Thermoplastic resin composition and molded article using the same

Abstract

To provide: a thermoplastic resin composition which has a small coefficient in dynamic friction, has good slidability and is excellent in blocking resistance; and a molding using the same.SOLUTION: A thermoplastic resin composition contains 80-99.9 pts.mass of (I) a thermoplastic resin based on 100 pts.mass of the total of the component (I) and the following component (II), and 0.1-20 pts.mass of (II) a silicone-acrylic core / shell resin based on 100 pts.mass of the total of the component (I) and the component (II). In the (II) silicone-acrylic core / shell resin, core particles are (A) organopolysiloxane, the shell layer has (B) poly(meth)acrylate, a mass ratio (A):(B) of the (A) organopolysiloxane to the (B) poly(meth)acrylate is 40:60 to 90:10, and a ratio ((β / α)×100) of the length (β) of the poly(meth)acrylate in the outer periphery of the core-shell resin to the entire length (α) of the outer periphery is 90% or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic resin composition containing a silicone acrylic core-shell resin and a molded article using the same. More specifically, it relates to a thermoplastic resin composition having excellent abrasion resistance and mold release properties while maintaining the performance of a thermoplastic resin, and a molded article using the same. [Background technology]

[0002] Conventionally, thermoplastic resins such as polystyrene, polymethyl methacrylate, polypropylene, polyethylene, polyvinyl chloride, polyacetal, polyurethane, polyester, ABS, and AS have been widely used as general-purpose resins due to their excellent moldability, processability, transparency, and ease of coloring, as well as their low cost. They are processed into various molded products, including films and sheets. However, when processed into films and sheets, soft resins such as polyethylene, polyvinyl chloride, and polypropylene are prone to blocking, producing crackling noises when unwinding rolls, and exhibiting stickiness between sheets. Furthermore, molded products made from harder resins such as polystyrene and polyacetal have poor release properties from molds, requiring improvements in processability. In addition, these resin molded products have poor sliding properties, necessitating improvements in sliding properties from both productivity and tactile aspects.

[0003] As a countermeasure, silicone oil, a lubricant and mold release agent with excellent chemical and physical stability, was added to the thermoplastic resin. However, most of the silicone oil near the surface of the molded product seeped out and was consumed in a short time, so although it showed excellent lubricity initially, it was insufficient in terms of maintaining long-term sliding properties. In addition, there was a problem of stickiness on the surface of the molded product, which reduced its commercial value.

[0004] To solve this problem, methods such as kneading spherical silicone powder (see, for example, Japanese Patent Publication Nos. 1-18408, 1-204950, and 7-39214), kneading silicone rubber with polytetrafluoroethylene powder (see Japanese Patent Publication No. 4-234450), kneading silicone oil with polyvinylidene fluoride powder (see Japanese Patent Publication No. 4-264152), and UV-curable resins with added spherical silica fine particles (see Japanese Patent Publication No. 7-102186) have been proposed. While these methods of incorporating powders or spherical fine particles are effective, they also have unsatisfactory properties. The amount of powder or other particles added is relatively high, at 2% by weight or more, making them unsuitable for molded products such as films that require transparency, and they are also economically disadvantageous. Furthermore, solid lubricants have the drawback of gradually decreasing sliding properties due to wear particles from abrasion.

[0005] Furthermore, a method has been proposed to obtain slippery films and other molded products by kneading an acrylic resin copolymerized with silicone macromonomers (graft copolymer) into a thermoplastic resin (see Japanese Patent Publication Nos. 1-214475, 4-173869, and 6-100746). However, because it has good compatibility with vinyl resins, it has excellent dispersibility, and as a result, the properties are insufficient with trace amounts. Moreover, the silicone graft acrylic resin itself is an irregularly shaped powder, which makes it prone to friction on the surface. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 1-18408 [Patent Document 2] Japanese Unexamined Patent Publication No. 1-204950 [Patent Document 3] Special Publication No. 7-39214 [Patent Document 4] Japanese Patent Application Publication No. 4-234450 [Patent Document 5] Japanese Patent Application Publication No. 4-264152 [Patent Document 6] Japanese Patent Application Laid-Open No. 7-102186 [Patent Document 7] Japanese Patent Application Laid-Open No. 1-214475 [Patent Document 8] Japanese Patent Application Laid-Open No. 4-173869 [Patent Document 9] Japanese Patent Application Laid-Open No. 6-100746 [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] Therefore, there is a demand for providing a thermoplastic resin composition that does not have the above-described problems, has a small coefficient of kinetic friction, good slipperiness, and excellent antiblocking properties, and a molded product using the same.

[0008] The present invention has been made in view of the above circumstances, and an object thereof is to provide a thermoplastic resin composition having excellent abrasion resistance and mold release properties, and a molded product using the same. [Means for Solving the Problems]

[0009] As a result of intensive studies to achieve the above object, the present inventor has found that a thermoplastic resin composition in which a silicone-acrylic core-shell resin having a specific structure is blended with a thermoplastic resin has excellent abrasion resistance and mold release properties and can solve the above problems, and has thus completed the present invention.

[0010] That is, the present invention is (I) a thermoplastic resin 80 to 99.9 parts by mass based on 100 parts by mass in total of the component (I) and the following component (II), and (II) a silicone-acrylic core-shell resin 0.1 to 20 parts by mass based on 100 parts by mass in total of the component (I) and the component (II) containing a thermoplastic resin composition, wherein the (II) silicone-acrylic core-shell resin has core particles that are (A) organopolysiloxane and has (B) a poly(meth)acrylate in the shell layer, The mass ratio of the (A) organopolysiloxane to the (B) poly(meth)acrylate is (A):(B) = 40:60 to 90:10, and the ratio ((β / α)×100) of the length (β) of the poly(meth)acrylate portion in the outer periphery to the total outer periphery length (α) of the core-shell resin is 90% or more, and the thermoplastic resin composition is provided. Furthermore, the present invention provides a resin molded article made of the thermoplastic resin composition, particularly a film or a sheet.

