Resin composition, molding material, resin molded article, and film and method for producing same

Abstract

A resin composition containing (A) a (meth) acrylic polymer as a random copolymer and / or a homopolymer and (B) a (meth) acrylic copolymer as a block copolymer and / or a graft copolymer, and a method for producing the same, the resin composition comprising (A) a (meth) acrylic polymer as a random copolymer and / or a homopolymer and (B) a (meth) acrylic copolymer as a block copolymer and / or a graft copolymer, the (meth) acrylic polymer (A) contains 50 mass% or more of repeating units derived from methyl methacrylate, and the (meth) acrylic polymer (A) contains a (meth) acrylic polymer (A1) having a mass average molecular weight of more than 130000 in terms of polystyrene as determined by gel permeation chromatography (GPC) measurement; and a (meth) acrylic copolymer (B) that contains, in the same molecule, a polymer (B1) that contains 50% by mass or more of units derived from methyl methacrylate and that has a glass transition temperature of higher than 0 DEG C, and a polymer (B2) that has a glass transition temperature of 0 DEG C or less, the (meth) acrylic copolymer (B) being a polymer that contains, in the same molecule, a polymer (B1) that contains 50% by mass or more of units derived from methyl methacrylate and a polymer (B2) that has a glass transition temperature of 0 DEG C or less.

Description

Technical Field

[0001] This invention relates to resin compositions, molding materials comprising the resin compositions, resin molded articles using the molding materials, films, and methods for manufacturing the same. Background Technology

[0002] Acrylic resins are widely used in front panels of liquid crystal displays and organic EL (electroluminescence) displays, signage, lighting products, home appliances, vehicle interior / exterior materials, industrial materials, building materials, lenses, light guide plates, light-concentrating components, and optical films for liquid crystal displays and organic EL displays.

[0003] In some of these applications, it is required that acrylic resin products possess flexibility. Furthermore, it is required that acrylic resins can be molded into thin and complex shapes using melt molding methods such as injection molding and extrusion molding. In other words, acrylic resins with excellent melt moldability are required.

[0004] As a technique to improve the impact resistance of acrylic resins, for example, Patent Document 1 discloses a resin composition which is formed by combining a rubber having a core-shell structure (core-shell rubber) with a (meth)acrylic resin, the core-shell structure having: a core portion composed of cross-linked rubber; and a shell portion that ensures compatibility and dispersibility with the (meth)acrylic polymer as a matrix.

[0005] The resin composition described in Patent Document 1 contains core-shell rubber, which tends to increase melt viscosity and decrease melt moldability. Therefore, there is a problem that the use of the resin composition is limited to resin articles with large thickness and simple shapes.

[0006] As a method for solving the above-mentioned problems, resin compositions obtained by incorporating block copolymers and / or graft copolymers into (meth)acrylate resins instead of core-shell rubber are known. In block copolymers and / or graft copolymers, two or more polymer segments are linked to each other by chemical bonds. Therefore, the phase separation structure of the resin composition formed by incorporating block copolymers and / or graft copolymers having poly(meth)acrylate chains into acrylic resins is nanoscale (referred to as "microphase separation structure"). Therefore, in such resin compositions and molded articles formed from such resin compositions, the characteristics of the acrylic resin as the matrix and the block copolymers and / or graft copolymers can be jointly exhibited. Moreover, the characteristics of each polymer segment of the block copolymer and / or graft copolymer can also be exhibited.

[0007] In a resin composition formed by incorporating the block copolymer and / or graft copolymer into an acrylic resin, a microphase separation structure is formed. Therefore, the resin molded body obtained by molding the resin composition can well maintain the transparency of the acrylic resin, and the properties (e.g., flexibility, impact resistance, etc.) of each polymer segment of the block copolymer and / or graft copolymer are excellent.

[0008] As a technique for improving the impact resistance of acrylic resins using block copolymers, for example, Patent Document 2 discloses a method for obtaining block copolymers by controlled free radical polymerization in the presence of nitroxide radicals. Specifically, it discloses a method for manufacturing cast sheets by polymerizing a syrup in a mold, thereby obtaining a sheet-like molded body containing block copolymers. Patent Document 2 describes that the obtained sheet-like molded body contains (meth)acrylic resin and a block copolymer having polymethyl methacrylate chains and n-butyl acrylate-styrene copolymer chains, exhibiting excellent impact resistance and transparency.

[0009] On the other hand, as a method for manufacturing the aforementioned block copolymers and / or graft copolymers, a known method involves pre-producing acrylic macromonomers (hereinafter referred to as "macromonomers") using trace amounts of cobalt complexes with extremely high chain transfer constants, and then copolymerizing these macromonomers with other monomers to produce block copolymers and / or graft copolymers. Catalytic chain transfer polymerization (CCTP) is a known method for manufacturing acrylic macromonomers using cobalt complexes. Macromonomers refer to polymers with polymerizable functional groups in their molecular structure; they are sometimes also called macromonomers.

[0010] Patent document 3 discloses the following technology: using CCTP to manufacture macromonomers, then using the obtained macromonomers to manufacture macromonomer copolymers, and then adding the obtained macromonomer copolymers to acrylic resins, thereby achieving both impact resistance and transparency.

[0011] Existing technical documents

[0012] Patent documents

[0013] Patent Document 1: Japanese Patent Publication No. 62-21804

[0014] Patent Document 2: Japanese Patent Application Publication No. 2008-274290

[0015] Patent Document 3: Japanese Patent Application Publication No. 2022-065185 Summary of the Invention

[0016] The problem that the invention aims to solve

[0017] In the method described in Patent Document 2, the synthesis of the block copolymer, the synthesis of polymethyl methacrylate as the matrix, and the manufacture of the molded body are carried out simultaneously. Therefore, it is not suitable for melt molding, and cannot be molded into thin-walled or complex shapes.

[0018] In the method described in Patent Document 3, a molded body with good impact resistance and flexibility can be obtained by using a molding material that can be melt-formed and has excellent moldability. However, if a membrane is manufactured, the resulting membrane is prone to cracking and has poor operability.

[0019] The object of the present invention is to provide a resin composition, a molding material using the resin composition, a resin molded body and a film formed by molding the molding material, and a method for manufacturing the thereof, wherein the resin composition, in an acrylic resin molding material comprising block copolymers and / or graft copolymers, can produce a film with good operability and excellent surface smoothness.

[0020] Solution for solving the problem

[0021] The inventors have discovered that the above-mentioned problems can be solved by combining and coordinating specific (meth)acrylic polymers.

[0022] That is, the present invention is based on the following principles.

[0023] [1] A resin composition comprising: a (meth)acrylic polymer (A) as a random copolymer and / or homopolymer; and a (meth)acrylic copolymer (B) as a block copolymer and / or graft copolymer, wherein the (meth)acrylic polymer (A) comprises more than 50% by mass of repeating units derived from methyl methacrylate, the (meth)acrylic polymer (A) comprises a (meth)acrylic polymer (A1) having a mass-average molecular weight (MA) of more than 130,000 as determined by gel permeation chromatography (GPC), the (meth)acrylic copolymer (B) being a polymer comprising polymer (B1) and polymer (B2) in the same molecule, wherein polymer (B1) is a polymer comprising more than 50% by mass of units derived from methyl methacrylate and having a glass transition temperature above 0°C, and polymer (B2) is a polymer having a glass transition temperature below 0°C.

[0024] [2] According to the resin composition of [1], wherein the (meth)acrylic polymer (A) further comprises (meth)acrylic polymer (A2), wherein the (meth)acrylic polymer (A2) has a melt flow rate of 7.0 g / 10 min or more at 230 °C and 37.3 N according to JIS K7210 or ISO 1133, and wherein the resin composition contains 3 to 15% by mass of the (meth)acrylic polymer (A2) relative to 100% by mass of the total resin composition.

[0025] [3] The resin composition according to [1] or [2], wherein the melt flow rate of the (meth)acrylic polymer (A1) according to JIS K7210 or ISO 1133 at 230°C and 37.3N is less than 7.0 g / 10 min.

[0026] [4] The resin composition according to any one of [1] to [3], wherein, relative to 100% by mass of the total resin composition, it comprises more than 15% by mass of the (meth)acrylic copolymer (B).

[0027] [5] The resin composition according to any one of [1] to [4], wherein the mass-average molecular weight of the (meth)acrylic copolymer (B) exceeds 300,000.

[0028] [6] The resin composition according to any one of [1] to [5], wherein the (meth)acrylic copolymer (B) comprises repeating units derived from macromonomer (b1) represented by the following general formula (1).

[0029] [Chemical Formula 1]

[0030]

[0031] In equation (1), R 0 ~R n Each can be independently a hydrogen atom, alkyl, cycloalkyl, aryl, or heterocyclic group. X 1 ~X n Each atom can be independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10000.

[0032] [7] A molding material comprising a resin composition according to any one of [1] to [6].

[0033] [8] The molding material according to [7], wherein the molding material is a molding material for film.

[0034] [9] The molding material according to [7], wherein the molding material is a molding material for extruded film.

[0035]

[10] A resin molded body, which is formed by molding a molding material according to any one of [7] to [9].

[0036]

[11] An optical film formed from a molding material according to any one of [7] to [9].

[0037]

[12] A polarizing protective film, which is formed from a molding material according to any one of [7] to [9].

[0038]

[13] A polarizer comprising a resin molded body according to

[10] .

[0039]

[14] An image display device comprising a resin molded body according to

[10] .

[0040]

[15] A method for manufacturing a resin composition, characterized in that the resin composition is manufactured by mixing a (meth)acrylic polymer (A) as a random copolymer and / or homopolymer and a (meth)acrylic copolymer (B) as a block copolymer and / or graft copolymer, wherein the (meth)acrylic polymer (A) comprises more than 50% by mass of repeating units derived from methyl methacrylate, the (meth)acrylic polymer (A) comprises a (meth)acrylic polymer (A1) having a mass-average molecular weight of more than 130,000 as determined by gel permeation chromatography (GPC), the (meth)acrylic copolymer (B) is a polymer containing polymer (B1) and polymer (B2) in the same molecule, wherein polymer (B1) is a polymer containing more than 50% by mass of units derived from methyl methacrylate and having a glass transition temperature higher than 0°C, and polymer (B2) is a polymer having a glass transition temperature lower than 0°C.

[0041]

[16] The method for manufacturing the resin composition according to

[15] , wherein the (meth)acrylic polymer (A) further comprises (meth)acrylic polymer (A2), wherein the (meth)acrylic polymer (A2) has a melt flow rate of 7.0 g / 10 min or more at 230 °C and 37.3 N according to JIS K7210 or ISO 1133, and wherein the resin composition contains 3 to 15% by mass of the (meth)acrylic polymer (A2) relative to 100% by mass of the total resin composition.

[0042]

[17] The method of manufacturing the resin composition according to

[15] or

[16] , wherein the melt flow rate of the (meth)acrylic polymer (A1) according to JIS K7210 or ISO 1133 at 230°C and 37.3N is less than 7.0 g / 10 min.

[0043]

[18] A method for manufacturing a resin composition according to any one of

[15] to

[17] , wherein the resin composition comprises 15% by mass or more of the (meth)acrylic copolymer (B) relative to a total of 100% by mass of the resin composition.

[0044]

[19] A method for manufacturing a resin composition according to any one of

[15] to

[18] , wherein the mass-average molecular weight of the (meth)acrylic copolymer (B) exceeds 300,000.

[0045]

[20] A method for manufacturing a resin composition according to any one of

[15] to

[19] , wherein the (meth)acrylic copolymer (B) comprises repeating units derived from a macromonomer (b1) represented by the following general formula (1).

[0046] [Chemical Formula 2]

[0047]

[0048] In equation (1), R 0 ~R n Each can be independently a hydrogen atom, alkyl, cycloalkyl, aryl, or heterocyclic group. X 1 ~X n Each atom can be independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10000.

[0049]

[21] A method for manufacturing a resin molded article, wherein the resin composition is manufactured by manufacturing a resin composition according to any one of the resin compositions described in

[15] to

[20] , and a molding material comprising the resin composition is molded.

