Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/04—Polymers provided for in subclasses C08C or C08F
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
  • C08F290/126—Polymers of unsaturated carboxylic acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
  • C08L33/12—Homopolymers or copolymers of methyl methacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

• the present invention relates to a resin composition, a molding material containing the resin composition, and a molded article using the molding material.
• acrylic resins have excellent transparency, weather resistance, high elasticity, and surface hardness, they are widely used in display front panels for liquid crystal and organic electroluminescence (EL) displays, signage, lighting, toys, containers, home appliances, vehicle parts such as interior and exterior parts for vehicles, medical parts, industrial materials, construction materials, lenses, light guides, light collecting components, and optical components such as optical films used in liquid crystal and organic electroluminescence (EL) displays.
• EL liquid crystal and organic electroluminescence
• acrylic resin products to be given flexibility, toughness, and impact resistance.
• acrylic resins with excellent melt moldability which allows them to be molded into thin or complex shapes using melt molding methods such as injection molding and extrusion molding.
• Patent Document 1 discloses a resin composition in which a rubber having a core-shell structure (core-shell rubber) having a core part made of crosslinked rubber and a shell part that ensures compatibility and dispersibility with a (meth)acrylic polymer that serves as a matrix is blended with a (meth)acrylic resin.
• core-shell rubber core-shell rubber
• the resin composition described in Patent Document 1 tends to have an increased melt viscosity and decreased melt moldability due to the inclusion of the core-shell rubber, which has resulted in a problem that the applications of the resin composition are limited to resin products with a large thickness or a simple shape.
• a resin composition in which a block copolymer and/or a graft copolymer is blended with a (meth)acrylic resin is known as a technique for improving the melt moldability of acrylic resin.
• a block copolymer and/or a graft copolymer two or more types of polymer segments are linked to each other by chemical bonds. For this reason, the phase separation structure of a resin composition in which a block copolymer and/or a graft copolymer having a poly(meth)acrylate chain is blended with an acrylic resin is nanometer-sized (called a "microphase separation structure").
• the resin composition in which the block copolymer and/or graft copolymer is blended with an acrylic resin forms a microphase separation structure. Therefore, the molded article obtained by molding the resin composition is known to be able to maintain the transparency of the acrylic resin well and to have excellent properties (e.g., flexibility, impact resistance, etc.) of each polymer segment of the block copolymer and/or graft copolymer.
• Patent Document 2 describes a method for obtaining a block copolymer by performing controlled radical polymerization in the presence of a nitroxide. Specifically, a technique is disclosed for obtaining a sheet-like molded product containing a block copolymer by putting a syrup into a mold and polymerizing it to produce a cast sheet. Patent Document 2 describes that the obtained sheet-like molded product contains a (meth)acrylic polymer and a block copolymer having a polymethyl methacrylate chain and an n-butyl acrylate-styrene copolymer chain, and has excellent impact resistance and transparency.
• a known method for producing the above-mentioned block copolymers and/or graft copolymers is to first produce an acrylic macromonomer (hereinafter referred to as "macromonomer") using a very small amount of a cobalt complex with an extremely high chain transfer constant, and then copolymerize the macromonomer with other monomers to produce the block copolymer and/or graft copolymer.
• a known method for producing an acrylic macromonomer using a cobalt complex is catalytic chain transfer polymerization (CCTP).
• CCTP catalytic chain transfer polymerization
• a macromonomer is a polymer that has a polymerizable functional group in its molecular structure, and is sometimes called a macromer.
• Patent Document 3 discloses a technology in which a macromonomer is produced by CCTP, the resulting macromonomer is used to produce a macromonomer copolymer, and the resulting macromonomer copolymer is then added to an acrylic resin, thereby achieving both impact resistance and transparency.
• Patent Document 3 uses a molding material that is melt moldable and has excellent moldability to obtain a molded product with good impact resistance.
• the toughness is low and the impact resistance value is insufficient in a notched Charpy impact test.
• the first aspect of the present invention aims to solve the problems of the conventional techniques described above, and to provide a resin composition, molding material, and molded article that have excellent toughness and impact resistance while maintaining excellent moldability in an acrylic resin molding material that contains a block copolymer and/or a graft copolymer.
• the second aspect of the present invention aims to provide a resin composition and molding material that can provide molded articles having excellent transparency and appearance quality achieved by solving the problems of the above-mentioned conventional techniques, and by exhibiting excellent moldability, excellent impact resistance, flexibility, and low haze.
• the inventors have discovered that the problems of the first invention and the second invention can be solved by combining and blending specific (meth)acrylic resins.
• the gist of the present invention is as follows:
• a resin composition comprising a (meth)acrylic polymer (A), a (meth)acrylic copolymer (B), and a rubber-like graft polymer (C) having a crosslinked structure
• the (meth)acrylic polymer (A) is a random copolymer and/or a homopolymer
• the (meth)acrylic polymer (A) contains 50% by mass or more of repeating units derived from methyl methacrylate
• the (meth)acrylic copolymer (B) is a block copolymer and/or a graft copolymer containing a polymer (B1) and a polymer (B2)
• the polymer (B1) contains 50% by mass or more of repeating units derived from methyl methacrylate and has a glass transition temperature of 0° C. or higher
• the resin composition, wherein the polymer (B2) has a glass transition temperature of less than 0°C.
• the resin composition further contains a (meth)acrylic polymer (D) which is a random copolymer and/or a homopolymer, the (meth)acrylic polymer (A) contains 50% by mass or more of repeating units derived from methyl methacrylate and has a mass average molecular weight of 50,000 to 200,000; the (meth)acrylic polymer (D) contains 50% by mass or more of repeating units derived from methyl methacrylate and has a mass average molecular weight of 500,000 or more;
• the resin composition according to any one of [1] to [4], wherein the (meth)acrylic polymer (D) is contained in an amount of 0.2 to 15% by mass relative to a total of 100% by mass of the resin composition.
• a resin composition comprising a (meth)acrylic polymer (A), a (meth)acrylic copolymer (B) and a (meth)acrylic polymer (D), the (meth)acrylic polymer (A) and the (meth)acrylic polymer (D) are random copolymers and/or homopolymers, the (meth)acrylic polymer (A) contains 50% by mass or more of repeating units derived from methyl methacrylate and has a mass average molecular weight of 50,000 to 200,000;
• the (meth)acrylic copolymer (B) is a block copolymer and/or a graft copolymer, the (meth)acrylic polymer (D) contains 50% by mass or more of repeating units derived from methyl methacrylate and has a mass average molecular weight of 500,000 or more;
• the resin composition contains the (meth)acrylic polymer (D) in an amount of 0.2 to 15% by mass relative to 100% by mass of the total
• the (meth)acrylic polymer (A) comprises a (meth)acrylic polymer (A2) having a melt flow rate of 7.0 g/10 min or more, as measured in accordance with JIS K7210 or ISO 1133 under conditions of 230° C. and 37.3 N;
• R 0 to R n each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.
• X 1 to X n each independently represent a hydrogen atom or a methyl group.
• Z is a terminal group.
• n is a natural number from 1 to 10,000.
• a vehicle part comprising the molded article according to [13].
• a vehicle exterior part comprising the molded article according to [13].
• a housing equipment member comprising the molded article according to [13].
• An optical member comprising the molded article according to [13].
• a medical device comprising the molded article according to [13].
• a container comprising the molded article according to [13].
• a molded body comprising the molding material described in [11] or [20].
• a film comprising the molded article according to [21].
• An optical film comprising the molded article according to [21].
• An image display device comprising the molded article according to [21].
• a film for housing facilities comprising the molded article according to [21].
• a vehicle part comprising the molded article according to [21].
• a vehicle exterior part comprising the molded article according to [21].
• the resin composition and molding material of the first aspect of the present invention have excellent melt moldability, and the molded article obtained by molding using this molding material has excellent toughness and impact resistance.
• the resin composition and molding material of the second invention of the present invention have excellent melt moldability, and the molded article obtained by molding using this molding material has excellent impact resistance, flexibility, and excellent transparency and appearance quality achieved by low haze.
• (meth)acrylic means one or both of “acrylic” and “methacrylic”.
• (meth)acrylate means one or both of “methacrylate” and “acrylate”. The same applies to "(meth)acryloyl”.
• the term "monomer” refers to an unpolymerized compound (a monomer component before polymerization).
• the terms “repeating unit” and “structural unit” refer to structural units constituting a polymer derived from a monomer formed by polymerization of the monomer. The structural units that make up a polymer are called “monomer units.”