Effects of the Invention

[0011] The thermoplastic resin composition of the present invention has a small coefficient of kinetic friction, good slidability, and excellent abrasion resistance and mold release properties. Therefore, the resin molded article has excellent workability in the production of molded articles and has great environmental advantages because a coupling agent is not required.

Brief Description of the Drawings

[0012] [Figure 1] FIG. 1 is a transmission electron microscope (TEM) image of the silicone-acrylic core-shell resin of Example 1 and data on the thickness of the shell layer. [Figure 2] FIG. 2 is a schematic diagram showing the silicone-acrylic core-shell resin of the present invention.

Modes for Carrying Out the Invention

[0013] The present invention is a thermoplastic resin composition containing the following components (I) and (II). (I) Thermoplastic resin 80 to 99.9 parts by mass with respect to a total of 100 parts by mass of the (I) component and the following (II) component, and (II) Silicone-acrylic core-shell resin 0.1 to 20 parts by mass with respect to a total of 100 parts by mass of the (I) component and the (II) component The (II) silicone-acrylic core-shell resin is a core-shell resin having a shell layer in which (B) poly(meth)acrylic acid ester is grafted onto core particles made of (A) organopolysiloxane, wherein the mass ratio of (A) organopolysiloxane to (B) poly(meth)acrylic acid ester is (A):(B)=40:60 to 90:10, and the ratio of the outer circumference length (β) of the poly(meth)acrylic acid ester portion to the total outer circumference length (α) of the core-shell resin ((β / α) × 100, hereinafter sometimes referred to as coverage rate) is 90% or more. The following provides a more detailed explanation of each component.

[0014] (I) The thermoplastic resin may be any conventionally known resin, but preferably it is a urethane resin, a polyvinyl chloride resin, an acrylic resin, a styrene-butadiene-acrylonitrile resin, a polyester resin, an amide resin, an acetal resin, or a polycarbonate resin. In this case, the thermoplastic resin should have a hardness (Shore A) of 80 or higher, preferably 95 or lower. In this invention, the hardness (Shore A) is measured in accordance with JIS K7215.

[0015] The amount of the thermoplastic resin (I) described above is 80 to 99.9 parts by mass per 100 parts by mass of the total of component (I) and the silicone-acrylic core-shell resin (II) described later. That is, per 100 parts by mass of the total of the thermoplastic resin (I) and the silicone-acrylic core-shell resin (II), the amount of thermoplastic resin (I) is 80 to 99.9 parts by mass, preferably 90 to 95 parts by mass, and the amount of silicone-acrylic core-shell resin (II) described later is 0.1 to 20 parts by mass, preferably 5 to 10 parts by mass. The amount of thermoplastic resin is 80 to 99.9% by mass, preferably 90 to 95% by mass, of the total amount of the resin composition. If the amount of thermoplastic resin is below the lower limit, the coating properties such as abrasion resistance of the molded resin product will deteriorate, which is undesirable. If it exceeds the upper limit, the surface will not be smooth and the tactile feel will be poor.

[0016] (II) The silicone acrylic core-shell resin is a core-shell resin having a core layer of (A) organopolysiloxane and a shell layer of (B) poly(meth)acrylic acid ester. The mass ratio of component (A) to component (B) is (A):(B) = 40:60 to 90:10, preferably 50:50 to 85:15.

[0017] The silicone-acrylic core-shell resin of the present invention is characterized in that the ratio ((β / α) × 100) of the length of the poly(meth)acrylic acid ester portion on the outer circumference to the total outer circumference length (α) of the core-shell resin is 90% or more, preferably 93% or more, and particularly preferably 95% or more. This results in excellent dispersibility when the silicone-acrylic core-shell resin is blended with a thermoplastic resin. In the present invention, the coverage rate (Z) of the acrylic resin on the outer circumference is also defined by the following formula. Coverage (Z) = [{(1) - (2)} / (1)] × 100 In the above formula, (1) is the theoretical total circumference length calculated from the diameter of the core-shell particles measured from the TEM image, and (2) is the length of the part of the shell in the TEM image where there is no difference in shading (measured value). The average value of 10 or more locations was used. In the above, the part of the shell in the TEM image where there is no difference in shading means the length of the part of the circumference where the acrylic resin is not bonded. That is, (1) = (total circumference length (α)), and {(1) - (2)} = length of the poly(meth)acrylic acid ester portion of the circumference (β). If the entire core particle is covered with poly(meth)acrylic acid ester, the value of (2) is 0, and the coverage rate is 100%. A schematic diagram of the core-shell particle is shown in Figure 2. In Figure 2, the symbol (1) represents the core particle (organosiloxane), the symbol (2) represents the poly(meth)acrylic acid ester portion in the shell layer, the dotted line indicated by the symbol (3) represents the total outer circumference (α), and the portion indicated by the symbol (4) is the portion where the acrylic resin is not bonded (as shown in (2) above).

[0018] The above (II) silicone acrylic core-shell resin is preferably a reaction product obtained by core-shell polymerization of (a) an organopolysiloxane represented by the following general formula (1), (b) a (meth)acrylic acid ester monomer, and optionally (c) a functional group-containing monomer copolymerizable therewith. [ka] In formula (1), R 1 R is a substituted or unsubstituted, non-aryl, monovalent hydrocarbon group having 1 to 20 carbon atoms, and 2 X is a phenyl group. X is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and Y is independently a group defined by X, or -[O-Si(X)2] d -X is a group represented by X, and at least one of the groups represented by X and Y is a hydroxyl group, a is a number greater than or equal to 0, b is a positive number that is between 30% and 100% of the total number of a, b, c, and e, c is a positive number that is between 0% and 60% of the total number of a, b, c, and e, and e is a number that is between 0% and 10% of the total number of a, b, c, and e.