[0050] Invention Effects

[0051] The resin composition and molding material of the present invention have excellent moldability, and can produce films with good operability and excellent surface smoothness.

[0052] Examples of operability of the membrane in this invention include: preventing cracks from propagating in an undesirable direction during membrane cutting; enabling the blade to travel smoothly; and suppressing dust generation during membrane cutting. Detailed Implementation

[0053] The following provides a detailed description of the methods for carrying out the present invention. The present invention is not limited to the following description and can be implemented in various ways within its scope.

[0054] In this invention, "(meth)acrylic acid" refers to one or both of "acrylic acid" and "methacrylic acid". "(meth)acrylate" refers to one or both of "methacrylate" and "acrylate". The same applies to "(meth)acryloyl".

[0055] In this invention, "monomer" refers to an unpolymerized compound (monomer component before polymerization), and "repeating unit" and "structural unit" refer to the constituent units that constitute the polymer derived from the monomer formed by monomer polymerization.

[0056] The building blocks that make up a polymer are called "monomer units".

[0057] "Repeating unit" or "structural unit" can be a unit formed directly through a polymerization reaction, or a unit formed by processing the polymer to convert a portion of the unit into a different structure.

[0058] In this invention, "mass%" represents the percentage of a specific component contained in 100% of the total mass.

[0059] Unless otherwise specified, the numerical range indicated by “~” in this specification refers to the range of values ​​recorded before and after “~” as the lower and upper limits. “A~B” means above A and below B.

[0060] In this invention, the mass-average molecular weight (Mw) of the (meth)acrylic polymer (A) refers to the relative molecular weight calculated using gel permeation chromatography (GPC) to convert it to polystyrene. The mass-average molecular weight (Mw) of the (meth)acrylic copolymer (B) refers to the relative molecular weight calculated using gel permeation chromatography (GPC) to convert it to polymethyl methacrylate (PMMA).

[0061] [Resin Composition]

[0062] The resin composition of the present invention comprises the (meth)acrylic polymer (A) and the (meth)acrylic copolymer (B) described later as essential components.

[0063] The (meth)acrylic polymer (A) includes the (meth)acrylic polymer (A1) described later as an essential component. Moreover, the (meth)acrylic polymer (A) preferably includes the (meth)acrylic polymer (A2) described later.

[0064] The (meth)acrylic acid copolymer (B) includes polymers (B1) and (B2) described later in the same molecule and has at least one of the structures of block copolymers and graft copolymers.

[0065] By including (meth)acrylic polymer (A1) as an essential component in the resin composition of the present invention, the film formed by molding the resin composition and molding material of the present invention can be made to have good operability.

[0066] By including (meth)acrylic acid copolymer (B) as an essential component in the resin composition of the present invention, the resulting resin composition and molding material exhibit excellent flowability, thereby improving the softness of the resin molded body and film obtained by molding the resin composition and molding material.

[0067] [(Meth)acrylic polymer (A)]

[0068] (Meth)acrylic polymer (A) is one of the components of the resin composition of the present invention.

[0069] (Meth)acrylic polymer (A) is a random copolymer and / or homopolymer containing (meth)acrylic polymer (A1) as an essential component.

[0070] The (meth)acrylic polymer (A) contains more than 50% by mass of repeating units derived from methyl methacrylate (hereinafter, sometimes referred to as "methyl methacrylate units") per 100% of its total mass. The (meth)acrylic polymer (A) preferably does not contain block structures and / or graft structures.

[0071] The methyl methacrylate unit comprises 100% by mass relative to the total mass of the (meth)acrylic polymer (A), preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0072] If the lower limit of the content ratio of methyl methacrylate units in (meth)acrylic polymer (A) is 50% or more relative to 100% of the total mass of (meth)acrylic polymer (A), then the heat resistance, hardness, scratch resistance, weather resistance, transparency, and processability of (meth)acrylic polymer (A) can be well maintained. There is no particular upper limit to the content ratio of methyl methacrylate units; (meth)acrylic polymer (A) can be a homopolymer with 100% methyl methacrylate units.

[0073] In addition to repeating units derived from methyl methacrylate, (A) acrylic polymers may also contain units derived from other comonomers that can copolymerize with methyl methacrylate (hereinafter, sometimes referred to as "comonomer units") from the viewpoint of improving thermal decomposition resistance.

[0074] In this case, by adjusting the type and content of comonomer units, the glass transition temperature (Tg), processability, heat resistance, refractive index, weather resistance, mold release properties, and thermal decomposition resistance of (meth)acrylic polymer (A) can be controlled.

[0075] From the perspective of maintaining the heat resistance, hardness, scratch resistance, weather resistance, transparency, and processability of the (meth)acrylic polymer (A), the upper limit of the content ratio of the comonomer unit in the (meth)acrylic polymer (A) is 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass, and particularly preferably 5% by mass or less, relative to 100% by mass of the total mass of the (meth)acrylic polymer (A).

[0076] There is no particular limitation on the lower limit of the content of the comonomer unit, and it may not contain the comonomer unit. That is, the (meth)acrylic polymer (A) may be a homopolymer with methyl methacrylate unit of 100% by mass.

[0077] Comonomers that form comonomer units of (meth)acrylic polymers (A) include, for example, the following (a) to (i).

[0078] a) Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, phenoxyethyl acrylate, and other (meth)acrylate monomers other than methyl methacrylate.

[0079] b) Hydroxyl-containing (meth)acrylate monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glyceryl (meth)acrylate.

[0080] c) Carboxyl-containing vinyl monomers such as (meth)acrylic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxypropyl succinate, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, and monomethyl itaconic acid.

[0081] d) Vinyl monomers containing anhydride groups, such as maleic anhydride and itaconic anhydride.

[0082] e) Glycidyl methacrylate, α-ethyl glycidyl methacrylate, 3,4-epoxybutyl methacrylate and other epoxy-containing vinyl monomers.

[0083] f) Dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and other amino-containing vinyl monomers of the (meth)acrylate system.

[0084] g) (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, diacetone acrylamide, maleic acid amide, maleimide and other vinyl monomers containing amide groups.

[0085] h) Vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, (meth)acrylonitrile, vinyl chloride, vinyl acetate, and vinyl propionate.

[0086] i) Multifunctional vinyl monomers such as divinylbenzene, ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, allyl methacrylate, N,N'-methylenebis(meth)acrylamide, etc.

[0087] They can be used individually or in combination with two or more.

[0088] Among them, considering the ease of obtaining the monomer, methyl acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred, and methyl acrylate is more preferred.

[0089] The mass-average molecular weight (Mw) of the (meth)acrylic polymer (A) determined by gel permeation chromatography (GPC) in this invention is not particularly limited, but is preferably 50,000 or more and 300,000 or less, more preferably 70,000 or more and 200,000 or less, and even more preferably 80,000 or more and 160,000 or less. If the lower limit of the Mw of the (meth)acrylic polymer (A) is 50,000 or more, the heat resistance, hardness, scratch resistance, weather resistance, and transparency of the (meth)acrylic polymer (A) are easily utilized. If the upper limit of the Mw of the (meth)acrylic polymer (A) is 300,000 or less, the melt viscosity is within an appropriate range, and the melt mixability and processability become good.

[0090] The content of the (meth)acrylic polymer (A) relative to 100% by mass of the total resin composition of the present invention is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more. If the content of the (meth)acrylic polymer (A) is 25% by mass or more, it effectively imparts properties characteristic of the (meth)acrylic polymer (A), such as heat resistance, weather resistance, and transparency. The content of the (meth)acrylic polymer (A) relative to 100% by mass of the total resin composition of the present invention is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less. If the content of the (meth)acrylic polymer (A) is 90% by mass or less, the content of the (meth)acrylic copolymer (B) increases relatively, thus making it easier to obtain molding materials with excellent moldability and films with excellent handling properties.

[0091] [(Meth)acrylic polymers (A1)]

[0092] (Meth)acrylic polymers (A1) are used as an essential component in the resin compositions of the present invention.

[0093] The (meth)acrylic polymer (A1) is characterized in that it is contained in the (meth)acrylic polymer (A) and the mass-average molecular weight of polystyrene, as determined by gel permeation chromatography (GPC), exceeds 130,000.

[0094] Furthermore, in order to meet the above-mentioned mass-average molecular weight conditions, the melt flow rate (MFR) of the (meth)acrylic polymer (A1) according to JIS K7210 or ISO 1133 at 230°C and 37.3N is preferably less than 7.0 g / 10 min, more preferably less than 4.0 g / 10 min, even more preferably less than 2.0 g / 10 min, and particularly preferably less than 1.0 g / 10 min.

[0095] There is no particular limit to the lower limit of the MFR of (meth)acrylic polymers (A1), which is usually above 0.1 g / 10 min.

[0096] By including (meth)acrylic polymer (A1), the following effect can be obtained: the operability of molding materials using the resin composition of the present invention and films formed from the molding materials can be improved.

[0097] Regarding the operability of the membrane, as mentioned above, for example, it can be cited that cracks are less likely to propagate in undesirable directions when cutting the membrane, allowing the cutting edge to travel smoothly. Furthermore, it can be cited that dust generation during membrane cutting can be suppressed.

[0098] The monomer units constituting the (meth)acrylic polymer (A1) and their preferred proportions are the same as those of the (meth)acrylic polymer (A) described above.

[0099] The mass-average molecular weight (Mw) of the (meth)acrylic polymer (A1) determined by gel permeation chromatography (GPC) to be equivalent to polystyrene is greater than 130,000, preferably 135,000 or more, more preferably 140,000 or more, and even more preferably 145,000 or more. If the Mw of the (meth)acrylic polymer (A1) exceeds 130,000, the operability of the resulting membrane becomes good. Furthermore, the mass-average molecular weight (Mw) of the (meth)acrylic polymer (A1) determined by gel permeation chromatography (GPC) to be equivalent to polystyrene is preferably 300,000 or less, more preferably 200,000 or less, and even more preferably 180,000 or less. If the Mw of the (meth)acrylic polymer (A1) is 300,000 or less, the moldability is good.

[0100] The proportion of the (meth)acrylic polymer (A1) relative to 100% by mass of the total resin composition of the present invention is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more. If the proportion of the (meth)acrylic polymer (A1) relative to 100% by mass of the total resin composition of the present invention is 10% by mass or more, the resulting film has good operability. The proportion of the (meth)acrylic polymer (A1) relative to 100% by mass of the total resin composition of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less. If the proportion of the (meth)acrylic polymer (A1) relative to 100% by mass of the total resin composition of the present invention is 90% by mass or less, the moldability is good.

[0101] Furthermore, the content of (meth)acrylic polymer (A1) relative to 100% by mass of the total (meth)acrylic polymer (A) is preferably 50% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 80% by mass or more. If the content of (meth)acrylic polymer (A1) relative to 100% by mass of the total (meth)acrylic polymer (A) is 50% by mass or more, the operability of the resulting membrane becomes good. The content of (meth)acrylic polymer (A1) relative to 100% by mass of the total (meth)acrylic polymer (A) can be 100% by mass. That is, the (meth)acrylic polymer (A) can be formed solely from (meth)acrylic polymer (A1).

[0102] [(Meth)acrylic polymer (A2)]

[0103] (Meth)acrylic polymer (A2) is an ingredient contained in the resin composition of the present invention as required.

[0104] (Meth)acrylic polymer (A2) is contained in (meth)acrylic polymer (A).

[0105] The function of the (meth)acrylic polymer (A2) is to adjust the flowability of the resin composition of the present invention during melt molding. Specifically, it has the function of adjusting the easing time of the molten resin as it is extruded from the die during the molding of the extruded film, thereby improving the smoothness of the cooled and solidified film surface. That is, by using an appropriate amount of the (meth)acrylic polymer (A2), the surface smoothness of the film can be improved, resulting in lower haze, and molding defects can be prevented, thus imparting good appearance quality.

[0106] From the viewpoint of achieving improved surface smoothness of the film and lower haze suppression, the melt flow rate (MFR) of the (meth)acrylic polymer (A2) measured according to JIS K7210 or ISO 1133 at 230°C and 37.3N is preferably 7.0 g / 10 min or more, more preferably 10.0 g / 10 min, and even more preferably 12.0 g / 10 min.