• the “repeating unit” or “structural unit” may be a unit formed directly by a polymerization reaction, or may be a unit in which a part of the unit is converted into a different structure by treating the polymer.
• mass % indicates the content of a particular component in a total amount of 100 mass %.
• ⁇ means a range that includes the numerical values written before and after " ⁇ " as the lower and upper limits.
• a ⁇ B means A or more and B or less.
• the mass average molecular weight (Mw) of the (meth)acrylic polymer (A), the (meth)acrylic polymer (D), and other (meth)acrylic polymers means the mass average molecular weight, which is the relative molecular weight determined using gel permeation chromatography (GPC) and converted into polystyrene.
• the mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) means the mass average molecular weight, which is the relative molecular weight determined using gel permeation chromatography (GPC) and converted into polymethyl methacrylate (PMMA).
• the resin composition of the first aspect of the present invention contains, as essential components, a (meth)acrylic polymer (A), a (meth)acrylic copolymer (B), and a rubber-like graft polymer (C) having a crosslinked structure.
• the resin composition of the first invention may contain a (meth)acrylic polymer (D) and other components, if necessary.
• the resin composition of the second aspect of the present invention contains, as essential components, a (meth)acrylic polymer (A), a (meth)acrylic copolymer (B), and a (meth)acrylic polymer (D).
• the (meth)acrylic polymer (A) may contain a (meth)acrylic polymer (A2) as necessary.
• the resin composition of the second invention may contain, as required, a rubbery graft polymer (C) having a crosslinked structure and other components.
• the "first invention” and the “second invention” will be collectively referred to as "the present invention.”
• the (meth)acrylic polymer (A) is one of the components of the resin composition of the present invention.
• the (meth)acrylic polymer (A) contains 50% by mass or more of repeating units derived from methyl methacrylate (hereinafter, sometimes referred to as "methyl methacrylate units") relative to 100% by mass of the total weight of the (meth)acrylic polymer (A), and is a random copolymer and/or a homopolymer.
• methyl methacrylate units repeating units derived from methyl methacrylate
• the methyl methacrylate unit is contained in an amount of 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total weight of the (meth)acrylic polymer (A) being 100% by mass.
• the lower limit of the content ratio of the methyl methacrylate unit in the (meth)acrylic polymer (A) is 50 mass% or more relative to 100 mass% of the total weight of the (meth)acrylic polymer (A), the heat resistance, hardness, scratch resistance, weather resistance, transparency and processability of the (meth)acrylic resin can be well maintained.
• the upper limit of the content of methyl methacrylate units is not particularly limited, and the (meth)acrylic polymer (A) may be a homopolymer of methyl methacrylate (the content of methyl methacrylate units is 100% by mass).
• the (meth)acrylic polymer (A) may contain, in addition to the repeating units derived from methyl methacrylate, units derived from other comonomers copolymerizable with methyl methacrylate (hereinafter, these may be referred to as “comonomer units”) depending on the purpose.
• the (meth)acrylic polymer (A) contains a repeating unit derived from an acrylate (hereinafter, may be referred to as an "acrylate unit") as a comonomer unit
• acrylate unit a repeating unit derived from an acrylate
• depolymerization of the (meth)acrylic polymer (A) when exposed to high-temperature conditions such as melt molding can be suppressed, and thermal decomposition resistance can be improved.
• functions such as the glass transition temperature (Tg), processability, heat resistance, refractive index, weather resistance, releasability, and thermal decomposition resistance of the (meth)acrylic polymer (A) can be controlled.
• the upper limit of the content ratio of the comonomer unit in the (meth)acrylic polymer (A) is preferably 20 mass% or less relative to the total mass (100 mass%) of the (meth)acrylic polymer (A), because the performance properties of the (meth)acrylic polymer (A), such as heat resistance, hardness, scratch resistance, weather resistance, transparency, and processability, can be well maintained.
• the lower limit of the content of the comonomer unit is not particularly limited, and as described above, the (meth)acrylic polymer (A) may not contain the comonomer unit, i.e., may be a homopolymer of methyl methacrylate.
• Examples of comonomers that form the comonomer units of the (meth)acrylic polymer (A) include the following a) to i).
• (meth)acrylate ester monomers other than methyl methacrylate such as methyl acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and phenoxyethyl (meth)acrylate.
• Hydroxyl group-containing (meth)acrylate monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerol (meth)acrylate.
• Carboxyl group-containing vinyl monomers such as (meth)acrylic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxypropyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, and monomethyl itaconate.
• vinyl monomers such as (meth)acrylic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)
• Vinyl monomers containing an acid anhydride group such as maleic anhydride and itaconic anhydride.
• Epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate, glycidyl ⁇ -ethyl acrylate, and 3,4-epoxybutyl (meth)acrylate.
• Amino group-containing (meth)acrylate vinyl monomers such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.
• Vinyl monomers containing an amide group such as (meth)acrylamide, N-t-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetone acrylamide, maleic acid amide, and maleimide.
• Vinyl monomers such as styrene, ⁇ -methylstyrene, vinyl toluene, (meth)acrylonitrile, vinyl chloride, vinyl acetate, and vinyl propionate.
• Polyfunctional vinyl monomers such as divinylbenzene, ethylene glycol di(meth)acrylate, 1,3-butylene glycol 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 (meth)acrylate, and N,N'-methylenebis(meth)acrylamide.
• divinylbenzene ethylene glycol di(meth)acrylate, 1,3-butylene glycol 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,
• methyl acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred in terms of the ease of obtaining the monomers. Furthermore, methyl acrylate is more preferred in terms of ensuring the rigidity and heat resistance of the resin composition, molding material, and molded article of the present invention.
• the polystyrene-equivalent mass average molecular weight (Mw) of the (meth)acrylic polymer (A) in the first invention 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.
• the (meth)acrylic polymer (A) in the second invention has a polystyrene-equivalent mass average molecular weight (Mw) of 50,000 to 200,000, preferably 70,000 to 150,000, and more preferably 80,000 to 120,000.
• Mw polystyrene-equivalent mass average molecular weight
• the (meth)acrylic resin is likely to exhibit its properties such as heat resistance, hardness, scratch resistance, weather resistance, transparency, etc.
• the upper limit of Mw of the (meth)acrylic polymer (A) is 200,000 or less, the melt viscosity falls within an appropriate range, and melt-kneadability and processability are improved.
• the (meth)acrylic polymer (A) may be used alone or in the form of a mixture of two or more types having different resin compositions, physical properties, etc.
• the content of the (meth)acrylic polymer (A) is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, based on 100% by mass of the total resin composition of the present invention.
• the properties characteristic of the (meth)acrylic resin such as heat resistance, weather resistance, and transparency, can be effectively imparted.
• the content of the (meth)acrylic polymer (A) is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, based on the total 100% by mass of the resin composition of the present invention.
• the content of the (meth)acrylic polymer (A) is 90% by mass or less, the content of the (meth)acrylic copolymer (B) or the rubber-like graft polymer (C) having a crosslinked structure and/or the (meth)acrylic polymer (D) increases, so that a resin composition, molding material, and molded article having a balanced moldability, toughness, impact resistance, or flexibility, moldability, transparency, etc. can be obtained.
• the (meth)acrylic polymer (A2) is used as a part of the (meth)acrylic polymer (A) in the resin composition of the second invention, if necessary.
• the role of the (meth)acrylic polymer (A2) is to adjust the fluidity during melt molding.
• an appropriate amount of (meth)acrylic polymer (A2) in the resin composition it is possible to keep the haze of the molded product produced by injection molding low, prevent molding defects, and provide a good appearance quality.
• the (meth)acrylic polymer (A2) preferably has a melt flow rate (MFR) measured in accordance with JIS K7210 or ISO 1133 at 230°C and 37.3N of 7.0 g/10 min or more, more preferably 10.0 g/10 min or more, and even more preferably 12.0 g/10 min or more.
• MFR melt flow rate
• the polystyrene-equivalent mass average molecular weight (Mw) of the (meth)acrylic polymer (A2) is, like the (meth)acrylic polymer (A), from 50,000 to 200,000, preferably from 70,000 to 150,000, and more preferably from 80,000 to 120,000.
• Mw mass average molecular weight
• the lower limit of Mw of the (meth)acrylic polymer (A2) is 50,000 or more, the (meth)acrylic resin is likely to exhibit its properties such as heat resistance, hardness, scratch resistance, weather resistance, transparency, etc.
• the upper limit of Mw of the (meth)acrylic polymer (A2) is 200,000 or less, the melt viscosity falls within an appropriate range, and melt-kneadability and processability are improved.