[0019] R 1 This refers to a substituted or unsubstituted, non-aryl, monovalent hydrocarbon group having 1 to 20 carbon atoms, such as alkyl groups including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, and cycloheptyl. Examples of substituted monovalent hydrocarbon groups include alkyl groups substituted with halogen atoms, acryloxy, methacryloxy, carboxyl, alkoxy, alkenyloxy, amino, or (meth)acryloxy-substituted amino groups. 1 Preferably, it is a methyl group.

[0020] X is independently a substituted or unsubstituted C1-C20 alkyl group, a C6-C20 aryl group, a C1-C20 alkoxy group, or a hydroxyl group. For example, in addition to the hydroxyl group, examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, phenyl group, tolyl group, naphthyl group, methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, tetradecyloxy group, etc. The same as above can be used as substituted alkyl groups.

[0021] Y is independent of the above X or -[O-Si(X)2] d -X is the base represented by -X. d is a number from 0 to 10, preferably from 0 to 5.

[0022] The method for producing the organopolysiloxane represented by formula (1) above is not particularly limited, but for example, it can be obtained by ring-opening polymerization of a cyclic organosiloxane. The cyclic organosiloxanes used as raw materials include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), 1,1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane, tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane, and 1,3,5,7-tetra(3-methacryloxypropyl)tetramethyl Examples include cyclotetrasiloxane, 1,3,5,7-tetra(3-acryloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(3-carboxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(3-vinyloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(p-vinylphenyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra[3-(p-vinylphenyl)propyl]tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(N-acryloyl-N-methyl-3-aminopropyl)tetramethylcyclotetrasiloxane, and 1,3,5,7-tetra(N,N-bis(lauroyl)-3-aminopropyl)tetramethylcyclotetrasiloxane.

[0023] Strong acids are preferred as polymerization catalysts for the polymerization of cyclic organosiloxanes, with examples including hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid. Dodecylbenzenesulfonic acid, which has emulsifying properties, is preferred.

[0024] Furthermore, when performing ring-opening emulsion polymerization of cyclic organosiloxanes, it is preferable to use a surfactant. Examples of such surfactants include anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salts, N-acyl taurate salts, aliphatic soaps, and alkyl phosphates, among which those that are readily soluble in water and do not have polyethylene oxide chains are preferred. More preferably are N-acyl amino acid salts, N-acyl taurate salts, aliphatic soaps, and alkyl phosphates, and particularly preferably sodium lauroyl methyl taurate and sodium myristoyl methyl taurate. By performing ring-opening emulsion polymerization in the presence of a surfactant, emulsion particles consisting of the organopolysiloxane represented by formula (1) above can be obtained.

[0025] The ring-opening emulsion polymerization temperature for cyclic organosiloxanes is preferably 50 to 75°C, and the polymerization time is preferably 10 hours or more, and more preferably 15 hours or more. Furthermore, it is particularly preferable to mature the polymer at 5 to 30°C for 10 hours or more after polymerization.

[0026] The (b)(meth)acrylic acid ester used in the present invention (hereinafter sometimes referred to as the acrylic component) refers to an acrylic acid ester monomer or methacrylic acid ester monomer that does not have functional groups such as hydroxyl groups, amide groups, or carboxyl groups. Preferably, it is an alkyl acrylate or alkyl methacrylate having an alkyl group having 1 to 10 carbon atoms. Furthermore, a monomer in which the glass transition temperature (hereinafter sometimes referred to as Tg) of the polymer of the acrylic component is 40°C or higher, preferably 60°C or higher, is preferred. Examples of such monomers include methyl methacrylate, isopropyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, and butyl acrylate. The upper limit of Tg is preferably 200°C or lower, and more preferably 150°C or lower. The glass transition temperature can be measured according to JIS K7121.

[0027] Furthermore, the functional group-containing monomer (c) copolymerizable with (b)(meth)acrylic acid ester may be any monomer having an unsaturated bond such as a carboxyl group, an amide group, a hydroxyl group, and a vinyl group or an allyl group. Examples include methacrylic acid, acrylic acid, acrylamide, allyl methacrylate, vinyl methacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate. By copolymerizing these, it is possible to improve the compatibility between the core-shell resin and the thermoplastic resin. Preferably, methacrylic acid, acrylic acid, and 2-hydroxyethyl methacrylate are used.

[0028] In the production of silicone acrylic core-shell resin, the amount of (b) (meth)acrylic acid ester is preferably 10 to 150 parts by mass, more preferably 20 to 100 parts by mass, per 100 parts by mass of (a) organopolysiloxane. If the amount of (b) component is too small, powderization becomes difficult, and if the amount of (b) component is too large, sufficient sliding properties will not be achieved. Furthermore, when (c) other functional group-containing monomers are blended, the amount is preferably 0.01 to 50 parts by mass, more preferably 0.01 to 20 parts by mass, and even more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the above-mentioned (a) component. If the amount of (c) component is too large, the surface sliding properties may not improve unless the obtained silicone acrylic core-shell resin is added in excess to the (I) thermoplastic resin.

[0029] The (II) silicone acrylic core-shell resin of the present invention is obtained by radical polymerization of (a) polyorganosiloxane (core particles) with (b) (meth)acrylic acid ester and, if necessary, (c) a functional group-containing monomer copolymerizable thereto. Specifically, component (b) and, if necessary, component (c) are reacted to an emulsion of (a) polyorganosiloxane at 25 to 55°C in the presence of a radical initiator, with additions made 2 to 10 times or continuously by dropwise addition over a predetermined period of time (2 to 8 hours). If components (b) and (c) are added all at once, core-shell particles may not be formed.

[0030] Radical initiators used here include persulfates such as potassium persulfate and ammonium persulfate, hydrogen persulfate solution, t-butyl hydroperoxide, and hydrogen peroxide. If necessary, redox systems using reducing agents such as sodium acidic sulfite, rongalit, L-ascorbic acid, tartaric acid, sugars, and amines can also be used.