[0107] There is no particular upper limit to the MFR of (meth)acrylic polymers (A2), which is usually below 30 g / 10 minutes.

[0108] The mass-average molecular weight (Mw) of the (meth)acrylic polymer (A2), determined by gel permeation chromatography (GPC) based on polystyrene, is preferably 50,000 or more and 200,000 or less, more preferably 70,000 or more and 150,000 or less, and even more preferably 80,000 or more and 120,000 or less. If the lower limit of the Mw of the (meth)acrylic polymer (A2) is 50,000 or more, the heat resistance, hardness, scratch resistance, weather resistance, and transparency properties of the (meth)acrylic polymer (A) are easily exhibited. If the upper limit of the Mw of the (meth)acrylic polymer (A2) is 200,000 or less, the melt viscosity and tempering time are within an appropriate range, and the melt mixability, processability, and surface smoothness of the resulting film are good.

[0109] The monomer units constituting the (meth)acrylic polymer (A2) are the same as those of the (meth)acrylic polymer (A) described above. The (meth)acrylic polymer (A2) preferably contains 2% to 20% by mass of the aforementioned comonomer units, more preferably 5% to 18% by mass of the aforementioned comonomer units, and even more preferably 10% to 15% by mass of the aforementioned comonomer units.

[0110] By including comonomer units in the (meth)acrylic polymer (A2) within the above-mentioned range, the melt flow rate of the (meth)acrylic polymer (A2) described above can be easily achieved.

[0111] When the (meth)acrylic polymer (A) includes the (meth)acrylic polymer (A2), the content of the (meth)acrylic polymer (A2) in 100% by mass of the resin composition of the present invention is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, further preferably 3% by mass or more and 15% by mass or less, and particularly preferably 3% by mass or more and 12% by mass or less. By setting the content of the (meth)acrylic polymer (A2) to 1% by mass or more, it is easy to obtain the effect of suppressing the haze of the obtained film and suppressing molding defects. By setting the content of the (meth)acrylic polymer (A2) to 20% by mass or less, it is possible to prevent the decrease in mechanical properties of the resin composition such as heat resistance and impact resistance.

[0112] [(Meth)acrylic acid copolymer (B)]

[0113] The resin composition of the present invention comprises (meth)acrylic copolymer (B).

[0114] (Meth)acrylic copolymer (B) is a block copolymer and / or graft copolymer comprising polymers (B1) and (B2) described later in the same molecule, having at least one structure of block copolymer and graft copolymer.

[0115] The block and / or graft structures of the (meth)acrylic copolymer (B) can be any of the following: diblock, triblock, multiblock, grafted, cyclic, star-shaped, comb-shaped, dendritic, trapezoidal, etc., or a combination of multiple such structures. Among these structures, considering the desired imparting of flexibility and ease of manufacture, the (meth)acrylic copolymer (B) preferably includes at least one of the following structures: diblock, triblock, or grafted.

[0116] In the (meth)acrylic copolymer (B), polymer (B1) has the function of imparting miscibility and compatibility to the (meth)acrylic polymer (A) and the function of handling the (meth)acrylic copolymer (B) in solid form.

[0117] In (meth)acrylic copolymers (B), polymer (B2) imparts flexibility, impact resistance, and moldability.

[0118] For example, a (meth)acrylic acid copolymer (B) can be a graft copolymer consisting of a polymer (B1) as the main chain, with graft chains of polymer (B2) branching and linked to the main chain containing polymer (B1). Alternatively, the main chain can be polymer (B2), and the side chains can be polymer (B1). A (meth)acrylic acid copolymer (B) can also be a block copolymer consisting of polymers containing polymer (B1) linked in series with polymers containing polymer (B2). Furthermore, it can also be a structure in which block copolymers are included in the main chain and / or side chains of the graft copolymer.

[0119] The lower limit of the mass-average molecular weight (Mw) of the (meth)acrylic copolymer (B) is preferably greater than 120,000, more preferably greater than 300,000, further preferably greater than 500,000, and particularly preferably greater than 700,000. If the Mw of the (meth)acrylic copolymer (B) exceeds 120,000, the resin composition, molding material, and molded article exhibit good flexibility and impact resistance.

[0120] The upper limit of the mass-average molecular weight (Mw) of the (meth)acrylic copolymer (B) is preferably 5,000,000 or less, more preferably 3,500,000 or less, and even more preferably 2,000,000 or less. If the Mw of the (meth)acrylic copolymer (B) is 5,000,000 or less, the resin composition, molding material, and the resulting film have good transparency.

[0121] In this invention, the mass-average molecular weight (Mw) of the (meth)acrylic copolymer (B) refers to the relative molecular weight, i.e., the mass-average molecular weight, calculated using gel permeation chromatography (GPC) with polymethyl methacrylate (PMMA).

[0122] The content of the (meth)acrylic copolymer (B) relative to 100% by mass of the total resin composition of the present invention is preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. If the content of the (meth)acrylic copolymer (B) is 15% by mass or more, it is easy to impart the fluidity as a molding material and the operability as a film, which are characteristics of the (meth)acrylic copolymer (B).

[0123] The content of the (meth)acrylic copolymer (B) relative to 100% by mass of the total resin composition of the present invention is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. If the content of the (meth)acrylic copolymer (B) is 70% by mass or less, the effect of the (meth)acrylic polymer (A) can be easily obtained, and a film with good heat resistance, surface hardness, transparency, etc. can be obtained.

[0124] [Polymer (B1)]

[0125] Polymer (B1) is a polymer containing more than 50% by mass of methyl methacrylate units and having a glass transition temperature above 0°C.

[0126] By using the same comonomer unit as the aforementioned (meth)acrylic polymer (A) in polymer (B1), the function of polymer (B1) can be effectively utilized, namely, to impart miscibility and compatibility to (meth)acrylic polymer (A).

[0127] The polymer (B1) preferably contains 70% or more methyl methacrylate units relative to 100% of its total mass, more preferably 80% or more methyl methacrylate units, even more preferably 90% or more methyl methacrylate units, and particularly preferably 95% or more methyl methacrylate units.

[0128] If the lower limit of the content of methyl methacrylate units in polymer (B1) is 70% or more, especially 80% or more, relative to 100% of the total mass of polymer (B1), then polymer (B1) has good affinity for (meth)acrylic polymer (A) and good miscibility and compatibility.

[0129] There is no particular upper limit to the proportion of methyl methacrylate units in polymer (B1), and polymer (B1) can be a homopolymer of 100% by mass of methyl methacrylate.

[0130] In addition to methyl methacrylate units, polymer (B1) may also contain other comonomer units that can be copolymerized with methyl methacrylate, depending on the purpose of the (meth)acrylic copolymer (B).

[0131] For example, by including acrylate units as comonomer units in polymer (B1), depolymerization of polymer (B1) can be suppressed when exposed to high-temperature conditions such as melt molding, thus improving its thermal decomposition resistance.

[0132] Furthermore, by adjusting the type and content of comonomer units, the glass transition temperature (Tg), processability, heat resistance, refractive index, weather resistance, mold release properties, and thermal decomposition resistance of the polymer (B1) can be controlled.

[0133] Considering the ability to maintain properties such as heat resistance, hardness, scratch resistance, weather resistance, transparency, and processability, the upper limit of the content of comonomer units in polymer (B1) relative to 100% by mass is preferably 20% by mass or less. There is no particular limitation on the lower limit of the content of comonomer units in polymer (B1), and polymer (B1) may not contain comonomer units, i.e., it can be a homopolymer of methyl methacrylate.

[0134] Comonomers that form comonomer units of polymer (B1), for example, comonomers that form comonomer units of (meth)acrylic polymer (A) and are described above as a) to i). They may be used alone or in combination of two or more.

[0135] From the perspective of ease of obtaining the monomer, methyl acrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate are preferred as comonomers included in polymer (B1), and methyl acrylate is more preferred.

[0136] The polymer (B1) preferably comprises building blocks derived from the macromonomer (b1) described later. In this case, methyl methacrylate units may also be included in the macromonomer (b1).

[0137] The glass transition temperature (Tg) of polymer (B1) is above 0°C, preferably 50°C or higher, more preferably 90°C or higher, and even more preferably 100°C or higher. By making the glass transition temperature (Tg) of polymer (B1) above 0°C, it is expected to improve the workability of the (meth)acrylic copolymer (B), and improve the heat resistance of the resin composition, molded article, and film of the present invention. There is no particular upper limit to the glass transition temperature (Tg) of polymer (B1), but from the viewpoint of ease of acquisition, it is generally below 130°C.

[0138] In this invention, the Tg of polymer (B1) can be calculated as follows: using the values ​​recorded in known literature such as the Polymer Handbook Fourth Edition 2003 as the Tg of the homopolymer of the monomers constituting polymer (B1), and using the Fox formula. Alternatively, dynamic viscoelasticity can be measured on the obtained resin molded body, and the value of tanδ can be used as Tg.

[0139] The lower limit of the mass-average molecular weight (Mw) of polymer (B1) is preferably 3,000 or more, more preferably 10,000 or more, further preferably 15,000 or more, and particularly preferably 20,000 or more. If the Mw of polymer (B1) is 3,000 or more, polymer (B1) has good affinity for (meth)acrylic polymer (A) and can be expected to impart miscibility and compatibility.

[0140] The upper limit of the mass-average molecular weight (Mw) of polymer (B1) is preferably 1,000,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, and particularly preferably 40,000 or less. If the Mw of polymer (B1) is 1,000,000 or less, the melt viscosity is within an appropriate range.

[0141] In this invention, the mass-average molecular weight (Mw) of polymer (B1) refers to the relative molecular weight, i.e., the mass-average molecular weight, calculated using gel permeation chromatography (GPC) with polymethyl methacrylate (PMMA).

[0142] Polymer (B1) can be a mixture of two or more polymers. In this case, the weight-average molecular weight (Mw) is calculated as the overall value of polymer (B1). When multiple polymers (B1) with different weight-average molecular weights (Mw) are used together, the polymer (B1) with a lower molecular weight plays a role in reducing slurry viscosity and preventing copolymer crosslinking, while the polymer (B1) with a higher molecular weight plays a role in ensuring compatibility with the matrix resin when used as an additive.

[0143] The proportion of polymer (B1) in the (meth)acrylic copolymer (B) relative to 100% by mass of the total mass of the (meth)acrylic copolymer (B) is preferably 35% by mass or more and 75% by mass or less. If the lower limit of the proportion of polymer (B1) is 35% by mass or more, it is easy to obtain a (meth)acrylic copolymer (B) with excellent miscibility and compatibility with the (meth)acrylic polymer (A). The lower limit of the proportion of polymer (B1) is preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more. If the upper limit of the proportion of polymer (B1) is 75% by mass or less, it is easy to obtain the effect of imparting softness from polymer (B2). The upper limit of the proportion of polymer (B1) is preferably 70% by mass or less, more preferably 65% ​​by mass or less.

[0144] [Polymer (B2)]

[0145] Polymer (B2) imparts properties such as film softness, impact resistance, and improved flowability during melt molding to (meth)acrylic copolymer (B) and the resin composition, molding material, and resin molded body of the present invention using (meth)acrylic copolymer (B).

[0146] The glass transition temperature (Tg) of polymer (B2) is below 0°C, preferably below -10°C, more preferably below -20°C, and even more preferably below -35°C. By setting the glass transition temperature (Tg) of polymer (B2) to below 0°C, improvements in flexibility, impact resistance, and melt flowability during molding can be expected. There is no particular limitation on the lower limit of the glass transition temperature (Tg) of polymer (B2), but from the viewpoint of ease of acquisition, it is generally above -70°C.

[0147] In this invention, the Tg of polymer (B2) can be calculated as follows: using the values ​​recorded in known literature such as the Polymer Handbook Fourth Edition 2003 as the Tg of the homopolymer of the monomers constituting polymer (B2), and using the Fox formula. Alternatively, dynamic viscoelasticity can be measured on the obtained resin molded body, and the value of tanδ can be used as Tg.