• the comonomer unit is the same as the comonomer unit contained in the above-mentioned (meth)acrylic polymer (A).
• the content of the comonomer units contained in the (meth)acrylic polymer (A2) is preferably from 2 to 20% by mass, more preferably from 5 to 18% by mass, and even more preferably from 10 to 15% by mass.
• the (meth)acrylic polymer (A2) contains 2% by mass or more of the comonomer unit, the above-mentioned melt flow rate is easily achieved.
• the (meth)acrylic polymer (A2) contains 20% by mass or less of the comonomer unit, the (meth)acrylic resin is more likely to exhibit its properties such as heat resistance, hardness, scratch resistance, weather resistance, and transparency.
• the content of the (meth)acrylic polymer (A2) in the resin composition of the second invention is preferably 1 mass% or more and 20 mass% or less, more preferably 2 mass% or more and 15 mass% or less, still more preferably 3 mass% or more and 15 mass% or less, and particularly preferably 3 mass% or more and 12 mass% or less, relative to 100 mass% of the resin composition.
• the content of the (meth)acrylic polymer (A2) 1% by mass or more, it is possible to effectively obtain the effects of suppressing haze of a molded product and suppressing molding defects.
• the resin composition of the present invention contains a (meth)acrylic copolymer (B).
• the (meth)acrylic copolymer (B) is a block copolymer and/or a graft copolymer. That is, the (meth)acrylic copolymer (B) has at least one of the structures of a block copolymer and a graft copolymer.
• the block and/or graft structure of the (meth)acrylic copolymer (B) according to the present invention may be any of diblock, triblock, multiblock, graft, cyclic, star, comb, dendritic, ladder, etc., or may be a combination of a plurality of these structures.
• these structures it is preferable to have at least one of the diblock, triblock, and graft structures, since they can impart excellent impact resistance and flexibility and are relatively easy to manufacture.
• the (meth)acrylic copolymer (B) is a block copolymer and/or a graft copolymer containing a polymer (B1) and a polymer (B2), the polymer (B1) containing 50% by mass or more of repeating units derived from methyl methacrylate and having a glass transition temperature of 0°C or more, and the polymer (B2) having a glass transition temperature of less than 0°C.
• the (meth)acrylic copolymer (B) preferably has a weight average molecular weight of 300,000 or more in terms of polymethyl methacrylate.
• the (meth)acrylic copolymer (B) according to the second invention preferably contains a polymer (B1) containing 50% by mass or more of repeating units derived from methyl methacrylate, and, as in the first invention, it is particularly preferable that the (meth)acrylic copolymer (B) contains the polymer (B1) and polymer (B2) described below.
• the polymer (B1) has a function of imparting miscibility and compatibility to the (meth)acrylic polymer (A) and a function of enabling the (meth)acrylic copolymer (B) to be handled as a solid.
• the polymer (B2) has the function of imparting flexibility, impact resistance and moldability.
• the (meth)acrylic copolymer (B) contains polymer (B1) and polymer (B2) in the same polymer molecule.
• the (meth)acrylic copolymer (B) may be a graft copolymer in which the main chain is constituted by polymer (B1) and a graft chain made of polymer (B2) is branched and connected to the main chain made of polymer (B1).
• the (meth)acrylic copolymer (B) may have a main chain made of polymer (B2) and a side chain made of polymer (B1).
• the (meth)acrylic copolymer (B) may be a block copolymer in which a polymer made of polymer (B1) and a polymer made of polymer (B2) are connected in series. Furthermore, the main chain and/or side chain of the graft copolymer may have a structure containing a block copolymer.
• the content of the (meth)acrylic copolymer (B) is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, based on 100% by mass of the total of the resin composition of the first invention. If the content of the (meth)acrylic copolymer (B) is 25% by mass or more, it is easy to impart the flowability and impact resistance, which are characteristics of the (meth)acrylic copolymer (B), to the resin composition.
• the content of the (meth)acrylic copolymer (B) is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on 100% by mass of the total resin composition of the first invention.
• the content of the (meth)acrylic copolymer (B) is 70% by mass or less, the content of the (meth)acrylic polymer (A) and the rubbery graft polymer (C) having a crosslinked structure can be ensured, and the effects of these components can be easily obtained, and a resin composition, molding material, and molded article having balanced moldability, toughness, impact resistance, etc. can be obtained.
• the content of the (meth)acrylic copolymer (B) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total 100% by mass of the resin composition of the second invention. If the content of the (meth)acrylic copolymer (B) is 10% by mass or more, it is easy to impart fluidity and flexibility, which are characteristics of the (meth)acrylic copolymer (B), to the resin composition.
• the content of the (meth)acrylic copolymer (B) is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total 100% by mass of the resin composition of the second invention.
• the content of the (meth)acrylic copolymer (B) is 70% by mass or less, the content of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (D) can be ensured, and the effects of these components can be easily obtained, and a resin composition, molding material, and molded article having a balanced flexibility, moldability, transparency, etc. can be obtained.
• the lower limit of the mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) according to the present invention is preferably 50,000 or more, more preferably 100,000 or more, even more preferably 200,000 or more, and particularly preferably 300,000 or more. If the mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) is 50,000 or more, the flexibility and impact resistance of the resin composition, molding material, and molded article are good. In particular, in the first aspect of the present invention, impact resistance is more easily obtained if the mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) is 300,000 or more.
• the mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) is preferably 500,000 or more, particularly preferably 800,000 or more.
• the upper limit of the mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) according to the present invention 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 mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) is 5,000,000 or less, the transparency of the resin composition, molding material, and molded article will be good.
• the mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) refers to the mass average molecular weight, which is the relative molecular weight determined using gel permeation chromatography (GPC) and converted into polymethyl methacrylate (PMMA).
• the polymer (B1) preferably contains 50% by mass or more of methyl methacrylate units.
• the function of the polymer (B1) to impart miscibility and compatibility to the (meth)acrylic polymer (A) can be effectively exerted.
• the polymer (B1) preferably contains 50% by mass or more of methyl methacrylate units, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on its total weight of 100% by mass.
• the lower limit of the content ratio of the methyl methacrylate unit in the polymer (B1) is 50 mass% or more relative to 100 mass% of the total weight of the polymer (B1)
• the polymer (B1) has good affinity for the (meth)acrylic polymer (A), and the miscibility and compatibility are good.
• the polymer (B1) may be a homopolymer having a content of methyl methacrylate units of 100% by mass.
• the polymer (B1) may contain, in addition to the methyl methacrylate units, comonomer units derived from other comonomers copolymerizable with methyl methacrylate depending on the purpose.
• comonomer units derived from other comonomers copolymerizable with methyl methacrylate depending on the purpose.
• the polymer (B1) contains an acrylate unit as a comonomer unit, depolymerization of the polymer (B1) when exposed to high temperature conditions such as melt molding can be suppressed, and thermal decomposition resistance can be improved.
• the functions of the polymer (B1) such as the glass transition temperature (Tg), processability, heat resistance, refractive index, weather resistance, releasability, and thermal decomposition resistance, can be controlled.
• the upper limit of the content of the comonomer unit in the polymer (B1) is preferably 50% by mass or less relative to the total mass of the polymer (B1), 100% by mass, since this allows the performance such as heat resistance, hardness, scratch resistance, weather resistance, transparency, and processability to be well maintained.
• the lower limit of the content of the comonomer unit may be 0% by mass.
• the comonomers that form the comonomer units of the polymer (B1) include, for example, a) to i) that are described above as the comonomers that form the comonomer units of the (meth)acrylic polymer (A), and one type may be used alone or two or more types may be used in combination.
• methyl acrylate methyl acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred, and methyl acrylate is more preferred.
• the polymer (B1) preferably contains a structural unit derived from the macromonomer (b1) described below.
• the methyl methacrylate unit may be contained in the macromonomer (b1).
• the glass transition temperature (Tg) of the polymer (B1) is 0° C. or higher, preferably 20° C. or higher, more preferably 40° C. or higher, and even more preferably 60° C. or higher.
• the glass transition temperature (Tg) of the polymer (B1) is 0° C. or higher, the (meth)acrylic copolymer (B) can be handled as a solid.
• the upper limit of the glass transition temperature of the polymer (B1) is not particularly limited, but is preferably 120° C. or lower, particularly preferably 110° C. or lower, in view of feasibility of using readily available raw materials.
• the glass transition temperature (Tg) of the polymer (B1) is also preferably within the above preferred range for the same reasons as above.