[0031] Furthermore, to improve stability, anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salts, N-acyl taurine salts, aliphatic soaps, and alkyl phosphates can be added. Nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxylentridecyl ether can also be added.

[0032] The polymerization temperature for components (b) and (c) is preferably 25 to 55°C, and more preferably 25 to 40°C. The polymerization time is preferably 2 to 8 hours, and more preferably 3 to 6 hours.

[0033] Furthermore, chain transfer agents can be added to adjust the molecular weight of the polymer.

[0034] The resulting silicone-acrylic core-shell resin (II) is a core-shell polymer having (a) polyorganosiloxane as the core layer and polymers of components (b) and (c) as the shell layer. Furthermore, the coverage rate of the (b) acrylic resin on the outer periphery is 90% or more, preferably 95% or more. More specifically, it is a core-shell resin emulsion in which poly(meth)acrylic acid esters are bonded to the surface of silicone emulsion particles made of silicone-acrylic core-shell resin.

[0035] The solids content of the silicone-acrylic core-shell resin emulsion is preferably 35 to 50% by mass. The viscosity (at 25°C) is preferably 500 mPa·s or less, and more preferably 50 to 500 mPa·s. Viscosity can be measured using a rotational viscometer.

[0036] The average particle size of the emulsion particles of the above-mentioned silicone-acrylic core-shell resin (II) is preferably 50 to 400 nm. The average particle size is a value measured using a TEM device.

[0037] The average particle size of the core layer of the silicone-acrylic core-shell resin (II) is preferably 20 to 300 nm. More preferably, it is 50 to 250 nm. The average particle size of the core layer is the value measured using the scale of the TEM device in the shadow difference portion of the TEM image.

[0038] The shell thickness of the silicone-acrylic core-shell resin (II) is preferably 1 to 50 nm. More preferably 5 to 30 nm. The shell thickness is the value obtained by subtracting the average particle diameter of the polyorganosiloxane (A) core from the average particle diameter of the silicone-acrylic core-shell resin (II) of the present invention and taking half of that value.

[0039] Furthermore, the thermoplastic resin composition may further contain other components described later. The amount of the silicone-acrylic core-shell resin (II) in the thermoplastic resin composition is 0.1 to 20% by mass, preferably 0.5 to 10% by mass, relative to the total mass of the thermoplastic resin composition. If the amount of the silicone-acrylic core-shell resin (II) is below the lower limit, no improvement in mold release properties will be observed, and if it exceeds the upper limit, the molded product will whiten and its slipperiness will also decrease, which is undesirable.

[0040] The resulting silicone-acrylic core-shell resin (II) emulsion is powdered by drying after salting out and by spray drying.

[0041] The obtained powder is kneaded with thermoplastic resin (I) using a dry blender (e.g., roll, kneader, Banba mixer, Plastmill, extruder, etc.), and then molded into the desired shape by extrusion molding or injection molding. The thermoplastic resin may be pre-processed into pellets or powder form. The molding temperature may be above the melting temperature of the resin mixture, preferably at a set temperature of 180-250°C. For example, pellets are obtained from a strand die using a twin-screw extruder of Laboplastmill (manufactured by Toyo Seiki Seisakusho). Using these pellets, a 3cm x 3cm x 2mm injection molded piece is formed at a temperature of 180-250°C using a small 80tf injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd.). Similarly, a film of approximately 200μm is formed from a T-die using a twin-screw extruder of Laboplastmill. In this case, transparency is required for the resin molded product, and it is preferable that the haze value of both the 2 mm thick resin molded product and the 200 μm thick resin molded product be 85% or less. If it exceeds 85%, the transparency will not be perceived at all, and problems may occur such as the color and pattern of the base material becoming completely invisible. The thickness of the molded product can be adjusted as appropriate, and for example, it can be molded to various thicknesses within the range of 10 μm to 10 mm.

[0042] Furthermore, the resin molded product of the present invention may contain antioxidants, colorants, ultraviolet absorbers, light stabilizers, antistatic agents, plasticizers, flame retardants, other resins, etc., to the extent that they do not affect its performance.

[0043] The resin molded products of the present invention are not particularly limited in their use, but can be used as materials for stationery, toys, home appliances, car seats, furniture, clothing, shoes, bags, sanitary products, and outdoor tents. [Examples]

[0044] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, parts and % refer to parts by mass and mass%, respectively.

[0045] Preparation of silicone-acrylic core-shell resin (II) [Manufacturing Example 1] Dissolve 600g of octamethylcyclotetrasiloxane and 6g of sodium lauryl sulfate in 54g of pure water, and dissolve 6g of dodecylbenzenesulfonic acid in 54g of pure water in a 2L polyethylene beaker. Emulsify uniformly using a homomixer, then gradually add 470g of water to dilute, and mix under a pressure of 300kgf / cm². 2 The mixture was passed through a high-pressure homogenizer twice to obtain a uniform white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 50-60°C for 24 hours. After aging at 10-20°C for 24 hours, it was neutralized to near neutral with 12 g of 10% sodium carbonate aqueous solution to obtain an emulsion. The emulsion had a non-volatile content (solid content) of 44.8% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in a non-flowing, soft gel state. The structure of the organopolysiloxane in the above emulsion is as shown by the following formula. [ka] (Two of X are methyl groups, one is a hydroxyl group, R 1 (This is a methyl group.) To the emulsion obtained above, 125g of deionized water was added, and 232g of methyl methacrylate (MMA) was added dropwise over 3-5 hours while a redox reaction was carried out at 30°C with a peroxide and a reducing agent. This resulted in a resin emulsion (solid content 45.2%) in which a polymethyl methacrylate (PMMA) shell layer was formed on the surface of the silicone emulsion particles. This was then spray-dried to reduce the volatile content to 1.2% to obtain a resin powder (silicone acrylic core-shell resin). The method for measuring the solid content is described below.