[0148] The proportion of polymer (B2) in the (meth)acrylic copolymer (B) relative to 100% by mass of the total mass of the (meth)acrylic copolymer (B) is preferably 25% by mass or more and 65% by mass or less. If the lower limit of the polymer (B2) content is 25% by mass or more, the improved flexibility, impact resistance, and moldability resulting from the (meth)acrylic copolymer (B) are readily obtained. The lower limit of the polymer (B2) content is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more. If the upper limit of the polymer (B2) content is 65% by mass or less, the (meth)acrylic copolymer (B) exhibits good workability. The upper limit of the polymer (B2) content is preferably 65% ​​by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, particularly preferably 50% by mass or less, and most preferably 45% by mass or less.

[0149] The refractive index of polymer (B2) is preferably set such that the difference between its refractive index and that of polymer (B1) and (meth)acrylic polymer (A) is small. This results in good transparency of the resin composition, molding material, and molded article of the present invention. The refractive index difference between polymer (B2) and polymer (B1) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0.02 or less. Similarly, the refractive index difference between polymer (B2) and (meth)acrylic polymer (A) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0.02 or less.

[0150] The weight-average molecular weight (Mw) of polymer (B2) is preferably 3,000 or more, more preferably 10,000 or more, even more preferably 15,000 or more, and particularly preferably 20,000 or more. If the Mw of polymer (B2) is 3,000 or more, it exhibits good impact resistance. Furthermore, the weight-average molecular weight (Mw) of polymer (B2) is preferably 2,500,000 or less, more preferably 2,000,000 or less, even more preferably 1,500,000 or less, and particularly preferably 1,000,000 or less. If the Mw of polymer (B2) is 2,500,000 or less, the transparency of the resin composition, molding material, and film of the present invention becomes good.

[0151] The mass-average molecular weight (Mw) of polymer (B2) can be calculated based on the total mass-average molecular weight (Mw) of the (meth)acrylic copolymer (B) and the weight ratio of polymer (B1) to polymer (B2). The weight ratio of polymer (B1) to polymer (B2) can be determined by... 1The molecular weight (Mw) of polymer (B) can be determined by methods such as H-NMR. For example, if the mass-average molecular weight (Mw) of the (meth)acrylic copolymer (B) is 100,000 and the polymer (B2) accounts for 40% of the total mass of the (meth)acrylic copolymer (B), the mass-average molecular weight (Mw) of polymer (B2) can be calculated as 100,000 × 0.4 = 400,000.

[0152] [Monomer (b2)]

[0153] Monomer (b2) is the monomer used as a raw material for polymer (B2). Monomer (b2) is not particularly limited as long as it can produce (meth)acrylate copolymers (B), and various polymerizable monomers can be used as needed. Specifically, considering the aspects of setting a low glass transition temperature (Tg) to impart flexibility, impact resistance, and moldability, as well as adjusting the refractive index, acrylates and aromatic vinyl compounds are preferred. Other monomers can also be used as needed.

[0154] The acrylate used in monomer (b2) is preferably 70% by mass or more, more preferably 79% by mass or more, and even more preferably 81% by mass or more, relative to 100% of the total mass of monomer (b2). If the lower limit of the acrylate content is 70% by mass or more, the (meth)acrylic copolymer (B) can be endowed with improved flexibility, impact resistance, and moldability. If the acrylate content of monomer (b2) is low, the effects of improving flexibility, impact resistance, and moldability may become insufficient.

[0155] There is no particular limit to the upper limit of the proportion of acrylate contained in monomer (b2), but it is preferably less than 100% by mass relative to the total mass of monomer (b2), more preferably 95% by mass or less, and even more preferably 90% by mass or less.

[0156] For acrylates, from the perspective of making the obtained resin molded articles have better impact resistance, the glass transition temperature (Tg) of the homopolymer of acrylate is preferably below 0°C.

[0157] In this invention, the Tg of the homopolymer of acrylate can be calculated by using values ​​recorded in known literature such as the Polymer Handbook (POLYMER HANDBOOK FOURTH EDITION 2003) and the Fox formula.

[0158] Acrylates used as monomers (b2) include, for example: methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, n-lauryl acrylate, n-stearyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, phenoxyethyl acrylate, etc.; hydroxyl-containing acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, glyceryl acrylate, etc.; 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxypropyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, etc. Acrylates containing carboxyl groups, such as 2-acryloyloxypropyl formate, 2-acryloyloxyethyl maleate, 2-acryloyloxypropyl maleate, 2-acryloyloxyethyl succinate, and 2-acryloyloxypropyl succinate; epoxy-containing acrylates, such as glycidyl acrylate, glycidyl α-ethyl acrylate, and 3,4-epoxybutyl acrylate; amino-containing acrylates, such as dimethylaminoethyl acrylate and diethylaminoethyl acrylate; and multifunctional acrylates, such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,6-hexanediol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, allyl acrylate, and N,N'-methylenebisacrylamide. These can be used alone or in combination of two or more.

[0159] Among the aforementioned monomers, 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, n-butyl acrylate, n-propyl acrylate, ethyl acrylate, and 2-hydroxyethyl acrylate are preferred from the perspective of the homopolymer having a Tg of 0°C or below. Furthermore, methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferred from the perspective of easy availability.

[0160] The aromatic vinyl compounds that can be used in the monomer (b2) are used to adjust the refractive index of the polymer (B2) and to adjust the polymerization rate when manufacturing the polymer (B2) and the (meth)acrylic copolymer (B).

[0161] The aromatic vinyl compound used in monomer (b2) is preferably 10 to 30% by mass relative to 100% by mass of the total mass of monomer (b2), more preferably 13 to 21% by mass, and even more preferably 15 to 19% by mass. If the aromatic vinyl compound contained in monomer (b2) is 10% by mass or more, the resin composition, molding material, and molded body of the present invention exhibit good transparency. If the aromatic vinyl compound contained in monomer (b2) is 30% by mass or less, the polymerization reaction rate during the manufacture of the (meth)acrylic copolymer (B) is sufficiently accelerated.

[0162] Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, p-tert-butylstyrene, vinylethylbenzene, vinyltoluene, vinylxylene, vinylnaphthalene, diphenylethylene, and divinylbenzene. Among these, styrene is preferred from the viewpoint of practicality and productivity. They can be used alone or in combination of two or more.

[0163] Monomer (b2) may, as needed, contain other monomers that can copolymerize with the acrylate and the aromatic vinyl compound.

[0164] Other monomers include, for example: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, n-stearyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, phenoxyethyl methacrylate, etc.; hydroxyl-containing methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, glyceryl methacrylate, etc.; 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxypropyl hexahydrophthalic acid, 2-... Methacrylates containing carboxyl groups, such as 2-methacryloyloxypropyl phthalate, 2-methacryloyloxyethyl maleate, 2-methacryloyloxypropyl maleate, 2-methacryloyloxyethyl succinate, and 2-methacryloyloxypropyl succinate; epoxy-containing methacrylates, such as glycidyl methacrylate and 3,4-epoxybutyl methacrylate; amino-containing methacrylates, such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; polyfunctional methacrylates, such as ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate; etc. One or more of these can be appropriately selected for use.

[0165] Furthermore, other monomers include, for example: vinyl monomers containing carboxyl groups such as (meth)acrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, and monomethyl itaconic acid; vinyl monomers containing anhydride groups such as maleic anhydride and itaconic anhydride; vinyl monomers containing amide groups such as (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, diacetone acrylamide, maleic acid amide, and maleimide; vinyl monomers such as (meth)acrylonitrile, vinyl chloride, vinyl acetate, and vinyl propionate; etc.

[0166] When using other monomers, their usage is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, relative to 100% by mass of the total monomer (b2). Alternatively, other monomers may not be used.

[0167] [Method for manufacturing (meth)acrylic acid copolymer (B)]

[0168] The manufacturing method of the (meth)acrylic acid copolymer (B) of the present invention includes, but is not limited to, living polymerization and methods using a macromonomer (b1) described later. Living polymerization methods include, for example, living radical polymerization and living anionic polymerization. Living radical polymerization methods include, for example, reversible addition-fragmentation chain transfer polymerization (RAFT), atom transfer radical polymerization (ATRP), nitroxide radical controlled polymerization (NMP), and living radical polymerization with an organic tellurium end (TERP). The method using a macromonomer (b1) has the advantage of being able to manufacture the (meth)acrylic acid copolymer (B) more easily. The method using a macromonomer (b1) also has the advantage of not requiring the removal of catalyst and auxiliary residues and end-treatment steps required in living polymerization methods, and is therefore preferred.

[0169] [Manufacturing method of (meth)acrylic copolymer (B) using macromonomers]

[0170] As a method for manufacturing (meth)acrylate copolymers (B) using macromonomers, the macromonomers can be used as raw materials for either polymer (B1) or polymer (B2). A macromonomer copolymer is obtained by copolymerizing the macromonomer with a comonomer that can copolymerize with the macromonomer. This macromonomer copolymer is then used as the (meth)acrylate copolymer (B).

[0171] Here, as an example, a method for producing a macromonomer copolymer by copolymerizing macromonomer (b1) with monomer (b2) using macromonomer (b1) as a raw material for polymer (B1) will be described. In this case, polymer (B2) has monomer (b2) as a monomer unit.

[0172] [Method for manufacturing macromonomer (b1)]

[0173] The macromonomer (b1) can be manufactured by known methods. Examples of methods for manufacturing the macromonomer include: methods using a cobalt chain transfer agent (US Patent 4,680,352), methods using α-substituted unsaturated compounds such as α-bromomethylstyrene as chain transfer agents (International Publication No. 88 / 04304), methods chemically bonding polymerizable groups (Japanese Patent Application Laid-Open No. 60-133007, US Patent 5,147,952, Japanese Patent Application Laid-Open No. 06-298,921), and methods based on thermal decomposition (Japanese Patent Application Laid-Open No. 11-240,854). Among these, the method using a cobalt chain transfer agent is preferred as a method for manufacturing the macromonomer (b1) from the perspective of fewer manufacturing steps and the use of catalysts with high chain transfer constants.

[0174] Methods for manufacturing macromonomers (b1) using cobalt chain transfer agents include, for example, bulk polymerization, solution polymerization, and aqueous dispersion polymerization methods such as suspension polymerization and emulsion polymerization. Among these, aqueous dispersion polymerization is preferred from the perspective of simplifying the recovery process of macromonomers (b1).

[0175] As the cobalt chain transfer agent used in this invention, the cobalt chain transfer agent shown in the following general formula (2) can be used. For example, the cobalt chain transfer agent described in Japanese Patent No. 3,587,530, Japanese Unexamined Patent Application Publication No. 6-23,209, Japanese Unexamined Patent Application Publication No. 7-35,411, US Patent No. 4,526,945, US Patent No. 4,694,054, US Patent No. 4,834,326, US Patent No. 4,886,861, US Patent No. 5,324,879, International Publication No. 95 / 17,435, and Japanese Unexamined Patent Application Publication No. 9-510,499 can be used.

[0176] [Chemical Formula 3]

[0177]

[0178] [In the formula, R] 11 ~R 14 Each can be independently alkyl, cycloalkyl, or aryl. X 11 ~X 14 Each can be independently an F atom, Cl atom, Br atom, OH group, alkoxy group, aryloxy group, alkyl group, or aryl group.

[0179] Specifically, examples of cobalt chain transfer agents include: bis(boryl difluorodimethyldioxyiminocyclohexane)cobalt(II), bis(boryl difluorodimethylglyoxime)cobalt(II), bis(boryl difluorodiphenylglyoxime)cobalt(II), cobalt(II) complexes of ortho-iminohydroxyimino compounds, cobalt(II) complexes of tetraazatetraalkylcyclotetradecaneteene, N,N'-bis(salicylene)ethylidene diaminocobalt(II) complexes, cobalt(II) complexes of dialkyldiazadioxodialkyldodecanediene, and cobalt(II)porphyrin complexes. Among these, bis(boryl difluorodiphenylglyoxime)cobalt(II) (R) which is stable in aqueous media and exhibits high chain transfer efficiency is preferred. 11 ~R 14 : Phenyl, X 11 ~X 14 (F atom). They can be used in more than one of them as appropriate.