• the Tg of polymer (B1) can be calculated by using the Fox formula and the numerical value described in a known document such as the Polymer Handbook (POLYMER HANDBOOK FOURTH EDITION 2003) as the Tg of a homopolymer of the monomer that is the constituent unit of polymer (B1).
• the dynamic viscoelasticity of the obtained molded body can be measured, and the value of tan ⁇ can be used as the Tg.
• the lower limit of the mass average molecular weight (Mw) of the polymer (B1) in the present invention 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 the polymer (B1) is 3,000 or more, the affinity of the polymer (B1) with the (meth)acrylic polymer (A) will be good, and miscibility and compatibility can be expected to be imparted.
• the upper limit of the mass average molecular weight (Mw) of the polymer (B1) in the present invention 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 polymer (B1) is 1,000,000 or less, the melt viscosity is in the appropriate range.
• the mass average molecular weight (Mw) of the polymer (B1) refers to the mass average molecular weight, which is the relative molecular weight determined using gel permeation chromatography (GPC) and converted into polymethyl methacrylate (PMMA).
• the polymer (B1) in the present invention may be a mixture of two or more types of polymers.
• the mass average molecular weight (Mw) is calculated as the value of the entire polymer (B1).
• Mw mass average molecular weight
• the polymer (B1) with a lower molecular weight plays a role in reducing the syrup viscosity and preventing the copolymer from 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.
• the content of the polymer (B1) in the (meth)acrylic copolymer (B) is preferably 35% by mass or more and 75% by mass or less, based on 100% by mass of the total weight of the (meth)acrylic copolymer (B).
• the lower limit of the content of the polymer (B1) is 35% by mass or more, it becomes easy to obtain a (meth)acrylic copolymer (B) having excellent miscibility and compatibility with the (meth)acrylic polymer (A).
• the lower limit of the content of the polymer (B1) is more preferably 40% by mass or more, even more preferably 45% by mass or more, and particularly preferably 50% by mass or more.
• the upper limit of the content of the polymer (B1) is 75% by mass or less, the effect of imparting moldability and flexibility by the polymer (B2) is easily obtained.
• the upper limit of the content of the polymer (B1) is more preferably 70% by mass or less, and even more preferably 65% by mass or less.
• the polymer (B2) imparts functions such as flexibility, impact resistance, and improved flowability during melt molding to the (meth)acrylic copolymer (B) and the resin composition, molding material, and molded article of the present invention using the same.
• the glass transition temperature (Tg) of the polymer (B2) is preferably 0°C or lower, more preferably -10°C or lower, even more preferably -20°C or lower, and particularly preferably -35°C or lower.
• the lower limit of the glass transition temperature (Tg) of the polymer (B2) is usually -60°C.
• the Tg of polymer (B2) can be calculated by using the Fox formula and the numerical value described in a known document such as the Polymer Handbook (POLYMER HANDBOOK FOURTH EDITION 2003) as the Tg of a homopolymer of a monomer that is a constituent unit of polymer (B2).
• dynamic viscoelasticity measurement can be performed on the obtained molded body, and the value of tan ⁇ can be used as the Tg.
• the content of the polymer (B2) in the (meth)acrylic copolymer (B) is preferably 25% by mass or more and 65% by mass or less with respect to 100% by mass of the total weight of the (meth)acrylic copolymer (B).
• the lower limit of the content of the polymer (B2) is more preferably 30% by mass or more, and even more preferably 35% by mass or more.
• the upper limit of the content of the polymer (B2) is 65% by mass or less, the (meth)acrylic copolymer (B) has good handleability.
• the upper limit of the content of the polymer (B2) is 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.
• the refractive index of the polymer (B2) is preferably set so that the difference in refractive index between the polymer (B1) and the methyl methacrylate (A) is small. This improves the transparency of the resin composition, molding material, and molded article of the present invention.
• the difference in refractive index between the polymer (B2) and the polymer (B1) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0.02 or less.
• the difference in refractive index between the polymer (B2) and the (meth)acrylic polymer (A) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0.02 or less.
• the mass average molecular weight (Mw) of the polymer (B2) in the present invention 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. When the Mw of the polymer (B2) is 3,000 or more, the impact resistance is good.
• the mass average molecular weight (Mw) of the polymer (B2) in the present invention 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. When the Mw of the polymer (B2) is 2,500,000 or less, the transparency of the resin composition and molding material of the present invention is good.
• the mass average molecular weight (Mw) of the polymer (B2) refers to the mass average molecular weight (Mw) which is the relative molecular weight determined using gel permeation chromatography (GPC) and converted into polymethyl methacrylate (PMMA).
• Monomer (b2) is a monomer unit used as a raw material for polymer (B2).
• Monomer (b2) is not particularly limited as long as it can produce (meth)acrylic copolymer (B), and various polymerizable monomers can be used as needed.
• Tg glass transition temperature
• other monomers can be used as needed.
• the acrylate used in the 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, based on the total weight of the monomer (b2) being 100% by mass. If the lower limit of the content of the acrylate is 70% by mass or more, the (meth)acrylic copolymer (B) is provided with an effect of improving flexibility, impact resistance, and moldability. On the other hand, if the content of the acrylate is low, the effect of improving flexibility, impact resistance, and moldability may be insufficient.
• the upper limit of the content of the acrylate contained in the monomer (b2) is not particularly limited, but is preferably less than 100 mass%, more preferably 95 mass% or less, and even more preferably 90 mass% or less, relative to 100 mass% of the total mass of the monomer (b2).
• the acrylate can impart superior impact resistance to the resulting molded article, and therefore the glass transition temperature (Tg) of a homopolymer of the acrylate is preferably lower than 0°C.
• Tg of the homopolymer of the acrylate can be calculated by using the Fox formula and the values described in known documents such as the Polymer Handbook (POLYMER HANDBOOK FOURTH EDITION 2003).
• Examples of the acrylate used in the monomer (b2) include acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-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, and phenoxyethyl acrylate; hydroxyl group-containing acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and glycerol acrylate; 2-acryloyloxyethyl hexahydr
• carboxy group-containing acrylates such as 2-acryloyloxypropyl phthalate, 2-acryloyloxyethyl maleate, 2-acryloyloxypropyl maleate, 2-acryloyloxyethyl succinate, 2-acryloyloxypropyl succinate; epoxy group-containing acrylates such as glycidyl acrylate, glycidyl ⁇ -ethyl acrylate, 3,4-epoxybutyl acrylate; amino group-containing acrylates such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate; and polyfunctional acrylates such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,6-hexanediol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, allyl acrylate, and N,N'-
• 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, n-butyl acrylate, n-propyl acrylate, ethyl acrylate, and 2-hydroxyethyl acrylate are preferred because the Tg of the homopolymer of the monomer is less than 0°C.
• methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferred because they are easily available.
• the aromatic vinyl used in monomer (b2) is used for the purpose of adjusting the refractive index of polymer (B2) and adjusting the polymerization rate when producing polymer (B2) and (meth)acrylic copolymer (B).
• the content of the aromatic vinyl used in the monomer (b2) is preferably 10 to 30 mass%, more preferably 13 to 21 mass%, and even more preferably 15 to 19 mass%, relative to 100 mass% of the total mass of the monomer (b2).
• the content of the aromatic vinyl in the monomer (b2) is 10% by mass or more, the resin composition, molding material, and molded article of the present invention can exhibit good transparency.
• the content of the aromatic vinyl in the monomer (b2) is 30% by mass or less, the polymerization reaction rate during the production of the (meth)acrylic copolymer (B) becomes sufficiently high.
• aromatic vinyls examples include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, p-t-butylstyrene, vinylethylbenzene, vinyltoluene, vinylxylene, vinylnaphthalene, diphenylethylene, divinylbenzene, etc.
• styrene is preferred from the viewpoints of practical properties and productivity. These can be used alone or in combination of two or more.
• the monomer (b2) of the present invention may contain other monomers copolymerizable with the acrylate and the aromatic vinyl, if necessary.
• Examples of other monomers include methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-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, and phenoxyethyl methacrylate; hydroxyl group-containing methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, and glycerol methacrylate; 2-
• carboxy group-containing methacrylates such as 2-methacryloyloxyethyl phthalate, 2-methacryloyloxypropyl phthalate, 2-methacryloyloxyethyl maleate, 2-methacryloyloxypropyl maleate, 2-methacryloyloxyethyl succinate, and 2-methacryloyloxypropyl succinate; epoxy group-containing methacrylates such as glycidyl methacrylate and 3,4-epoxybutyl methacrylate; amino group-containing methacrylates such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; polyfunctional methacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dim
• examples of other monomers include carboxyl group-containing vinyl monomers such as (meth)acrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, and monomethyl itaconate; acid anhydride group-containing vinyl monomers such as maleic anhydride and itaconic anhydride; amide group-containing vinyl monomers such as (meth)acrylamide, N-t-butyl(meth)acrylamide, N-methylol(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; and the like.