[0046] [Manufacturing Example 2] 600 g of octamethylcyclotetrasiloxane, a solution of 6 g of sodium lauryl sulfate in 54 g of pure water, and a solution of 6 g of dodecylbenzenesulfonic acid in 54 g of pure water were charged into a 2 L polyethylene beaker, emulsified uniformly with a homomixer, and then gradually diluted by adding 470 g of water. At a pressure of 300 kgf / cm 2 it was passed through a high-pressure homogenizer twice to obtain a uniform white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, a thermometer, and a reflux condenser, and subjected to a polymerization reaction at 50 - 60 °C for 24 hours. After aging at 10 - 20 °C for 24 hours, it was neutralized to near neutrality with 12 g of a 10% aqueous sodium carbonate solution. The obtained emulsion had a non-volatile content (solid content) of 44.8% after drying at 105 °C for 3 hours, and the organopolysiloxane in the emulsion was in a non-flowing soft gel state. The structure of the organopolysiloxane in the above emulsion is as follows. [Chemical formula] (Two of X are methyl groups, one is a hydroxy group, and R 1 is a methyl group) 50 g of ion-exchanged water was added to the emulsion obtained above, and a redox reaction was carried out at 30 °C with a peroxide and a reducing agent while dropping 95 g of methyl methacrylate (MMA) over 3 - 5 hours, thereby forming a resin emulsion (solid content 45.0%) with a PMMA shell layer on the surface of the silicone emulsion particles. By spray-drying this, the volatile content was volatilized to 1.1% to obtain a resin powder (silicone-acrylic core-shell resin). The method for measuring the solid content is as described below.

[0047] [Production Example 3] 600 g of octamethylcyclotetrasiloxane, a solution of 6 g of sodium lauryl sulfate in 54 g of pure water, and a solution of 6 g of dodecylbenzenesulfonic acid in 54 g of pure water were charged into a 2 L polyethylene beaker, emulsified uniformly with a homomixer, and then gradually diluted by adding 470 g of water. At a pressure of 300 kgf / cm 2The mixture was passed twice through a high-pressure homogenizer to obtain a homogeneous white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 50-60°C for 24 hours. After aging at 10-20°C for 24 hours, it was neutralized to near neutral with 12 g of 10% sodium carbonate aqueous solution. The resulting emulsion had a non-volatile content (solids) of 44.8% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in a non-flowing, soft gel state. The structure of the organopolysiloxane in the above emulsion is as shown by the following formula. [ka] (Two of X are methyl groups, one is a hydroxyl group, R 1 (This is a methyl group.) To the emulsion obtained above, 442g of deionized water was added, and 807g of methyl methacrylate (MMA) was added dropwise over 3-5 hours while a redox reaction was carried out at 30°C with a peroxide and a reducing agent. This resulted in a resin emulsion (solid content 45.3%) in which a PMMA shell layer was formed on the surface of the silicone emulsion particles. This was then spray-dried to reduce the volatile content to 1.2% to obtain a resin powder (silicone acrylic core-shell resin). The method for measuring the solid content is described below.

[0048] [Manufacturing Example 4] Dissolve 300g of octamethylcyclotetrasiloxane, 300g of diphenyldimethylsiloxane (Shin-Etsu Chemical Co., Ltd. KF-54), and 24g of 50% alkyldiphenyl ether disulfonate sodium (Perex SS-L, Kao Corporation) in 45g of pure water, and dissolve 6g of dodecylbenzenesulfonic acid in 54g of pure water in a 2L polyethylene beaker. Emulsify uniformly using a homomixer, then gradually add 490g of water to dilute, and apply a pressure of 300kgf / cm². 2The mixture was passed through a high-pressure homogenizer twice to obtain a homogenized white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 55°C for 10-20 hours. After maturation at 10°C for 10-20 hours, the pH was neutralized to near neutral with 12 g of 10% sodium carbonate aqueous solution. The resulting emulsion had a non-volatile content (solids) of 47.5% after drying at 105°C for 3 hours. The organopolysiloxane in the emulsion was in the form of a non-flowing soft gel. The structure of the organopolysiloxane in the above emulsion is as shown by the following formula. [ka] (Two of X are methyl groups and one is a hydroxyl group, R 1 R is a methyl group, 2 (This is a phenyl group.) To the emulsion obtained above, 167g of deionized water was added, and 249g of methyl methacrylate (MMA) was added dropwise over 3-5 hours while a redox reaction was carried out at 30°C with a peroxide and a reducing agent. This resulted in a resin emulsion (solid content 45.6%) in which a PMMA shell layer was formed on the surface of the silicone emulsion particles. This was then spray-dried to reduce the volatile content to 1.0% to obtain a resin powder (silicone acrylic core-shell resin). The method for measuring the solid content is described below.

[0049] [Manufacturing Example 5] Dissolve 600g of octamethylcyclotetrasiloxane, 1g of hexamethyldisiloxane (M2), and 6g of sodium lauryl sulfate in 54g of pure water, and dissolve 6g of dodecylbenzenesulfonic acid in 54g of pure water in a 2L polyethylene beaker. Emulsify uniformly using a homomixer, then gradually add 470g of water to dilute, and apply a pressure of 300kgf / cm². 2The mixture was passed through a high-pressure homogenizer twice to obtain a homogenized white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 50-60°C for 24 hours. After maturation at 10-20°C for 24 hours, it was neutralized to near neutral with 12g of 10% sodium carbonate aqueous solution. After drying at 105°C for 3 hours, the non-volatile content (solids) of the emulsion was 45.4%, and the organopolysiloxane in the emulsion was in a non-flowing, soft gel state. The structure of the organopolysiloxane in the above emulsion is as shown by the following formula. [ka] (R 1 (where X is a methyl group, and all X are methyl groups.) To the emulsion obtained above, 133g of deionized water was added, and 160g of methyl methacrylate (MMA) and 74g of butyl acrylate (BA) were added dropwise over 3-5 hours while a redox reaction was carried out at 30°C with peroxides and reducing agents to obtain a resin emulsion (solid content 44.9%) in which a PMMA shell layer was formed on the surface of the silicone emulsion particles. This was then spray-dried to volatilize the volatile content to 1.2% to obtain a resin powder (silicone acrylic core-shell resin).