[0180] The amount of cobalt chain transfer agent used is preferably 5 to 350 ppm relative to the monomer used to obtain the macromonomer (b1). If the amount of cobalt chain transfer agent used is 5 ppm or more, the decrease in molecular weight is more likely to be sufficient. If the amount of cobalt chain transfer agent used is 350 ppm or less, the obtained macromonomer (b1) is less likely to be colored.

[0181] The lower limit of the mass-average molecular weight (Mw) of the macromonomer (b1) is preferably 3,000 or more, more preferably 10,000 or more, further preferably 15,000 or more, and particularly preferably 20,000 or more. If the Mw of the macromonomer (b1) is 3,000 or more, the polymer (B1) derived from the macromonomer (b1) has good affinity for the (meth)acrylic polymer (A), and can be expected to impart miscibility and compatibility.

[0182] The upper limit of the mass-average molecular weight (Mw) of the macromonomer (b1) is preferably 1,000,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, and particularly preferably 40,000 or less. If the Mw of the macromonomer (b1) is 1,000,000 or less, the melt viscosity of the (meth)acrylic acid copolymer (B) is within an appropriate range.

[0183] In this invention, the mass-average molecular weight (Mw) of the macromonomer (b1) refers to the relative molecular weight, i.e., the mass-average molecular weight, calculated using gel permeation chromatography (GPC) with polymethyl methacrylate (PMMA).

[0184] Solvents used in solution polymerization to obtain macromonomers (b1) include, for example: 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; esters such as ethyl acetate; carbonates such as ethylene carbonate; and supercritical carbon dioxide. They can be used alone or in combination of two or more.

[0185] [Method for manufacturing macromolecular monomer copolymers]

[0186] The method for manufacturing macromonomer copolymers includes a step of carrying out a polymerization reaction of a polymerizable mixture comprising the polymerizable composition (X) described later and a polymerization initiator.

[0187] The polymerizable composition (X) contains a macromonomer (b1) represented by the following general formula (1) and a comonomer that can copolymerize with the macromonomer (b1). The comonomer is selected from monomers (b2) that can copolymerize with the macromonomer (b1).

[0188] [Chemical Formula 4]

[0189]

[0190] In equation (1), R 0 ~R n Each can be independently a hydrogen atom, alkyl, cycloalkyl, aryl, or heterocyclic group. X 1 ~X n Each atom can be independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10000.

[0191] <R 0 ~R n >

[0192] In the above equation (1), R 0 ~R n The alkyl, cycloalkyl, aryl, or heterocyclic groups may optionally have substituents.

[0193] As R 0 ~R n Alkyl groups, for example, branched or straight-chain alkyl groups having 1 to 20 carbon atoms. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl. Among these, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl are preferred from the perspective of easy availability, methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl are more preferred, and methyl is particularly preferred.

[0194] As R 0 ~R n The cycloalkyl group can be categorized as follows: cycloalkyl groups with 3 to 20 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tert-butylcyclohexyl, isobornyl, and adamantyl. For ease of acquisition, cyclopropyl, cyclobutyl, and adamantyl are preferred.

[0195] As R 0 ~R n Aryl groups, for example, include aryl groups with 6 to 18 carbon atoms. Specific examples include phenyl, benzyl, and naphthyl.

[0196] As R 0 ~R n Heterocyclic groups, for example, include heterocyclic groups with 5 to 18 carbon atoms. Specific examples include γ-lactone, ε-caprolactone, and morpholino groups. Heteroatoms contained in the heterocycle include oxygen, nitrogen, and sulfur atoms.

[0197] As R0 ~R n The substituents can be independently listed from the group consisting of alkyl, aryl, carboxyl, alkoxycarbonyl (-COOR'), carbamoyl (-CONR'R''), cyano, hydroxyl, amino, amide (-NR'R''), halogen atom, allyl, epoxy, alkoxy (-OR'), and groups exhibiting hydrophilic or ionic properties. It should be noted that, as examples of R' or R'', independently listed are groups or atoms related to R... 0 ~R n The same groups (excluding heterocyclic groups).

[0198] As R 0 ~R n The substituent is an alkoxycarbonyl group, for example, the methoxycarbonyl group.

[0199] As R 0 ~R n The carbamoyl group of the substituent, for example, N-methylcarbamoyl and N,N-dimethylcarbamoyl.

[0200] As R 0 ~R n The amide group of the substituent, for example, is dimethylamide.

[0201] As R 0 ~R n The halogen atom of the substituent can be, for example, fluorine, chlorine, bromine and iodine atoms.

[0202] As R 0 ~R n The alkoxy group with substituents, for example, alkoxy groups having 1 to 12 carbon atoms. As a specific example, methoxy groups can be listed.

[0203] As R 0 ~R n Substituents that exhibit hydrophilic or ionic properties include, for example, alkali salts of carboxyl groups or alkali salts of sulfoxyl groups, poly(olefin) groups such as poly(olefin) groups such as poly(olefin) groups and quaternary ammonium groups.

[0204] R 0 ~R n Preferably, it is selected from at least one of alkyl and cycloalkyl groups, more preferably alkyl.

[0205] As an alkyl group, methyl, ethyl, n-propyl or isopropyl are preferred, and methyl is more preferred from the viewpoint of ease of acquisition.

[0206] <X 1~X n >

[0207] In the above formula (1), from the viewpoint of the ease of synthesis of the macromonomer (b1), regarding X 1 ~X n In comparison to X 1 ~X n The total molar content is 100 mol%, preferably 80 mol% or more of which are methyl groups.

[0208] <z>

[0209] In the formula (1), Z is the terminal group of the macromonomer (b1). As terminal groups of the macromonomer (b1), examples include hydrogen atoms and groups derived from free radical polymerization initiators, similar to those of polymers obtained by known free radical polymerization.

[0210] There is no particular limitation on the lower limit of the content ratio of methyl methacrylate units in the macromonomer (b1). If the content ratio of methyl methacrylate units is 50% by mass or more relative to 100% by mass of the total mass of macromonomer (b1), it is beneficial to improve impact resistance and transparency. The lower limit of the content ratio of methyl methacrylate units is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0211] There is no specific upper limit to the content of methyl methacrylate units. The macromonomer (b1) can be 100% by mass of methyl methacrylate units. The content of methyl methacrylate units relative to 100% by mass of the total mass of macromonomer (b1) can be 99% by mass or less.

[0212] In the method for manufacturing macromolecular monomer copolymers, the polymerization reaction is preferably carried out using free radical polymerization. Examples of free radical polymerization methods include bulk polymerization methods such as bulk polymerization and casting polymerization; solution polymerization; and aqueous dispersion polymerization methods such as suspension polymerization and emulsion polymerization.

[0213] From the perspective of simplifying the recycling process of the macromolecular monomer copolymer, aqueous dispersion polymerization methods such as suspension polymerization and emulsion polymerization are preferred. From the perspective of good operability of the obtained polymer particles, suspension polymerization is more preferred.

[0214] In suspension polymerization, the macromonomer copolymer is obtained in the form of spherical particles with an average particle size of approximately 5 μm to 1 mm. The resulting spherical particles exhibit good handling properties and minimize concerns about dust dispersion during extrusion / molding and other processing operations, making them preferred as resin compositions. The spherical particles are further preferred considering the good moldability of the resin composition obtained by suspension polymerization. The rationale is not yet certain, but it is speculated that trace amounts of abnormal polymers and residual emulsifiers generated in emulsion polymerization act as foreign matter and cause thickening, resulting in suspension polymerization being superior to emulsion polymerization.

[0215] Details of suspension polymerization will be described later.

[0216] The polymerization reaction in the manufacture of macromonomer copolymers can also be carried out using bulk polymerization methods such as bulk polymerization or casting polymerization. In this case, the polymerization process includes heating the polymerizable mixture to polymerize it.

[0217] In the case of manufacturing macromonomer copolymers by solution polymerization, macromonomers (b1) can also be manufactured by solution polymerization. In this state, monomers (b2) and thermal polymerization initiators are added to the solution to carry out copolymerization, thereby obtaining macromonomer copolymers.

[0218] In the method for manufacturing macromolecular monomer copolymers of the present invention, the polymerizable mixture may also contain a sulfur-containing chain transfer agent.

[0219] Here, sulfur-containing chain transfer agents refer to thiol compounds such as n-butylthiol and n-octylthiol, which are added as chain transfer agents during polymerization to adjust the molecular weight of the copolymer.

[0220] When the polymerizable composition contains a sulfur-containing chain transfer agent, the upper limit of its content is preferably less than 0.01 parts by mass relative to 100 parts by mass of the polymerizable composition (X). If the upper limit of the sulfur-containing chain transfer agent content is less than 0.01 parts by mass, the broadening of the compositional distribution of the copolymer can be suppressed, resulting in good impact resistance of the obtained resin molded article. There is no particular limitation on the lower limit of the sulfur-containing chain transfer agent content, but the polymerizable composition is more preferably free of sulfur-containing chain transfer agent.

[0221] In the manufacture of macromonomer copolymers, polymerization can be carried out in such a way that the mass-average molecular weight (Mw) of the resulting macromonomer copolymer is above 240,000 and below 3,500,000.

[0222] The lower limit of the mass-average molecular weight (Mw) of the macromonomer copolymer is preferably 240,000 or more, more preferably 300,000 or more, and even more preferably 600,000 or more. If the Mw of the macromonomer copolymer is 240,000 or more, the resin composition, molding material, and molded article of the present invention have good flexibility and impact resistance.

[0223] The upper limit of the mass-average molecular weight (Mw) of the macromonomer copolymer is preferably 3,500,000 or less, more preferably 3,000,000 or less, and even more preferably 2,000,000 or less. If the Mw of the macromonomer copolymer is 3,500,000 or less, the resin composition, molding material, and molded article of the present invention exhibit good transparency and moldability. The above-mentioned upper and lower limits can be combined arbitrarily.

[0224] In this invention, the mass-average molecular weight (Mw) of the macromolecular monomer copolymer refers to the relative molecular weight, i.e., the mass-average molecular weight, calculated using gel permeation chromatography (GPC) with polymethyl methacrylate (PMMA).

[0225] There are no particular limitations on the method for controlling the mass-average molecular weight (Mw) of macromonomer copolymers to be above 240,000. Regarding the Mw of macromonomer copolymers, it can be controlled by those skilled in the art through adjustments to the polymerization method, the type and amount of polymerization initiator, the amount of chain transfer agent, polymerization temperature, etc., according to known techniques.

[0226] [Polymerizable Composition (X)]

[0227] The polymeric composition (X) is one of the raw materials for the (meth)acrylic copolymer (B).

[0228] The proportions of macromonomer (b1) (b1, unit: mass%) and monomer (b2, unit: mass%) contained in the polymeric composition (X) relative to the total mass of the polymeric composition (X) are preferably b1:b2 = 35-75 mass%: 65-25 mass%, more preferably b1:b2 = 40-70 mass%: 60-30 mass%, further preferably b1:b2 = 45-70 mass%: 55-30 mass, particularly preferably b1:b2 = 50-65 mass%: 50-35 mass, and most preferably b1:b2 = 55-65 mass%: 45-35 mass.

[0229] The proportions of macromonomer (b1) (b1, unit: mass%) and monomer (b2, unit: mass%) contained in the polymeric composition (X) relative to 100% of the total mass of the polymeric composition (X) are preferably b1:b2 = 35:65 mass% to 75:25 mass%, more preferably b1:b2 = 40:60 mass% to 70:30 mass%, even more preferably b1:b2 = 45:55 mass% to 70:30 mass%, particularly preferably b1:b2 = 50:50 mass% to 65:35 mass%, and most preferably b1:b2 = 55:45 mass% to 65:35 mass.