• carboxyl group-containing vinyl monomers such as (meth)acrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, and monomethyl
• the proportion of other monomers used 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 of monomers (b2). Other monomers may not be used.
• Examples of a method for producing the (meth)acrylic copolymer (B) according to the present invention include a living polymerization method and a method using a macromonomer (b1) described below.
• Examples of the living polymerization method include a living radical polymerization method and a living anionic polymerization method.
• Examples of the living radical polymerization method include reversible addition-fragmentation chain transfer polymerization (RAFT), atom transfer radical polymerization (ATRP), nitroxide-mediated polymerization (NMP), and organotellurium-propagating living radical polymerization (TERP).
• the method using the macromonomer (b1) is advantageous in that the (meth)acrylic copolymer (B) can be produced relatively easily.
• the method using the macromonomer (b1) is preferable because it has the advantage that it does not require the removal of catalyst or auxiliary residues or terminal treatment steps, which are necessary in the living polymerization method.
• the macromonomer may be used as a raw material for either the polymer (B1) or the polymer (B2). Specifically, the macromonomer is copolymerized with a comonomer copolymerizable with the macromonomer to obtain a macromonomer copolymer. This macromonomer copolymer is used as the (meth)acrylic copolymer (B).
• macromonomer (b1) is used as a raw material for polymer (B1), and macromonomer (b1) is copolymerized with monomer (b2) to produce a macromonomer copolymer.
• polymer (B2) has monomer (b2) as a monomer unit.
• the macromonomer (b1) can be produced by a known method.
• Examples of the method for producing the macromonomer include a method using a cobalt chain transfer agent (U.S. Pat. No. 4,680,352), a method using an ⁇ -substituted unsaturated compound such as ⁇ -bromomethylstyrene as a chain transfer agent (WO 88/04304), a method of chemically bonding a polymerizable group (JP-A-60-133007, U.S. Pat. No. 5,147,952, and JP-A-06-298921), and a method using thermal decomposition (JP-A-11-240854).
• the method for producing the macromonomer (b1) is preferably a method using a cobalt chain transfer agent, since it requires fewer production steps and uses a catalyst with a high chain transfer constant.
• Examples of the method for producing the macromonomer (b1) using a cobalt chain transfer agent include bulk polymerization, solution polymerization, and aqueous dispersion polymerization methods such as suspension polymerization and emulsion polymerization. Among these, the aqueous dispersion polymerization method is preferred from the viewpoint of simplifying the recovery step of the macromonomer (b1).
• the cobalt chain transfer agent used in the present invention may be a cobalt chain transfer agent represented by the following general formula (2).
• cobalt chain transfer agents that can be used include those described in Japanese Patent No. 3,587,530, JP-A-6-23209, JP-A-7-35411, U.S. Patent Nos. 45,269,945, 4,694,054, 4,834,326, 4,886,861, 5,324,879, WO 95/17435, and JP-T-510,499.
• R 11 to R 14 each independently represent an alkyl group, a cycloalkyl group, or an aryl group.
• X 11 to X 14 each independently represent an F atom, a Cl atom, a Br atom, an OH group, an alkoxy group, an aryloxy group, an alkyl group, or an aryl group.
• cobalt chain transfer agent examples include bis(boron difluorodimethyldioximinocyclohexane)cobalt(II), bis(boron difluorodimethylglyoximate)cobalt(II), bis(boron difluorodiphenylglyoximate)cobalt(II), cobalt(II) complexes of vicinaliminohydroxyimino compounds, cobalt(II) complexes of tetraazatetraalkylcyclotetradecatetraenes, N,N'-bis(salicylidene)ethylenediaminocobalt(II) complexes, cobalt(II) complexes of dialkyldiazadioxodialkyldodecadienes, and cobalt(II) porphyrin complexes.
• the amount of the cobalt chain transfer agent used is preferably 5 ppm to 350 ppm per 100 parts by mass of the monomer used to obtain the macromonomer (b1). If the amount of the cobalt chain transfer agent used is 5 ppm or more, the molecular weight is likely to be sufficiently reduced. If the amount of the cobalt chain transfer agent used is 350 ppm or less, the obtained macromonomer (b1) is less likely to be discolored.
• Examples of the solvent used when obtaining the macromonomer (b1) by the solution polymerization method include hydrocarbons such as toluene; ethers such as diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane and chloroform; ketones such as acetone; alcohols such as methanol; nitriles such as acetonitrile; vinyl esters such as ethyl acetate; carbonates such as ethylene carbonate; and supercritical carbon dioxide. These may be used alone or in combination of two or more.
• the method for producing the macromonomer copolymer includes a step of polymerizing a polymerizable mixture containing a polymerizable composition (X) and a polymerization initiator, which will be described later.
• the polymerizable composition (X) contains a macromonomer (b1) represented by the following general formula (1) and a comonomer copolymerizable with the macromonomer (b1).
• the comonomer is appropriately selected from the monomers (b2) that are copolymerizable with the macromonomer (b1).
• R 0 to R n each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.
• X 1 to X n each independently represent a hydrogen atom or a methyl group.
• Z is a terminal group.
• n is a natural number from 1 to 10,000.
• the alkyl group, cycloalkyl group, aryl group or heterocyclic group of R 0 to R n may have a substituent.
• alkyl group of R 0 to R n examples include branched or linear alkyl groups having 1 to 20 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group.
• methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, and octyl group are preferred, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, and t-butyl group are more preferred, and methyl group is particularly preferred.
• Examples of the cycloalkyl group for R 0 to R n include cycloalkyl groups having 3 to 20 carbon atoms. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a t-butylcyclohexyl group, an isobornyl group, an adamantyl group, etc. Among these, the cyclopropyl group, the cyclobutyl group, and the adamantyl group are preferred from the viewpoint of availability.
• the aryl group of R 0 to R n includes, for example, an aryl group having a carbon number of 6 to 18. Specific examples include a phenyl group, a benzyl group, and a naphthyl group.
• heterocyclic group of R 0 to R n examples include heterocyclic groups having 5 to 18 carbon atoms. Specific examples include a ⁇ -lactone group, an ⁇ -caprolactone group, and a morpholine group. Examples of the heteroatom contained in the heterocycle include an oxygen atom, a nitrogen atom, and a sulfur atom.
• R 0 to R n may have include, independently, a group or atom selected from the group consisting of an alkyl group, an aryl group, a carboxy group, an alkoxycarbonyl group (-COOR'), a carbamoyl group (-CONR'R'', a cyano group, a hydroxy group, an amino group, an amide group (-NR'R'', a halogen atom, an allyl group, an epoxy group, an alkoxy group (-OR'), and a group exhibiting hydrophilicity or ionicity.
• R' or R'' each independently include the same groups as R 0 to R n (excluding heterocyclic groups).
• Examples of the alkoxycarbonyl group as the substituent for R 0 to R n include a methoxycarbonyl group.
• Examples of the carbamoyl group as a substituent for R 0 to R n include an N-methylcarbamoyl group and an N,N-dimethylcarbamoyl group.
• An example of the amide group as the substituent of R 0 to R n is a dimethylamide group.
• Examples of the halogen atom as a substituent for R 0 to R n include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Examples of the alkoxy group as the substituents of R 0 to R n include alkoxy groups having a carbon number of 1 to 12. A specific example is a methoxy group.
• Examples of the hydrophilic or ionic groups as the substituents of R 0 to R n include cationic substituents such as alkali salts of a carboxy group or alkali salts of a sulfoxyl group, poly(alkylene oxide) groups such as a polyethylene oxide group or a polypropylene oxide group, and quaternary ammonium bases.
• Each of R 0 to R n is preferably at least one selected from an alkyl group and a cycloalkyl group, and more preferably an alkyl group.
• the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group or an i-propyl group, and from the viewpoint of availability, a methyl group is more preferable.
• Z is a terminal group of the macromonomer (b1).
• the terminal group of the macromonomer (b1) include a hydrogen atom and a group derived from a radical polymerization initiator, similar to terminal groups of polymers obtained by known radical polymerization.
• the lower limit of the content of the methyl methacrylate unit contained in the macromonomer (b1) is not particularly limited, and if it is 50% by mass or more with respect to 100% by mass of the total mass of the macromonomer (b1), it is advantageous for improving impact resistance and transparency.