[0050] [Comparative Manufacturing Example 1] Dissolve 600g of octamethylcyclotetrasiloxane and 6g of sodium lauryl sulfate in 54g of pure water, and dissolve 6g of dodecylbenzenesulfonic acid in 54g of pure water in a 2L polyethylene beaker. Emulsify uniformly using a homomixer, then gradually add 470g of water to dilute, and mix under a pressure of 300kgf / cm². 2The mixture was passed twice through a high-pressure homogenizer to obtain a homogeneous white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 50-60°C for 24 hours. After aging at 10-20°C for 24 hours, it was neutralized to near neutral with 12 g of 10% sodium carbonate aqueous solution. The resulting emulsion had a non-volatile content (solids) of 44.8% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in a non-flowing, soft gel state. The structure of the organopolysiloxane in the above emulsion is as shown by the following formula. [ka] (Of the above X groups, two are methyl groups and one is a hydroxyl group, R 1 (This is a methyl group.) To the emulsion obtained above, 125g of deionized water was added, followed by the addition of 232g of methyl methacrylate (MMA) all at once. After stirring for 1 hour, a redox reaction was carried out at 30°C for 3-5 hours while dropwise adding peroxide and a reducing agent. As a result, the shell layer was not sufficiently formed, and most of the PMMA was incorporated into the core. In other words, a resin emulsion (solid content 45.5%) in which PMMA was incorporated into the emulsion particles was obtained. The coverage rate of the shell layer (methacrylic acid ester) was calculated to be 20% using the method described later. This was then spray-dried to volatilize the volatile content to 1.2% to obtain a resin powder (silicone acrylic core shell resin).

[0051] [Comparative Manufacturing Example 2] Dissolve 600g of octamethylcyclotetrasiloxane and 6g of sodium lauryl sulfate in 54g of pure water, and dissolve 6g of dodecylbenzenesulfonic acid in 54g of pure water in a 2L polyethylene beaker. Emulsify uniformly using a homomixer, then gradually add 470g of water to dilute, and mix under a pressure of 300kgf / cm². 2The mixture was passed through a high-pressure homogenizer twice to obtain a homogenized white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 50-60°C for 24 hours. After maturation at 10-20°C for 24 hours, it was neutralized to near neutral with 12 g of 10% sodium carbonate aqueous solution. The resulting emulsion had a non-volatile content (solids) of 44.8% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in a non-flowing, soft gel state. The structure of the organopolysiloxane in the above emulsion is as shown by the following formula. [ka] (X has two methyl groups and one hydroxyl group, R 1 (This is a methyl group.) To the emulsion obtained above, 689g of deionized water was added, and 1256g of methyl methacrylate (MMA) was added dropwise over 3-5 hours while a redox reaction was carried out at 30°C with a peroxide and a reducing agent. This resulted in a resin emulsion (solid content 45.2%) in which a PMMA shell layer was formed on the surface of the silicone emulsion particles. This was then spray-dried to reduce the volatile content to 1.2% to obtain a resin powder (silicone acrylic core-shell resin). The method for measuring the solid content is described below.

[0052] [Comparative Manufacturing Example 3] Dissolve 600g of octamethylcyclotetrasiloxane and 6g of sodium lauryl sulfate in 54g of pure water, and dissolve 6g of dodecylbenzenesulfonic acid in 54g of pure water in a 2L polyethylene beaker. Emulsify uniformly using a homomixer, then gradually add 470g of water to dilute, and mix under a pressure of 300kgf / cm². 2The mixture was passed twice through a high-pressure homogenizer to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 50-60°C for 24 hours. After maturation at 10-20°C for 24 hours, it was neutralized to near neutral with 12g of 10% sodium carbonate aqueous solution. The obtained emulsion had a non-volatile content (solid content) of 44.8% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in a non-flowing, soft gel state. The structure of the organopolysiloxane in the emulsion is as shown in the formula below. The emulsion particles are a silicone resin without a shell structure in the outer layer and are in a soft gel state, so they could not be converted into powder by spray drying. [ka] (Of the above X groups, two are methyl groups and one is a hydroxyl group, R 1 (This is a methyl group.)

[0053] [Comparative Manufacturing Example 4] Comparative manufacturing example 4 relates to an emulsion resin obtained by further incorporating a conventional silane coupling agent (3-methacryloxypropylmethyldimethoxysilane, KBM-502 manufactured by Shin-Etsu Chemical Co., Ltd.) and emulsion graft polymerization of an organopolysiloxane having an f unit with a methacryloxypropyl group, represented by the following formula (1'), and methyl methacrylate.

[0054] Dissolve 599.4g of octamethylcyclotetrasiloxane, 0.6g of KBM-502, and 6g of sodium lauryl sulfate in 54g of pure water, and dissolve 6g of dodecylbenzenesulfonic acid in 54g of pure water in a 2L polyethylene beaker. Emulsify uniformly using a homomixer, then gradually add 470g of water to dilute, and apply a pressure of 300kgf / cm². 2The mixture was passed through a high-pressure homogenizer twice to obtain a homogenized white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerization was carried out at 50-60°C for 24 hours. After maturation at 10-20°C for 24 hours, it was neutralized to near neutral with 12 g of 10% sodium carbonate aqueous solution. The resulting emulsion had a non-volatile content (solids) of 45.3% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel. The structure of the organopolysiloxane in the above emulsion is as shown by the following formula. [ka] (In the formula, two of X are methyl groups and one is a hydroxyl group, R 1 R is a methyl group, 3 (where Z is a methacryloxypropyl group and Z is a methyl group) To the emulsion obtained above, 125g of deionized water was added, and 232g of methyl methacrylate (MMA) was added dropwise over 3-5 hours while a redox reaction was carried out at 30°C with a peroxide and a reducing agent. This resulted in a resin emulsion (solid content 45.1%) in which a PMMA shell layer was formed on the surface of the silicone emulsion particles. This was then spray-dried to reduce the volatile content to 1.2% to obtain a resin powder (silicone acrylic core-shell resin). The method for measuring the solid content is described below.