[0230] If the lower limit of the proportion of macromonomer (b1) in the polymeric composition (X) is 35% by mass or more relative to 100% by mass of the total mass of the polymeric composition (X), or the upper limit of the proportion of monomer (b2) is 65% by mass or less, the workability of the macromonomer copolymer is good. If the lower limit of the proportion of monomer (b2) in the polymeric composition (X) is 25% by mass or more relative to 100% by mass of the total mass of the polymeric composition (X), or the upper limit of the proportion of macromonomer (b1) is 75% by mass or less, the impact resistance of the resin composition containing the macromonomer copolymer and the resulting resin molded article can be well maintained.

[0231] [Preparation of macromonomer copolymers using suspension polymerization]

[0232] The following is a detailed description of the polymerization reaction carried out using suspension polymerization.

[0233] In the manufacturing methods of macromolecular monomer copolymers, when using suspension polymerization to manufacture macromolecular monomer copolymers, the following methods (1) and (2) can be specifically listed.

[0234] (1) A method comprising the steps i) to v) below. This method is a method for separately manufacturing the macromonomer (b1) and the macromonomer copolymer of the present invention.

[0235] (2) A method in which steps i) to v) below are replaced by steps I) to II) below. This method is a method for continuously manufacturing the macromonomer (b1) and the macromonomer copolymer of the present invention.

[0236] i) Slurry preparation process

[0237] A slurry is prepared by dissolving a bead-shaped macromolecular monomer (b1) manufactured by suspension polymerization in a solution containing monomer (b2), and is used as a polymerizable composition (X).

[0238] In preparing the polymerizable composition (X), the mixture containing macromonomer (b1) and monomer (b2) can be heated at a temperature below the boiling point of monomer (b2) to promote the dissolution of macromonomer (b1). The preferred temperature for preparing the polymerizable composition (X) is in the range of 20°C to 100°C, more preferably in the range of 40°C to 80°C. If the free radical polymerization initiator used does not react at the temperature required to prepare the polymerizable composition (X), the free radical polymerization initiator can be mixed into the polymerizable composition (X) to obtain a polymerizable mixture, which is then heated.

[0239] ii) Free radical polymerization initiator dissolution process

[0240] If the free radical polymerization initiator reacts at the temperature at which the polymerizable composition (X) is obtained in step i), the polymerizable composition (X) is temporarily cooled to below room temperature, and then the free radical polymerization initiator is added to dissolve it uniformly, resulting in a polymerizable mixture. The temperature of the polymerizable composition (X) at which the free radical polymerization initiator is added is preferably set below the temperature obtained by subtracting 15°C from the 10-hour half-life temperature of the free radical polymerization initiator.

[0241] iii) Preparation process of aqueous solution

[0242] The polymeric mixture and an aqueous solution are mixed and stirred to prepare a suspension in which droplets of the polymeric mixture are dispersed in the aqueous solution. The aqueous solution refers to an aqueous solution used to disperse the polymeric mixture, and may contain dispersants, electrolytes, and other additives. By appropriately selecting the combination of dispersants and electrolytes, the dispersibility of the droplets of the polymeric mixture formed in the aqueous solution can be controlled.

[0243] From the perspective of good dispersibility of the droplets in the polymeric mixture, deionized water is preferably used in the aqueous solution.

[0244] Examples of dispersants include: alkali metal salts of poly(meth)acrylic acid, copolymers of alkali metal salts of (meth)acrylic acid and (meth)acrylates, copolymers of alkali metal salts of sulfonyl methacrylic acid and (meth)acrylates, alkali metal salts of polystyrene sulfonic acid, copolymers of alkali metal salts of styrene sulfonic acid and (meth)acrylates, or copolymers containing combinations of these monomers; polyvinyl alcohol, methylcellulose, starch, and hydroxyapatite with a saponification degree of 70% to 100%.

[0245] They can be used individually or in combination of two or more.

[0246] Among them, copolymers of alkali metal salts of sulfonyl acrylate and (meth)acrylate with good dispersion stability during suspension polymerization are preferred.

[0247] The dispersant is used, for example, in the range of 0.0005 to 0.5 parts by mass relative to 100 parts by mass of the polymeric composition (X).

[0248] Examples of electrolytes include sodium carbonate, sodium sulfate, and manganese sulfate.

[0249] Electrolytes are used, for example, in the range of 0.01 to 1.0 parts by mass relative to 100 parts by mass of the polymeric composition (X).

[0250] I) Slurry preparation process

[0251] A polymerizable composition (X) is prepared by adding a solution containing monomer (b2) to a bead-like macromonomer (b1) produced by suspension polymerization while it is dispersed in an aqueous solution.

[0252] The temperature at which the macromonomer (b1) is dissolved in the solution containing monomer (b2) is preferably in the range of 20°C to 100°C, more preferably in the range of 40°C to 90°C, and even more preferably in the range of 50°C to 80°C. The aqueous solution can be the same as that described in iii) above.

[0253] II) Free radical polymerization initiator dissolution process

[0254] If the free radical polymerization initiator reacts at the temperature at which the polymerizable composition (X) obtained in step I) is prepared, the polymerizable composition (X) is temporarily cooled to below room temperature, and then the free radical polymerization initiator is added to dissolve it uniformly, resulting in a polymerizable mixture. The temperature at which the free radical polymerization initiator is added is preferably set below the temperature obtained by subtracting 15°C from the 10-hour half-life temperature of the free radical polymerization initiator.

[0255] When a polymerization reaction is carried out in the presence of a free radical polymerization initiator, known organic peroxides such as 2,4-dichlorobenzoyl peroxide and tert-butyl peroxypentanoate, and known azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylpentanonitrile) can be used as free radical polymerization initiators.

[0256] The amount of free radical polymerization initiator can be appropriately selected by those skilled in the art according to known techniques. Generally, the amount of free radical polymerization initiator is 0.0001 to 10 parts by mass relative to 100 parts by mass of the polymerizable composition (X).

[0257] iv) Polymerization reaction process

[0258] Next, the resulting suspension is stirred and heated to initiate the polymerization reaction. Preferably, the polymerizable mixture and the aqueous solution before heating are subjected to degassing under reduced pressure and nitrogen replacement to remove dissolved oxygen in advance.

[0259] The polymerization temperature during the polymerization reaction is an important condition for obtaining macromonomer copolymers in high yield. The polymerization temperature referred to here is the temperature of the suspension. The polymerization temperature is preferably 50°C to 90°C, more preferably 60°C to 85°C, and even more preferably 65°C to 80°C. If the polymerization temperature is too low, there is a concern that the reaction will proceed slowly and the polymerization time will be prolonged. If the polymerization temperature is too high, the adduct radicals, which are reaction intermediates, will preferentially break down, tending to reduce the yield of the macromonomer copolymer.

[0260] In the later stages of the polymerization reaction, the suspension may be heated to increase the reaction rate of the polymerizable composition (X) and to eliminate unreacted free radical polymerization initiators. The preferred temperature for heating the suspension is 80°C or higher, more preferably 85°C or higher. The heating time can be determined by calculating the time until the free radical polymerization initiators disappear, typically from 30 minutes to about 2 hours.

[0261] v) Recycling process

[0262] Following the aforementioned process, the suspension is cooled to below room temperature, and then the resulting bead-like copolymer is recovered using known methods such as filtration. Depending on the requirements, washing processes for removing impurities such as dispersants and electrolytes, removal processes for beads containing air bubbles, and drying processes may be performed.

[0263] The resulting bead-like macromolecular monomer copolymer is used as the (meth)acrylic copolymer (B) of the present invention.

[0264] [Core-shell rubber (C)]

[0265] The resin composition of the present invention may contain core-shell rubber (C) as needed.

[0266] Core-shell rubber (C) is a different component from (meth)acrylic copolymer (B).

[0267] Core-shell rubber (C) is a particle-shaped rubber comprising a core formed of rubber components and a shell component having functions such as compatibility with the matrix.

[0268] Core-shell rubber (C) is used for the purpose of imparting softness and impact resistance to the resin compositions, molding materials, resin molded articles and films of the present invention.

[0269] The core-shell rubber (C) can be appropriately selected from commonly available core-shell rubbers. Types of core-shell rubbers include: acrylic rubber containing acrylate as repeating units, butadiene rubber containing butadiene as repeating units, butadiene-acrylic composite rubber containing both butadiene and acrylate as repeating units, and silicone-acrylic composite rubber containing dimethylsiloxane and acrylate as repeating units.

[0270] Among these, considering the improvement of the transparency of the resin composition, it is preferable that the refractive index of the core is close to that of the (meth)acrylic polymer (A). From the viewpoint of refractive index, as the type of core, acrylic rubber containing acrylate as repeating unit and butadiene-acrylic composite rubber containing butadiene and acrylate as repeating units are preferred.

[0271] From the perspective of improving the weather resistance of the resin composition, acrylic rubber and silicone-acrylic composite rubber containing dimethylsiloxane and acrylate as repeating units are preferred as the type of core.

[0272] From the perspective of improving toughness and impact resistance, the preferred types of cores are butadiene rubber containing butadiene as a repeating unit, butadiene-acrylic composite rubber containing butadiene and acrylate as repeating units, and organosilicon-acrylic composite rubber containing dimethylsiloxane and acrylate as repeating units.

[0273] The type of core can be appropriately selected based on the required performance of the resin molded body and the film. Multiple core-shell rubbers of different types can also be used in combination.

[0274] The core-shell rubber (C) is not particularly limited, but it is preferred to have a multi-layer structure with three or more layers, including an inner layer, an intermediate layer and a graft layer.

[0275] The average particle size of the core-shell rubber (C) is preferably 50 nm or more, more preferably 100 nm or more, and even more preferably 200 nm or more. The average particle size of the core-shell rubber (C) is preferably 1000 nm or less, more preferably 700 nm or less, and even more preferably 500 nm or less. If the average particle size is 50 nm or more, it can function as a rubber, improving toughness and impact resistance. If the average particle size is 1000 nm or less, the particle number increases, resulting in good toughness and impact resistance.

[0276] Core-shell rubber (C) is a cause of foreign matter defects during the manufacture of extruded films, therefore its use is preferably minimal. When using core-shell rubber (C), its content relative to 100% by mass of the resin composition of the present invention is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. Most preferably, core-shell rubber (C) is not used.

[0277] [Anti-blocking agent (D)]

[0278] When using the resin composition of the present invention to manufacture a film, an anti-blocking agent (D) is preferably added to prevent the film from sticking together during winding. The anti-blocking agent (D) is also known as an anti-blocking agent (AB agent) or a lubricant. Various commonly available anti-blocking agents can be used.

[0279] As an anti-blocking agent (D), various resin particles and inorganic particles can be used. Examples of resin particles include: acrylic particles, polystyrene particles, polyester particles, organosilicon microparticles, polyvinyl chloride particles, etc. Examples of inorganic particles include: colloidal silica, fumed silica, zeolite, needle-like silica, talc, alumina, mineral powder, etc.

[0280] Among these, acrylic particles are preferred from the perspective that the resin composition of the present invention contains a (meth)acrylic polymer (A). By selecting acrylic particles, the refractive index difference with the resin composition of the present invention becomes smaller, and resin molded articles and films with excellent transparency can be obtained.

[0281] During the melt mixing of the resin composition, the anti-blocking agent maintains the particle shape; therefore, cross-linked acrylic particles are preferred. Furthermore, to prevent resin blockage, pressure loss, and filter clogging during melt mixing and melt molding, the anti-blocking agent preferably does not contain large particles. For these reasons, cross-linked acrylic particles with small particle size and few coarse particles are preferred as the anti-blocking agent (D). Considering the reduction of coarse particles, monodisperse cross-linked acrylic particles are preferred.

[0282] The average particle size of the anti-blocking agent (D) is preferably 10 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, and most preferably 1 μm or less. If the average particle size of the anti-blocking agent (D) is 10 μm or less, it can exert its anti-blocking properties with a small amount added, and its impact on transparency can be minimized. The average particle size of the anti-blocking agent (D) is preferably 10 nm or more, more preferably 50 nm or more, and more preferably 100 nm or more. If the average particle size of the anti-blocking agent (D) is 10 nm or more, it can exert its anti-blocking properties.