• the lower limit of the content of the methyl methacrylate unit is preferably 50% 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.
• the upper limit of the content of the methyl methacrylate units is not particularly limited, and may be 100% by mass of the methyl methacrylate units, or may be 99% by mass or less relative to 100% by mass of the total mass of the macromonomer (b1).
• the polymerization reaction is preferably carried out using a radical polymerization method, for example, a bulk polymerization method such as a block polymerization method or a cast polymerization method, or a solution polymerization method, or an aqueous dispersion polymerization method such as a suspension polymerization method or an emulsion polymerization method.
• a radical polymerization method for example, a bulk polymerization method such as a block polymerization method or a cast polymerization method, or a solution polymerization method, or an aqueous dispersion polymerization method such as a suspension polymerization method or an emulsion polymerization method.
• Aqueous dispersion polymerization methods such as suspension polymerization and emulsion polymerization are preferred because they can simplify the recovery process of the macromonomer copolymer, and suspension polymerization is more preferred because the resulting polymer particles are easy to handle.
• the macromonomer copolymer is obtained as spherical particles with an average particle size of about 5 ⁇ m to 1 mm.
• the obtained spherical particles are easy to handle, and there is little concern about dust scattering when used in processing operations such as extrusion and molding, making them suitable for use as resin compositions.
• Spherical particles are also preferable because they improve the moldability of the resin composition obtained by the suspension polymerization method.
• suspension polymerization method is superior to the emulsion polymerization method because, while in emulsion polymerization, trace amounts of abnormal polymerized products and remaining emulsifiers, etc., can cause foreign matter and thickening, the suspension polymerization method does not have such problems.
• the suspension polymerization method will be described in detail later.
• the polymerization reaction in the production of the macromonomer copolymer can be carried out using a bulk polymerization method such as a mass polymerization method or a cast polymerization method, and can include a step of heating the polymerizable mixture to polymerize it.
• a bulk polymerization method such as a mass polymerization method or a cast polymerization method
• the polymerizable mixture may contain a sulfur-containing chain transfer agent.
• the sulfur-containing chain transfer agent herein refers to a mercaptan compound such as n-butyl mercaptan or n-octyl mercaptan which is added as a chain transfer agent in order to adjust the molecular weight of the copolymer during polymerization.
• the upper limit of the content is preferably less than 0.01 parts by mass relative to 100 parts by mass of the polymerizable composition (X).
• the upper limit of the content of the sulfur-containing chain transfer agent is less than 0.01 parts by mass, the composition distribution of the copolymer can be prevented from becoming broad, and the impact resistance of the obtained molded product can be improved.
• the lower limit of the content of the sulfur-containing chain transfer agent is not particularly limited, it is preferable that the polymerizable composition does not contain a sulfur-containing chain transfer agent.
• polymerization can be carried out so that the mass average molecular weight (Mw) of the resulting macromonomer copolymer is 240,000 or more and 3,500,000 or less.
• 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.
• the mass average molecular weight (Mw) of the macromonomer copolymer is 240,000 or more, the flexibility and impact resistance of the resin composition, molding material, and molded article of the present invention are good.
• the upper limit of the mass average molecular weight (Mw) of the 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 mass average molecular weight (Mw) of the macromonomer copolymer is 3,500,000 or less, the moldability of the resin composition and molding material of the present invention will be good, and the transparency of the molded product will be good.
• the above upper and lower limits can be arbitrarily combined.
• the method for controlling the mass average molecular weight (Mw) of the copolymer to be 240,000 or more is not particularly limited, and a person skilled in the art can control the molecular weight by adjusting the polymerization method, the type and amount of polymerization initiator, the amount of chain transfer agent, the polymerization temperature, etc., according to well-known techniques.
• the polymerizable composition (X) is one of the raw materials for the (meth)acrylic copolymer (B).
• the lower limit of the content of the macromonomer (b1) in the polymerizable composition (X) is 35% by mass or more, or the lower limit of the content of the monomer (b2) is 35% by mass or more, based on 100% by mass of the total mass of the polymerizable composition (X).
• the upper limit of the content is 65% by mass or less, the macromonomer copolymer becomes easy to handle.
• the lower limit of the content of the monomer (b2) in the polymerizable composition (X) is 25% by mass or more relative to the total mass of the polymerizable composition (X), or the lower limit of the content of the macromonomer (b1) is 25% by mass or more relative to the total mass of the polymerizable composition (X),
• the upper limit of the content is 75% by mass or less, the impact resistance of the resin composition containing the macromonomer copolymer and the resulting molded article can be well maintained.
• a syrup is prepared by dissolving the bead-like macromonomer (b1) produced by suspension polymerization in a solution containing a monomer (b2), and this syrup is designated as a polymerizable composition (X).
• a mixture containing the macromonomer (b1) and the monomer (b2) can be heated at a temperature equal to or lower than the boiling point of the monomer (b2) to promote dissolution of the macromonomer (b1).
• the temperature at which the polymerizable composition (X) is prepared is preferably in the range of 20°C to 100°C, more preferably in the range of 40°C to 80°C. If the radical polymerization initiator used does not react at the temperature at which the polymerizable composition (X) is prepared, the radical polymerization initiator can be mixed into the polymerizable composition (X) to obtain a polymerizable mixture, and then the polymerizable mixture can be heated.
• the radical polymerization initiator reacts at the temperature at which the polymerizable composition (X) obtained in the step i) is prepared, the polymerizable composition (X) is once cooled to room temperature or below, and then the radical polymerization initiator is added and dissolved uniformly to obtain a polymerizable mixture.
• the temperature of the polymerizable composition (X) when the radical polymerization initiator is added is preferably a temperature equal to or lower than the 10-hour half-life temperature of the radical polymerization initiator minus 15°C.
• aqueous solution is an aqueous solution for dispersing the polymerizable mixture, and may contain a dispersant, an electrolyte, and other auxiliary agents.
• the water used in the aqueous solution is preferably deionized water, as this improves the dispersibility of the droplets of the polymerizable mixture.
• the dispersant examples include an alkali metal salt of poly(meth)acrylic acid, a copolymer of an alkali metal salt of (meth)acrylic acid and a (meth)acrylic acid ester, a copolymer of an alkali metal salt of a sulfoalkyl (meth)acrylate and a (meth)acrylic acid ester, an alkali metal salt of polystyrenesulfonic acid, a copolymer of an alkali metal salt of styrenesulfonic acid and a (meth)acrylic acid ester, or a copolymer consisting of a combination of these monomers; polyvinyl alcohol with a saponification degree of 70 to 100%, methyl cellulose, starch, and hydroxyapatite.
• copolymers of an alkali metal salt of a sulfoalkyl (meth)acrylate and a (meth)acrylic acid ester and copolymers of an alkali metal (meth)acrylate and a (meth)acrylic acid ester are preferred because of their good dispersion stability during suspension polymerization.
• the dispersant is used in an amount of, for example, 0.0005 to 0.5 parts by mass with respect to 100 parts by mass of the polymerizable composition (X).
• electrolyte examples include sodium carbonate, sodium sulfate, and manganese sulfate.
• the electrolyte is used in an amount of, for example, 0.01 to 1.0 part by mass with respect to 100 parts by mass of the polymerizable composition (X).
• the bead-like macromonomer (b1) produced by suspension polymerization is dispersed in an aqueous solution, and a solution containing a monomer (b2) is added to the dispersed macromonomer (b1) to prepare the polymerizable composition (X).
• the temperature at which the macromonomer (b1) is dissolved in the solution containing the 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 further preferably in the range of 50° C. to 80° C.
• the aqueous solution the same aqueous solution as in the above-mentioned iii) can be used.
• the radical polymerization initiator reacts at the temperature at which the polymerizable composition (X) obtained in the step I) is prepared, the polymerizable composition (X) is once cooled to room temperature or below, and then the radical polymerization initiator is added and uniformly dissolved to obtain a polymerizable mixture.
• the temperature of the polymerizable composition (X) when the radical polymerization initiator is added is preferably a temperature equal to or lower than the 10-hour half-life temperature of the radical polymerization initiator minus 15°C.
• the radical polymerization initiator can be a known organic peroxide such as 2,4-dichlorobenzoyl peroxide or t-butyl peroxypivalate, or a known azo compound such as 2,2'-azobisisobutyronitrile or 2,2'-azobis(2,4-dimethylvaleronitrile).
• the amount of the radical polymerization initiator to be added can be appropriately selected by a person skilled in the art according to well-known techniques. Usually, the amount of the radical polymerization initiator to be added is 0.0001 to 10 parts by mass per 100 parts by mass of the total amount of the polymerizable composition (X).