[0055] <Measurement of coverage> The coverage (Z) of the silicone acrylic core-shell resin was calculated by applying the following formula to images measured using a transmission electron microscope (TEM, JEM-2100TM, manufactured by JEOL Ltd.). Coverage (Z) = [{(1) - (2)} / (1)] × 100 In the above formula, (1) is the total length of the theoretical outer perimeter calculated from the diameter of the core-shell particles measured from the TEM image, and (2) is the measured value of the part of the shell in the TEM image where there is no difference in shading (a portion of the length of the outer perimeter). If the entire core particle is covered with poly(meth)acrylic acid ester, the value of (2) is 0, and the coverage is 100%. The average value was obtained by measuring 10 or more particles in the TEM image.

[0056] <Method for measuring solid content> Approximately 1 g of each silicone acrylic core-shell resin (sample) obtained in the examples and comparative examples was accurately weighed onto an aluminum foil dish, placed in a drying oven maintained at approximately 105°C, heated for 1 hour, then removed from the drying oven and allowed to cool in a desiccator. The weight of the dried sample was measured, and the evaporation residue was calculated using the following formula.

number

[0057] <Method for measuring the average particle size of silicone acrylic core shell resin> The particle size of each silicone acrylic core-shell resin (resin emulsion particles) was measured using the JEOL JEM-2100TM.

[0058] <Method for measuring shell thickness> Using a JEOL JEM-2100TM TEM, a 5000-fold diluted silicone acrylic core-shell resin (resin emulsion) was dried at room temperature on a grid. Observation was then performed, and the thickness of the shell layer was measured using the instrument's scale based on the difference in shading between the silicone and acrylic layers. The shell thickness was calculated by subtracting the average particle diameter of the polyorganosiloxane core from the average particle diameter of the silicone acrylic core-shell resin and then dividing by 2. The average value obtained from measurements of 10 particles (N=10) in the TEM image was used. Figure 1 shows a measurement image of the silicone acrylic core-shell resin of Example 1. This is one data point out of N=10, and the shell layer thickness is 13.5 nm. The average value for N=10 is 15 nm.

[0059] The composition (parts by weight) and physical properties of the organopolysiloxane contained in the above emulsion are summarized in Table 1 below. Note that the pH in the table is the pH of the emulsion dispersion medium (25°C), and the weight-average molecular weight was measured by gel permuration chromatography (GPC) analysis (solvent: THF, polystyrene equivalent, 25°C).

[0060] [Table 1] *D4 is octamethylcyclotetrasiloxane, KF-54 is diphenyldimethylsiloxane, and M2 is hexamethyldisiloxane.

[0061] The composition (parts by weight) and evaluation of the silicone-acrylic core shell resin are shown in Table 2 below.

[0062] [Table 2]

[0063] Preparation and evaluation of thermoplastic resin compositions [Examples 1-7, Comparative Examples 1-4, Reference Example 5] Using a strand die in a laboplast mill (manufactured by Toyo Seiki Seisakusho), thermoplastic urethane resin and silicone acrylic core-shell resin powder obtained in the above manufacturing example or comparative manufacturing example were blended in the proportions shown in Table 3 or 4 below, and mixed at a molding temperature of 200°C to prepare a resin composition (resin pellets). Subsequently, the resin composition (resin pellets) was heat-processed in a small injection molding machine (2cm x 2cm x 2mm mold) to obtain a resin molded product.

[0064] The thermoplastic urethane resins used in the examples and comparative examples are as follows: • Product name: "Elastran ET-597-10" BASF thermoplastic polyurethane (polyester-based), Shore A hardness "97" Product name: "Miractran XN-2000" Thermoplastic polyurethane (polycarbonate type) manufactured by Tosoh Corporation, Shore A hardness "85"

[0065] <Mold releasability> The mold was cooled to a temperature of 60°C, and the molded product was released from the mold using an ejector pin 10 times. The percentage of times the product released (fell) naturally out of the 10 attempts is shown in Table 3 or 4 as a percentage (for example, if 8 out of 10 times the product released naturally, it is shown as "80%", and if all 10 times the product released naturally, it is shown as "100%"). The ejector pin is built into the mold.

[0066] [Table 3]

[0067] [Table 4]

[0068] As shown in Table 4 above, molded articles obtained from thermoplastic resin compositions prepared using the siloxane emulsion of Comparative Production Example 2, which does not satisfy the mass ratio of the present invention in the core-shell structure, have poor release properties (Comparative Example 4). Similarly, molded articles obtained from thermoplastic resin compositions prepared using the silicone acrylic core-shell resin powder of Comparative Production Example 1, which has too little acrylic resin coating on the outer periphery, also have poor release properties (Comparative Example 3). In contrast, molded articles obtained from the thermoplastic resin composition of the present invention all exhibit excellent release properties (Examples 1-7). In particular, although the molded articles obtained from the thermoplastic resin composition of the present invention do not use a silane coupling agent, they exhibit release properties equivalent to those of molded articles obtained from thermoplastic resin compositions prepared with a conventional silane coupling agent (Reference Example 5).