[0283] The amount of anti-blocking agent added relative to 100% by mass of the total resin composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. If the amount of anti-blocking agent (D) added is 0.01% by mass or more, anti-blocking properties can be achieved. The amount of anti-blocking agent (D) added relative to 100% by mass of the total resin composition of the present invention is preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.5% by mass or less. If the amount of anti-blocking agent (D) added is 2% by mass or less, disadvantages such as decreased transparency can be suppressed.

[0284] [Other ingredients]

[0285] The resin composition of the present invention may contain other components besides the above-mentioned (meth)acrylic polymer (A), (meth)acrylic copolymer (B), core-shell rubber (C) and anti-blocking agent (D).

[0286] Other components are added to the resin composition as needed. Examples of such other components include: mold release agents, antioxidants, heat stabilizers, impact modifiers, flexibility enhancers, weather resistance enhancers, colorants, inorganic pigments, organic pigments, carbon black, ferrites, conductivity enhancers, ultraviolet absorbers, infrared absorbers, inorganic fillers, reinforcing agents, plasticizers, anti-plasticizers, neutralizers, crosslinking agents, flame retardants, preservatives, insect repellents, fragrances, free radical supplements, sound-absorbing materials, etc. These other components can be used individually or in combination of two or more.

[0287] [Methods for manufacturing resin compositions and molding materials]

[0288] The resin composition of the present invention can be manufactured by mixing raw materials according to conventional methods, and the method is not particularly limited. As a mixing method, for example, a method of heating and melting the raw materials in a single-screw extruder or a twin-screw extruder at about 220 to 280°C can be listed.

[0289] The resin composition of the present invention is processed into granules after being heated and melt-mixed, thus making it suitable for use as a molding material, such as a molding material for film, and in particular a molding material for extruded films.

[0290] [Resin Molded Body]

[0291] The resin composition and molding material of the present invention are shaped by known melt molding methods such as extrusion molding, injection molding, compression molding, and blow molding to become resin molded bodies.

[0292] The shape of the resin molded article of the present invention is not particularly limited, for example, film-like, sheet-like, plate-like, generally box-shaped, and three-dimensional shape with curved surface.

[0293] [Use of the resin molded body]

[0294] Regarding the resin molded body of the present invention, it has excellent flexibility that enables it to be handled as a film and transparency within a wide range of use temperatures. Therefore, the resin molded body of the present invention can be applied to front panels of displays such as liquid crystals and organic ELs, sign supplies, lighting supplies, household electrical appliances, interior / exterior materials for vehicles, industrial materials, building materials, lenses, light guide plates, light condensing members, optical films for displays such as liquid crystals and organic ELs, etc.

[0295] For example, as the resin molded body obtained by molding the molding material of the present invention, a polarizing plate protective film and a polarizing plate can be cited. The resin molded body of the present invention is useful as a constituent member of these image display devices.

[0296] Examples

[0297] Hereinafter, examples and comparative examples will be cited to explain the present invention in further detail. The present invention is not limited by the following examples.

[0298] Hereinafter, "parts" means "parts by mass".

[0299] [Evaluation method]

[0300] The evaluation in the examples and comparative examples was carried out by the following method.

[0301] (Weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the macromonomer (b1))

[0302] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the macromonomer (b1) obtained in the examples and comparative examples were measured using gel permeation chromatography (GPC). 10 mg of the obtained copolymer was dissolved in 10 mL of tetrahydrofuran, and the solution obtained by filtering with a 0.45 μm filter was used as a sample for GPC measurement.

[0303] In the measurement, in a gel permeation chromatography measuring device (manufactured by Tosoh Corporation, model name: HLC-8320 type), a polymer measurement guard column (manufactured by Tosoh Corporation, trade name: TSK-GUARD COLUMN SUPER H-H) and two polymer measurement chromatography columns (manufactured by Tosoh Corporation, trade name: TSK-GEL SUPER HM-H) were connected in series and used.

[0304] A differential refractometer (RI) was used as the detector.

[0305] The measurement was carried out under the following conditions: separation column temperature: 40 °C, mobile phase: tetrahydrofuran, flow rate of the mobile phase: 0.6 mL / minute, sample injection volume: 10 μL.

[0306] Several polymethyl methacrylates (PMMA) with known molecular weights (produced by Polymer Laboratories, peak molecular weight (Mp) 1560–19,500,000) were used as standard polymers to prepare standard curves, and the relative molecular weights Mw and Mn, converted to PMMA, were determined.

[0307] (Mass-average molecular weight (Mw) and number-average molecular weight (Mn) of macromonomer copolymers)

[0308] The mass-average molecular weight (Mw) and number-average molecular weight (Mn) of the macromonomer copolymers (B) obtained in the Examples and Comparative Examples were determined using gel permeation chromatography (GPC). 10 mg of the obtained copolymer was dissolved in 10 mL of tetrahydrofuran, and the solution obtained by filtration through a 0.45 μm filter was used as the sample for GPC determination.

[0309] In the assay, a polymer assay guard column (Tosoh Corporation, trade name: TSK-GUARD COLUMN SUPER HH) and an ultra-high molecular weight assay column (Tosoh Corporation, trade name: TSK-GEL GMHHR-H) are connected in series on a high performance liquid chromatography (HPLC) apparatus (Tosoh Corporation, model name: HLC-8320).

[0310] The detector uses a differential refractometer (RI).

[0311] The determination was performed under the following conditions: column temperature: 40℃, mobile phase: tetrahydrofuran, mobile phase flow rate: 0.6 mL / min, sample injection volume: 10 μL.

[0312] Several polymethyl methacrylates (PMMA) with known molecular weights (produced by Polymer Laboratories, peak molecular weight (Mp) 1560–19,500,000) were used as standard polymers to prepare standard curves, and the relative molecular weights Mw and Mn, converted to PMMA, were determined.

[0313] (Membrane operability: Evaluation of cutter toughness)

[0314] Based on the state of making a cut on the extruded film obtained in the Examples and Comparative Examples with scissors, the following evaluation was conducted on the movement of the blade using a cutting knife (manufactured by OLFA, trade name: Type A). The angle of the blade relative to the film was adjusted to approximately 45° to 60°.

[0315] ◎: In 10 tests, the blade can travel more than 9 times.

[0316] ○: In 10 tests, the blade can travel more than 5 times but less than 9 times.

[0317] ×: In 10 tests, the blade travels less than 5 times, or it cannot travel at all.

[0318] (Other membrane evaluation: membrane surface smoothness)

[0319] Indoors, fluorescent lamps are reflected onto the extruded films obtained in the examples and comparative examples, and the surface smoothness is judged by whether the image of the fluorescent lamp projected onto the film appears clear.

[0320] ○: There are no small bumps or dents; the edges of the fluorescent light appear to be straight.

[0321] △: You can see some minor bumps and the edges of the fluorescent light look slightly messy.

[0322] ×: It has small bumps and the edges of the fluorescent light look messy.

[0323] (Other membrane evaluations: anti-blocking properties)

[0324] The extruded films obtained in the examples and comparative examples were rubbed against each other in an overlapping state to evaluate the ease of film movement.

[0325] ○: Membrane movement.

[0326] ×: The membrane does not move.

[0327] [raw materials]

[0328] The abbreviations of the compounds used in the examples and comparative examples are shown below.

[0329] MMA: Methyl methacrylate (manufactured by Mitsubishi Chemical).

[0330] MA: Methyl acrylate (manufactured by Mitsubishi Chemical).

[0331] BA: n-Butyl acrylate (manufactured by Mitsubishi Chemical).

[0332] ST: Styrene (manufactured by FUJIFILM Wako Pure Chemical).

[0333] Dispersant (1): The dispersant manufactured in manufacturing example 1.

[0334] Chain transfer agent (1): The chain transfer catalyst manufactured in manufacturing example 2.

[0335] Polymerization initiator (1): 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate (manufactured by Nippon Oil Company, trade name: PEROCTA O).

[0336] Polymerization initiator (2): 2,2'-azobis(2-methylbutyronitrile) (manufactured by FUJIFILM Wako Pure Chemical Co., Ltd., trade name: V-59).

[0337] (Meth)acrylic polymers (A1-1): (Meth)acrylic polymers containing more than 90% by mass of methyl methacrylate units, with a mass-average molecular weight of 140,000 and an MFR of less than 1.0 g / 10 minutes (230°C, 37.3 N).

[0338] (Meth)acrylic polymers (A1-2): (Meth)acrylic polymers containing more than 90% by mass of methyl methacrylate units, with a mass-average molecular weight of 150,000 and an MFR of less than 1.0 g / 10 minutes (230°C, 37.3 N).

[0339] (Meth)acrylic polymers (A1-3): (Meth)acrylic polymers containing more than 90% by mass of methyl methacrylate units, with a mass-average molecular weight of 170,000 and an MFR of less than 1.0 g / 10 minutes (230°C, 37.3 N).

[0340] (Meth)acrylic polymer (A2-1): A (meth)acrylic polymer containing more than 80% by mass of methyl methacrylate units, with a mass-average molecular weight of 100,000 and an MFR of 14 g / 10 min (230 °C, 37.3 N).

[0341] (Meth)acrylic polymer (A-1): A (meth)acrylic polymer containing more than 95% by mass of methyl methacrylate units, with a mass-average molecular weight of 100,000 and an MFR of 2 g / 10 min (230 °C, 37.3 N).

[0342] (Meth)acrylic polymer (A-2): A (meth)acrylic polymer containing more than 90% by mass of methyl methacrylate units, with a mass-average molecular weight of 120,000 and an MFR of 14 g / 10 min (230 °C, 37.3 N).

[0343] Anti-blocking agent (D) (MX-80H3wT): Trade name, manufactured by Zongyan Chemical Co., Ltd., cross-linked acrylic monodisperse particles, average particle size: 0.8μm.

[0344] [Manufacturing Example 1: Synthesis of Dispersant (1)]

[0345] In a reaction apparatus equipped with a stirrer, cooling pipe, and thermometer, 61.6 parts of a 17% (w / w) potassium hydroxide aqueous solution, 19.1 parts of MMA, and 19.3 parts of deionized water were added. The liquid in the reaction apparatus was then stirred at room temperature until an exothermic peak was observed, and the mixture was stirred for 4 hours. The reaction solution was then cooled to room temperature to obtain a potassium methacrylate aqueous solution.

[0346] Next, in a polymerization apparatus equipped with a stirrer, cooling pipes, and a thermometer, 900 parts of deionized water, 70 parts of a 42% by mass aqueous solution of sodium 2-ethanesulfonate methacrylate (manufactured by Mitsubishi Chemical, trade name: ACRYESTER SEM-Na), 16 parts of the aforementioned potassium methacrylate aqueous solution, and 7 parts of MMA were added and stirred. While nitrogen purging was performed in the polymerization apparatus, the liquid in the reaction apparatus was heated to 50°C. 0.053 parts of V-50 (manufactured by FUJIFILM Wako Pure Chemical, 2,2'-azobis(2-methylpropanediamine) dihydrochloride, trade name) as a polymerization initiator were added to the polymerization apparatus, and the liquid in the reaction apparatus was heated to 60°C. After adding the polymerization initiator, 1.4 parts of MMA were added in batches every 15 minutes, for a total of 5 additions (7 parts of total MMA). Then, while stirring the liquid in the polymerization apparatus, it was kept at 60°C for 6 hours, and then cooled to room temperature to obtain a dispersant with 8% by mass of solid components as a transparent aqueous solution (1).

[0347] [Manufacturing Example 2: Synthesis of Chain Transfer Agent (1)]

[0348] In a synthesis apparatus equipped with a stirring device, 2.00 g (8.03 mmol) of cobalt(II) acetate tetrahydrate (manufactured by FUJIFILMWako Pure Chemical Co., Ltd., Wako Special Grade), 3.86 g (16.1 mmol) of diphenyl oxime (manufactured by Tokyo Chemical Co., Ltd., EP Grade), and 100 mL of diethyl ether that had been deoxygenated by nitrogen bubbling were added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 2 hours.