• the polymerization temperature during the polymerization reaction is an important condition for obtaining a macromonomer copolymer in high yield.
• the polymerization temperature here refers to 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 long. If the polymerization temperature is too high, the cleavage of the adduct radical, which is a reaction intermediate, will take precedence, and the yield of the macromonomer copolymer will tend to decrease.
• the suspension can be heated in order to increase the reaction rate of the polymerizable composition (X) and to eliminate the unreacted radical polymerization initiator.
• the temperature to which the suspension is heated is preferably 80°C or higher, and more preferably 85°C or higher.
• the heating time can be determined by calculating the time it takes for the radical polymerization initiator to disappear, and is usually about 30 minutes to 2 hours.
• the suspension is cooled to room temperature or lower, and the resulting bead-like copolymer is recovered by a known method such as filtration. If necessary, a washing step for removing impurities such as dispersants and electrolytes, a step for removing beads containing air bubbles, a drying step, etc. may be performed.
• the finally obtained bead-like macromonomer copolymer is referred to as the (meth)acrylic copolymer (B) of the present invention.
• the resin composition of the first invention contains a rubbery graft polymer (C) having a crosslinked structure.
• the resin composition of the second invention may contain a rubbery graft polymer (C) having a crosslinked structure.
• the rubbery graft polymer (C) having a cross-linked structure is different from the (meth)acrylic copolymer (B), and is a particulate rubber (core-shell rubber) that contains a core made of a rubber portion and a shell component that has functions such as compatibility with the matrix.
• core-shell rubber particulate rubber
• the core-shell rubber of the rubbery graft polymer (C) having a cross-linked structure is used for the purpose of imparting flexibility and impact resistance to the resin composition, molding material, and molded article of the present invention.
• the use of the rubbery graft polymer (C) having a cross-linked structure is effective in achieving toughness improvement that is difficult to achieve with the (meth)acrylic copolymer (B) and obtaining good results in a notched Charpy impact test.
• the acrylic copolymer (B) may cause anisotropy in the mechanical properties due to the orientation of the rubber component in the flow direction during injection molding.
• the core-shell rubber has less deformation of the rubber domain during injection molding due to the cross-linking of the rubber particles, and the combined use of the acrylic copolymer (B) and the rubbery graft polymer (C) having a cross-linked structure has the effect of eliminating anisotropy.
• the rubber-like graft polymer (C) having a crosslinked structure can be appropriately selected from those that are generally available.
• types of cores in core-shell rubbers include acrylic rubbers containing acrylate as a structural unit, butadiene rubbers containing butadiene as a structural unit, butadiene-acrylic composite rubbers containing butadiene and acrylate as structural units, and silicone-acrylic composite rubbers containing dimethylsiloxane and acrylate as structural units.
• the type of the core is preferably an acrylic rubber containing acrylate as a constituent unit, or a butadiene-acrylic composite rubber containing butadiene and acrylate as constituent units.
• the type of core is preferably an acrylic rubber or a silicone-acrylic composite rubber containing dimethylsiloxane and acrylate as constituent units, since this provides good weather resistance to the resin composition.
• core In terms of improving toughness and impact resistance, preferred types of core are butadiene rubber containing butadiene as a structural unit, butadiene-acrylic composite rubber containing butadiene and acrylate as structural units, and silicone-acrylic composite rubber containing dimethylsiloxane and acrylate as structural units. Furthermore, from the viewpoint of achieving both improved toughness and impact resistance and weather resistance, silicone-acrylic composite rubber is particularly preferred.
• the type of the core can be appropriately selected depending on the performance required for the molded article. A plurality of core-shell rubbers having different types of cores may be used in combination.
• the rubbery graft polymer (C) having a crosslinked structure is not particularly limited, but it is preferable that it has a multilayer structure of three or more layers including an inner layer, an intermediate layer, and a graft layer.
• the mass average particle diameter of the rubbery graft polymer (C) having a crosslinked structure is preferably 50 nm or more, more preferably 100 nm or more, and even more preferably 200 nm or more.
• the mass average particle diameter of the rubbery graft polymer (C) having a crosslinked structure is preferably 1000 nm or less, more preferably 700 nm or less, even more preferably 600 nm or less, and particularly preferably 500 nm or less. If the mass average particle size is 50 nm or more, it functions as a rubber and can improve toughness and impact resistance.If the mass average particle size is 1000 nm or less, the number of particles increases and toughness and impact resistance are improved.
• the mass average particle size of the rubber-like graft polymer (C) having a crosslinked structure is measured by the method described in the Examples section below.
• the content ratio of the rubber graft polymer (C) having a crosslinked structure in the resin composition of the first invention, and the lower limit of the content ratio of the rubber graft polymer (C) having a crosslinked structure in the resin composition of the second invention when the resin composition contains the rubber graft polymer (C) having a crosslinked structure is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the total 100% by mass of the resin composition of the present invention.
• the upper limit of the content of the rubbery graft polymer (C) having a crosslinked structure is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on 100% by mass of the total of the resin composition of the present invention.
• the content of the rubbery graft polymer (C) having a crosslinked structure is 50% by mass or less, good moldability can be ensured for the resin composition of the present invention and the molding material.
• the resin composition of the second invention contains a (meth)acrylic polymer (D) different from the (meth)acrylic polymer (A) and the (meth)acrylic copolymer (B).
• the resin composition of the first invention may also contain this (meth)acrylic polymer (D).
• the (meth)acrylic polymer (D) has the effect of suppressing the haze of the molded article of the present invention produced by injection molding, while suppressing molding defects and improving the appearance quality.
• the (meth)acrylic polymer (D) is a random copolymer and/or a homopolymer.
• the (meth)acrylic polymer (D) contains 50% by mass or more of methyl methacrylate units and has a mass average molecular weight (Mw) of 500,000 or more.
• the proportion of the repeating units derived from methyl methacrylate relative to the total of 100% by mass of the (meth)acrylic polymer (D) is from 50 to 100% by mass, more preferably from 60 to 90% by mass, and even more preferably from 70 to 85% by mass.
• the proportion of repeating units derived from methyl methacrylate contained in the (meth)acrylic polymer (D) is 50% by mass or more, the compatibility and miscibility between the (meth)acrylic polymer resin (A) and the (meth)acrylic polymer (D) are good.
• the softening temperature can be adjusted and the thermal decomposition resistance can be improved.
• various performances can be balanced.
• Examples of comonomers that form comonomer units other than the methyl methacrylate units contained in the (meth)acrylic polymer (D) include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and n-butyl acrylate. By copolymerizing these comonomers with methyl methacrylate, it is possible to improve the thermal decomposition resistance of the (meth)acrylic copolymer (D) during melt molding.
• the lower limit of the polystyrene-equivalent mass average molecular weight (Mw) of the (meth)acrylic polymer (D) in the present invention is 500,000 or more, preferably 700,000 or more, and more preferably 1,000,000 or more.
• the upper limit of the mass average molecular weight (Mw) of the (meth)acrylic polymer (D) is preferably 10,000,000 or less, more preferably 6,000,000 or less, and even more preferably 4,000,000 or less. If the mass average molecular weight (Mw) of the (meth)acrylic polymer (D) is 10,000,000 or less, the moldability is good.
• commercially available (meth)acrylic polymers (D) can also be used.
• Commercially available (meth)acrylic polymers (D) include, for example, acrylic polymer processing aids, such as Metablen (registered trademark) P type manufactured by Mitsubishi Chemical Corporation. Examples of Metablen (registered trademark) P type include P-531A, P-530A, P-551A, P-550A, P-501A, and P-570A.
• the (meth)acrylic polymer (D) may be used alone or in combination with two or more different polymers having different resin compositions, physical properties, etc.
• the content of the (meth)acrylic polymer (D) in the resin composition of the second invention, and the content of the (meth)acrylic polymer (D) in the resin composition of the first invention when the resin composition contains the (meth)acrylic polymer (D) are 0.2 mass% or more, preferably 0.5 mass% or more, and more preferably 1.0 mass% or more, based on 100 mass% of the total resin composition of the present invention. If the content of the (meth)acrylic polymer (D) is 0.2 mass% or more, the haze of the molded article of the present invention produced by injection molding is kept low, and molding defects such as flow marks and jetting are suppressed, thereby improving the appearance quality.
• the upper limit of the content of the (meth)acrylic polymer (D) is 15% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less, based on 100% by mass of the total of the resin composition of the present invention. If the content of the (meth)acrylic polymer (D) is 15% by mass or less, the influence on the moldability of the resin composition of the present invention and the molding material is suppressed.
