexyl) terephthalate, tris(2-ethylhexyl) trimellitate, and diisononyl cyclohexane-1,2-dicarboxylate.

11. The resin composition according to claim 1, wherein the plasticizer (A2) comprises diisononyl cyclohexane-1,2-dicarboxylate.

12. the resin composition further contains a stabilizer (A3), 2. The resin composition according to claim 1, wherein the stabilizer (A3) is at least one selected from the group consisting of calcium-zinc stabilizers and epoxidized vegetable oils.

13. The resin composition according to claim 1, wherein the haze value of a 1 mm thick sheet measured in accordance with Japanese Industrial Standard JIS K 7136:2000 is less than 50%.

14. the resin composition further contains a (meth)acrylic polymer (P) different from the (meth)acrylic copolymer (B), the proportion of the (meth)acrylic polymer (P) is 0.1 to 20 parts by mass relative to 100 parts by mass in total of the vinyl chloride polymer (A1), the (meth)acrylic copolymer (B), and the plasticizer (A2), The content of methyl methacrylate units in the (meth)acrylic polymer (P) is 50% by mass or more based on a total of 100% by mass, and The resin composition according to claim 1, wherein the (meth)acrylic polymer (P) has a mass average molecular weight of 100,000 or more.

15. the resin composition further contains anti-blocking particles (Q), the ratio of the anti-blocking particles (Q) to 100 parts by mass of the (meth)acrylic copolymer (B) is 0.1 parts by mass or more and 20 parts by mass or less, 2. The resin composition according to claim 1, wherein the median diameter of the anti-blocking particles (Q) measured using a particle size distribution analyzer is 35% or less of the median diameter of the (meth)acrylic copolymer (B).

16. A method for producing a resin composition containing a vinyl chloride polymer (A1), a plasticizer (A2), and a (meth)acrylic copolymer (B), comprising: the (meth)acrylic copolymer (B) is a block copolymer or a graft copolymer containing a polymer (B1) and a polymer (B2), The polymer (B1) contains a monomer unit (b1) represented by the following formula (1): the proportion of the (meth)acrylic copolymer (B) in the total of 100% by mass of the resin composition is 10% by mass or less, the proportion of the monomer units (b1) in the total 100% by mass of the monomer units contained in the polymer (B1) is 70% by mass or more, the content of the plasticizer (A2) is 10 to 150 parts by mass per 100 parts by mass of the vinyl chloride polymer (A1). 【Chemistry 3】 (In formula (1), R ３ represents a hydrogen atom or a methyl group, R ４ represents an alkylene group having 1 to 4 carbon atoms, and R ５ represents a hydrocarbon group having 1 to 6 carbon atoms, and p is a natural number from 1 to 10.

17. A method for producing the resin composition according to claim 16, comprising the following step (I): [Step (I)] a step of mixing the vinyl chloride polymer (A1) and the (meth)acrylic copolymer (B) at 150°C or higher.

18. A molding material comprising the resin composition according to any one of claims 1 to 15.

19. An article molded from the molding material according to claim 18.

20. 20. The article of claim 19, which is in contact with plasma proteins.

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