[0069] [Examples 2, 8-12, Comparative Examples 6-9, Reference Example 10] Using a T-die in a Laboplast Mill (manufactured by Toyo Seiki Seisakusho), the above-mentioned thermoplastic urethane resin and the silicone acrylic core-shell resin powder obtained in the above-mentioned manufacturing example or comparative manufacturing example were mixed in the proportions shown in Table 5 or 6 below, and molded at approximately 200°C to produce a resin molded product (film) having a thickness of approximately 200 μm. The thermoplastic polyurethane is Elastoran ET-597-10 or Miractoran XN-2000, as described above.

[0070] <Static and Dynamic Friction Coefficients> The friction coefficient was determined from the frictional force using a HEIDON TYPE-R (manufactured by Shinto Kagaku Co., Ltd.). The friction coefficient was calculated from the frictional force when a 200g metal indenter was brought into contact with the coating perpendicularly and moved at a speed of 3 cm / min. The results are shown in Table 5 or 6.

[0071] [Table 5]

[0072] [Table 6]

[0073] [Examples 13-17, Comparative Examples 11-13, Reference Example 14] Using a T-die in a Laboplast Mill (manufactured by Toyo Seiki Seisakusho), a pellet pre-compounded by adding 65 parts of DINP (a plasticizer) and stabilizers to 100 parts by weight of polyvinyl chloride resin with a degree of polymerization of 1300, was mixed with silicone acrylic core-shell resin powder obtained in the above manufacturing example or comparative manufacturing example in the proportions shown in Table 7 or 8 below. The mixture was then molded at approximately 140°C to produce a resin molded product (film) with a thickness of approximately 200 μm. Furthermore, polyvinyl chloride resin (PVC) is made by mixing 100 parts by weight of polyvinyl chloride resin having a degree of polymerization of 1300 with 65 parts by weight of the plasticizer DINP and stabilizers, and then forming it into pellets.

[0074] [Table 7]

[0075] [Table 8]

[0076] As shown in Tables 5 and 7, molded articles obtained from the thermoplastic resin composition of the present invention have a lower coefficient of friction and superior wear resistance compared to the comparative examples, which do not contain silicone acrylic core-shell resin powder (comparison between Examples 2 and 8-11 and Comparative Example 6, comparison between Example 12 and Comparative Example 7, and comparison between Examples 13-17 and Comparative Example 11). In particular, molded articles obtained from the thermoplastic resin composition of the present invention, although not using a silane coupling agent, exhibit a lower coefficient of friction and superior wear resistance comparable to molded articles obtained from conventional thermoplastic resin compositions containing a silane coupling agent (Reference Examples 10 and 14). On the other hand, molded articles obtained from thermoplastic resin compositions prepared using the siloxane emulsion of Comparative Production Example 2, which does not satisfy the mass ratio of the present invention in the core-shell structure, have a high coefficient of friction and poor wear resistance (Comparative Examples 9 and 13). Similarly, molded articles obtained from thermoplastic resin compositions prepared using the silicone acrylic core-shell resin powder of Comparative Production Example 1, which has too little acrylic resin coating on the outer circumference, also have a high coefficient of friction and poor wear resistance (Comparative Examples 8 and 12). [Explanation of symbols]

[0077] (1) Core particle (organopolysiloxane) (2) Shell layer (poly(meth)acrylic acid ester) (3) Perimeter length of the shell layer (value from (1)) (4) Length of the portion on the outer circumference that does not contain poly(meth)acrylic acid ester (value of (2))

Claims

1. (I) Thermoplastic resin: 80 to 99.9 parts by mass per 100 parts by mass of the total of component (I) and component (II) below, and (II) Silicone-acrylic core shell resin 0.1 to 20 parts by mass per 100 parts by mass of the total of component (I) and component (II) A thermoplastic resin composition containing, The (II) silicone-acrylic core-shell resin is characterized in that the core particles are (A) organopolysiloxane, the shell layer has (B) poly(meth)acrylic acid ester, the mass ratio of (A) organopolysiloxane to (B) poly(meth)acrylic acid ester is (A):(B) = 40:60 to 90:10, and the ratio ((β / α) × 100) of the length of the poly(meth)acrylic acid ester portion on the outer circumference to the total outer circumference (α) of the core-shell resin is 90% or more, and the average particle diameter of the (II) silicone-acrylic core-shell resin is 50 to 400 nm. In the (II) silicone-acrylic core shell resin, the core particles are (a) an organopolysiloxane consisting of the following general formula (1), and the shell layer has (b) a polymer of (meth)acrylic acid ester monomers. 【Chemistry 1】 (In the formula, R １ R is an unsubstituted alkyl group having 1 to 20 carbon atoms. ２ (where X is a phenyl group, X is independently an unsubstituted C1-C20 alkyl group, a C6-C20 aryl group, a C1-C20 alkoxy group, or a hydroxyl group, Y is independently a group defined by X, where at least one of the groups represented by X is a hydroxyl group, and at least one of the groups represented by Y is a hydroxyl group, a is a number of 0 or more, b is a positive number that is 30-100% of the total number of a, b, c, and e, c is a positive number that is 0-60% of the total number of a, b, c, and e, and e is a number that is 0-10% of the total number of a, b, c, and e) The thermoplastic resin composition wherein the mass ratio of component (a) to component (b) is (a):(b) = 40:60 to 90:

10.

2. The thermoplastic resin composition according to claim 1, wherein the (II) silicone-acrylic core shell resin has a shell layer with a thickness of 1 nm to 50 nm.

3. The thermoplastic resin composition according to claim 1 or 2, wherein the (I) thermoplastic resin is at least one selected from urethane resin, vinyl chloride resin, acrylic resin, styrene-butadiene-acrylonitrile resin, polyester resin, amide resin, acetal resin, and polycarbonate resin.

4. A thermoplastic resin composition according to any one of claims 1 to 3, which does not contain a silane coupling agent.

5. A resin molded article obtained by injection molding or extrusion molding of a thermoplastic resin composition according to any one of claims 1 to 4.

6. The resin molded product according to claim 5, wherein the resin molded product is in the form of a film or a sheet.

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