[0349] Next, 20 mL of boron trifluoride diethyl ether complex (manufactured by Tokyo Chemical Co., Ltd., EP grade) was added, and the mixture was stirred for 6 hours. The resulting product was filtered. The filtered solid was washed with diethyl ether and dried at 100 MPa and 20°C for 12 hours to obtain 5.02 g (7.93 mmol, yield 99% by mass) of chain transfer agent (1) as a brownish-yellow solid.

[0350] [Manufacturing Example 3: Synthesis of Macromonomer (b1)]

[0351] In a polymerization apparatus equipped with a mixer, cooling pipe, and thermometer, 145 parts by weight of deionized water, 0.1 parts by weight of sodium sulfate (Na2SO4), and 0.26 parts by weight of dispersant (1) (8% by weight of solid content) prepared in Manufacturing Example 1 were added and stirred to prepare a homogeneous aqueous solution. Next, 95 parts by weight of MMA, 5.0 parts by weight of MA, 0.0014 parts by weight of chain transfer agent (1) prepared in Manufacturing Example 2, and 0.25 parts by weight of polymerization initiator (1) were added to prepare an aqueous dispersion.

[0352] Next, the polymerization apparatus was thoroughly nitrogen-purged. The aqueous dispersion was heated to 80°C and held for 3 hours, then heated to 90°C and held for 2 hours. The reaction mixture was then cooled to 40°C to obtain an aqueous suspension of the macromonomer. This aqueous suspension was filtered through a filter cloth. The filter media was washed with deionized water and dried at 40°C for 16 hours to obtain bead-like macromonomers (b1).

[0353] The obtained macromonomer (b1) has a number-average molecular weight (Mn) of 21,300 and a mass-average molecular weight (Mw) of 39,100.

[0354] The Tg of homopolymer of methyl methacrylate (MMA) is 105 °C (POLYMER HANDBOOK FOURTHEDITION 2003), and the Tg of homopolymer of methyl acrylate (MA) is 10 °C (POLYMER HANDBOOK FOURTHEDITION 2003). When calculated using the Fox formula, the Tg of the macromonomer (b1) is 99 °C.

[0355] [Manufacturing Example 4: (Meth)acrylic Copolymer (B)]

[0356] In a polymerization apparatus equipped with a mixer, cooling pipe, and thermometer, 60 parts of the macromonomer (b1) obtained in Manufacturing Example 3, 150 parts of deionized water, 0.26 parts of dispersant (1), and 0.3 parts of sodium sulfate were added and stirred to obtain an aqueous suspension. Next, the polymerization apparatus was heated to 70°C, and 33.2 parts of BA and 6.8 parts of ST were slowly added. Then, the mixture was stirred and kept at 70°C for 1 hour to dissolve the macromonomer (b1) in BA and ST, obtaining a dispersion. Next, the polymerization apparatus was cooled to 40°C, and 0.5 parts of polymerization initiator (2) were added and stirred for 30 minutes to dissolve it. Next, the polymerization apparatus was thoroughly nitrogen-purged, and the aqueous dispersion was heated to 82°C and kept at 4 hours, then heated to 90°C and kept at 1 hour. Then, the mixture was cooled to below 40°C, filtered through a filter cloth, and the filtrate was washed with deionized water. Using a hot air circulating dryer, the water-washed filter material was dried at 40°C for 12 hours to obtain (meth)acrylic copolymer (B) as a bead-shaped macromolecular monomer copolymer.

[0357] The number-average molecular weight (Mn) of the obtained (meth)acrylic acid copolymer (B) is 75,000, and the mass-average molecular weight (Mw) is 1,300,000.

[0358] The Tg of the homopolymer of styrene (ST) is 100°C (POLYMER HANDBOOK FOURTH EDITION 2003), and the Tg of the homopolymer of n-butyl acrylate (BA) is -54°C (POLYMER HANDBOOK FOURTH EDITION 2003). When calculated using the Fox formula, the Tg of the polymer (B2) contained in the (meth)acrylic copolymer (B) is -37.5°C.

[0359] [Example 1]

[0360] A granular resin composition was prepared using a twin-screw extruder (product name: TEM-26SX, 26mmφ, L / D≈48) manufactured by Shibaura Machinery Co., Ltd.

[0361] Using 70 parts of (A1-1) as a (meth)acrylic polymer (A1) and 30 parts of the (meth)acrylic copolymer (B) obtained in Manufacturing Example 4, a granular resin composition (molding material) was obtained by melt mixing using a 26mmφ screw-type twin-screw extruder (manufactured by Shibaura Machinery Co., Ltd., model name: TEM-26SX) at a barrel temperature of 200-230°C and a die temperature of 230°C.

[0362] Using the obtained resin composition particles, a 50 μm thick extruded film was produced by forming a film at 240°C using a single-screw extruder (GMENGINEERING Co., Ltd., GM30-35) equipped with a T-die. The extruded film was evaluated as described above. The evaluation results are shown in Table 1.

[0363] [Examples 2-5, Comparative Examples 1 and 2]

[0364] Following the same procedure as in Example 1, a particulate resin composition was prepared, and an extruded film was produced and evaluated using the resin composition described in Table 1. The formulation of the resin composition and the evaluation results of the obtained film are shown in Table 1.

[0365] [Table 1]

[0366]

[0367] Comparing Examples 1-5 with Comparative Examples 1 and 2, it can be seen that in Examples 1-5, the (meth)acrylic polymer (A), as a random copolymer and / or homopolymer, contains more than 50% by mass of methyl methacrylate units, and includes a (meth)acrylic polymer (A1) with a mass-average molecular weight exceeding 130,000 based on polystyrene determined by gel permeation chromatography (GPC), thereby resulting in good cutter toughness and excellent membrane operability. In particular, the cutter toughness of Examples 4 and 5, which use a (meth)acrylic polymer (A1) with a high mass-average molecular weight, is very good.

[0368] However, the (A1-1), (A1-2), and (A1-3) polymers used as (meth)acrylic polymers (A1) in Examples 1-5 have low flowability, so they cannot be used for melt molding of the film alone. By combining the (meth)acrylic polymer (A1) with the (meth)acrylic copolymer (B), a film with good blade resistance can be melt molded.

[0369] Furthermore, in Examples 2-5, it was shown that by including (meth)acrylic polymer (A2), the surface smoothness of the obtained film also became good.

[0370] Furthermore, in Examples 3 to 5, it was shown that the anti-adhesion effect was also achieved by including the anti-adhesion agent (D).

[0371] Industrial availability

[0372] The resin composition and molding material of the present invention contain (meth)acrylic polymer (A1) and (meth)acrylic copolymer (B) as constituent components. The resin molded article according to the present invention is formed by molding the molding material, thus obtaining a film with good operability and, consequently, good surface smoothness.

[0373] The present invention has been described in detail using specific methods, but it will be apparent to those skilled in the art that various modifications can be made without departing from the intent and scope of the invention.

[0374] This application is based on Japanese Patent Application 2023-151439, filed on September 19, 2023, the entire contents of which are incorporated herein by reference.< / z>

Claims

1. A resin composition comprising: a (meth)acrylic polymer (A) as a random copolymer and / or homopolymer; and (B) is a (meth)acrylic copolymer that is a block copolymer and / or graft copolymer, wherein... The (meth)acrylic polymer (A) contains more than 50% by mass repeating units derived from methyl methacrylate. The (meth)acrylic polymer (A) includes (meth)acrylic polymers (A1) with a mass-average molecular weight exceeding 130,000 as determined by gel permeation chromatography (GPC). The (meth)acrylic copolymer (B) is a polymer containing polymer (B1) and polymer (B2) in the same molecule. The polymer (B1) is a polymer containing more than 50% by mass of units derived from methyl methacrylate and having a glass transition temperature above 0°C. The polymer (B2) is a polymer with a glass transition temperature below 0°C.

2. The resin composition according to claim 1, wherein, The (meth)acrylic polymer (A) further comprises (meth)acrylic polymer (A2). The (meth)acrylic polymer (A2) according to JIS K7210 or ISO 1133 has a melt flow rate of 7.0 g / 10 min or more at 230 °C and 37.3 N. The resin composition contains 3 to 15% by mass of the (meth)acrylic polymer (A2) relative to 100% by mass of the total resin composition.

3. The resin composition according to claim 1, wherein, The (meth)acrylic polymer (A1) according to JIS K7210 or ISO 1133 has a melt flow rate of less than 7.0 g / 10 min at 230 °C and 37.3 N.

4. The resin composition according to claim 1, wherein, The resin composition comprises more than 15% by mass of the (meth)acrylic copolymer (B) relative to 100% by mass of the total composition.

5. The resin composition according to claim 1, wherein, The mass-average molecular weight of the (meth)acrylic copolymer (B) exceeds 300,000.

6. The resin composition according to claim 1, wherein, The (meth)acrylic copolymer (B) comprises repeating units derived from the macromonomer (b1) represented by the following general formula (1). [Chemical Formula 1] In equation (1), R 0 ~R n Each is independently a hydrogen atom, alkyl, cycloalkyl, aryl, or heterocyclic group, X 1 ~X n Each is an independent hydrogen atom or a methyl group, Z is a terminal group, and n is a natural number from 1 to 10000.

7. A molding material comprising a resin composition according to any one of claims 1 to 6.

8. The molding material according to claim 7, wherein, The molding material is a film molding material.

9. The molding material according to claim 7, wherein, The molding material is a molding material for extruded films.

10. A resin molded body, said resin molded body being formed from the molding material according to claim 7.

11. An optical film formed from the molding material according to claim 7.

12. A polarizing protective film, wherein the polarizing protective film is formed from the molding material according to claim 7.

13. A polarizer comprising a resin molded body according to claim 10.

14. An image display device comprising a resin molded body according to claim 10.

15. A method for manufacturing a resin composition, characterized in that, The method is a method for manufacturing a resin composition by mixing a (meth)acrylic polymer (A) as a random copolymer and / or homopolymer and a (meth)acrylic copolymer (B) as a block copolymer and / or graft copolymer, wherein, The (meth)acrylic polymer (A) contains more than 50% by mass repeating units derived from methyl methacrylate. The (meth)acrylic polymer (A) includes (meth)acrylic polymers (A1) with a mass-average molecular weight exceeding 130,000 as determined by gel permeation chromatography (GPC). The (meth)acrylic copolymer (B) is a polymer containing polymer (B1) and polymer (B2) in the same molecule. The polymer (B1) is a polymer containing more than 50% by mass of units derived from methyl methacrylate and having a glass transition temperature above 0°C. The polymer (B2) is a polymer with a glass transition temperature below 0°C.

16. The method for manufacturing the resin composition according to claim 15, wherein, The (meth)acrylic polymer (A) further comprises (meth)acrylic polymer (A2). The (meth)acrylic polymer (A2) according to JIS K7210 or ISO 1133 has a melt flow rate of 7.0 g / 10 min or more at 230 °C and 37.3 N. The resin composition contains 3 to 15% by mass of the (meth)acrylic polymer (A2) relative to 100% by mass of the total resin composition.

17. The method for manufacturing the resin composition according to claim 15, wherein, The (meth)acrylic polymer (A1) according to JIS K7210 or ISO 1133 has a melt flow rate of less than 7.0 g / 10 min at 230 °C and 37.3 N.

18. The method for manufacturing the resin composition according to claim 15, wherein, The resin composition comprises more than 15% by mass of the (meth)acrylic copolymer (B) relative to 100% by mass of the total composition.

19. The method for manufacturing the resin composition according to claim 15, wherein, The mass-average molecular weight of the (meth)acrylic copolymer (B) exceeds 300,000.

20. The method for manufacturing the resin composition according to claim 15, wherein, The (meth)acrylic copolymer (B) comprises repeating units derived from the macromonomer (b1) represented by the following general formula (1). [Chemical Formula 2] In equation (1), R 0 ~R n Each is independently a hydrogen atom, alkyl, cycloalkyl, aryl, or heterocyclic group, X 1 ~X n Each is an independent hydrogen atom or a methyl group, Z is a terminal group, and n is a natural number from 1 to 10000.

21. A method for manufacturing a resin molded article, wherein the method for manufacturing the resin molded article is to manufacture a resin composition by means of a method for manufacturing a resin composition according to any one of claims 15 to 20, and to mold a molding material comprising the resin composition.

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