• the resin composition of the present invention may contain other components in addition to the (meth)acrylic polymer (A), the (meth)acrylic copolymer (B), the rubber-like graft polymer (C) having a crosslinked structure, and the (meth)acrylic polymer (D).
• Examples of other components include release agents, antioxidants, heat stabilizers, impact resistance modifiers, flexibility imparting agents, weather resistance modifiers, colorants, inorganic pigments, organic pigments, carbon black, ferrite, electrical conductivity imparting agents, ultraviolet absorbers, infrared absorbers, lubricants, inorganic fillers, reinforcing agents, plasticizers, antiplasticizers, neutralizing agents, crosslinking agents, flame retardants, preservatives, insect repellents, fragrances, radical scavengers, sound absorbing materials, and core-shell rubber. These other components may be used alone or in combination of two or more.
• the resin composition of the present invention can be produced by mixing the raw materials in a conventional manner, and the method is not particularly limited.
• the raw materials are placed in a single-screw extruder or a twin-screw extruder and heated to melt and knead at about 220 to 280°C.
• the resin composition of the present invention can be suitably used as a molding material by processing it into pellets after heating, melting and kneading.
• the resin composition and molding material of the present invention are shaped into a molded article by a known melt molding method such as extrusion molding, injection molding, compression molding, blow molding, etc.
• the shape of the molded article of the present invention is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, a roughly box-like shape, and a three-dimensional shape having a curved surface portion.
• the resin composition and molding material of the first invention are particularly excellent in moldability, toughness, and impact resistance, and can therefore be suitably used as an injection molding material or an extrusion molding material.
• the resin composition and molding material of the second invention are particularly excellent in moldability, flexibility and transparency, and can therefore be suitably used as a material for injection molding and extrusion molding.
• the molded article of the first aspect of the invention is excellent in toughness and impact resistance, particularly impact resistance in a notched Charpy impact test.
• the molded article of the second invention is excellent in flexibility, impact resistance and transparency.
• the molded article of the present invention can be suitably used for optical components such as display front panels for liquid crystal or organic electroluminescence (EL) displays, signboards, lighting products, toys, containers, home appliances, vehicle parts such as vehicle interior and exterior parts, medical components, housing equipment components, industrial materials, construction materials, lenses, light guide plates, light collecting components, and optical films used in liquid crystal or organic electroluminescence (EL) displays (image display devices), etc.
• EL liquid crystal or organic electroluminescence
• the film-shaped molded product of the second invention not only has excellent impact resistance and transparency over a wide temperature range, but also does not easily turn white when folded.
• the film-shaped molded product of the second invention is less likely to break when folded repeatedly, making it suitable for use in foldable displays, etc.
• Weight average molecular weight (Mw) and number average molecular weight (Mn) of macromonomer (b1) The mass average molecular weight (Mw) and number average molecular weight (Mn) of the macromonomer (b1) obtained in the Examples, Comparative Examples, and Reference Examples were measured by gel permeation chromatography (GPC). 10 mg of the obtained copolymer was dissolved in 10 mL of tetrahydrofuran, and the solution was filtered through a 0.45 ⁇ m filter to prepare a sample for GPC measurement.
• a polymer measurement guard column (manufactured by Tosoh Corporation, product name: TSK-GUARD COLUMN SUPER H-H) and two polymer measurement columns (manufactured by Tosoh Corporation, product name: TSK-GEL SUPER HM-H) were connected in series to a gel permeation chromatography measurement device (manufactured by Tosoh Corporation, model name: HLC-8320).
• a differential refractometer (RI) was used as a detector.
• Mass average molecular weight (Mw) and number average molecular weight (Mn) of macromonomer copolymer The mass average molecular weight (Mw) and number average molecular weight (Mn) of the macromonomer copolymer, which is the (meth)acrylic copolymer (B) obtained in the Examples, Comparative Examples, and Reference Examples, were measured using gel permeation chromatography (GPC). 10 mg of the obtained copolymer was dissolved in 10 mL of tetrahydrofuran, and the solution filtered through a 0.45 ⁇ m filter was used as a sample for GPC measurement.
• GPC gel permeation chromatography
• a high-performance liquid chromatography measurement device manufactured by Tosoh Corporation, model name: HLC-8320 type
• a polymer measurement guard column manufactured by Tosoh Corporation, product name: TSK-GUARD COLUMN SUPER H-H
• one super polymer measurement column manufactured by Tosoh Corporation, product name: TSK-GEL GMHHR-H
• RI differential refractometer
• the mass average particle size of the rubber graft polymer (C) having a crosslinked structure was measured as follows.
• the obtained latex was diluted with distilled water to prepare a diluted latex with a solid content concentration of about 3%, and 0.1 mL of the diluted latex was used as a sample to measure the particle size distribution using a CHDF2000 type particle size distribution analyzer manufactured by MATEC Corporation, USA, under the conditions of a flow rate of 1.4 mL/min, a pressure of about 2.76 MPa (about 4000 psi), and a temperature of 35° C.
• a capillary cartridge for particle separation and a carrier liquid were used, and the liquid was made almost neutral.
• monodisperse polystyrene with a known particle size manufactured by DUKE Corporation of the United States was used as a standard particle size substance, and particle sizes at a total of 12 points from 20 nm to 800 nm were measured to create a calibration curve.
• the raw materials of the resin composition were melt-kneaded using a 26 mm ⁇ screw-type twin-screw extruder (manufactured by Shibaura Machine Co., Ltd., model name: TEM-26SX) to obtain a pellet-shaped resin composition (molding material).
• the obtained resin composition was injection-molded using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., model name: SE100EV-A) at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C.
• the flexural modulus (unit: MPa) of the test pieces of the rod-shaped molded articles was measured using a Tensilon universal testing machine (manufactured by Orientec Co., Ltd., product name: RTC-1250A) in accordance with JIS K7171.
• the flexural modulus was determined from a stress-strain curve obtained under conditions of room temperature of 23° C. and a test speed of 2 mm/min.
• the Charpy impact strength (unit: kJ/m2) was measured using a Charpy impact tester (manufactured by Toyo Seiki Co., Ltd., product name: DG- CP ) in accordance with JIS K7111 using the rod-shaped molded bodies as test pieces (with and without notches).
• melt flow rate (Moldability evaluation: Melt flow rate) As an index of melt moldability of the resin compositions obtained in the Examples, Comparative Examples, and Reference Examples, the melt flow rate (MFR) (unit: g/10 min) was measured in accordance with JIS K7210 (Method A) using a melt indexer (manufactured by Techno Seven Co., Ltd., device name: L243) at a temperature of 230° C. and a load of 37.3 N. The heating time of the resin composition was 4 minutes, and the sample cutting time interval was 10 to 120 seconds depending on the MFR value of the sample.
• V-50 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 2,2'-azobis(2-methylpropionamidine) dihydrochloride, product name
• V-50 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 2,2'-azobis(2-methylpropionamidine) dihydrochloride, product name
• MMA was added in portions every 15 minutes for a total of 5 times (total amount of MMA: 7 parts).
• the liquid in the polymerization apparatus was stirred and held at 60°C for 6 hours, and then cooled to room temperature to obtain a transparent aqueous solution of dispersant (1) with a solid content of 8% by mass.
• the obtained macromonomer had a number average molecular weight (Mn) of 21,300 and a mass average molecular weight (Mw) of 39,100.
• the Tg of the homopolymer of methyl methacrylate (MMA) is 105°C (POLYMER HANDBOOK FOURTH EDITION 2003), and the Tg of the homopolymer of methyl acrylate (MA) is 10°C (POLYMER HANDBOOK FOURTH EDITION 2003).
• the Tg of the macromonomer (b1) corresponding to polymer (B1) was calculated to be 99°C using the Fox formula.
• the polymerization apparatus was cooled to 40 ° C., and then 0.5 parts of the polymerization initiator (2) was added and stirred for 30 minutes to dissolve.
• the polymerization apparatus was fully replaced with nitrogen, and the aqueous dispersion was heated to 82 ° C. and held for 4 hours, and then heated to 90 ° C. and held for 1 hour. After cooling to 40 ° C. or less, it was filtered through a filter cloth, and the filtrate was washed with deionized water. The filtered product was then dried at 40° C. for 12 hours using a hot air circulation dryer to obtain a bead-shaped macromonomer copolymer, a (meth)acrylic copolymer (B).
• the obtained (meth)acrylic copolymer (B) had a number average molecular weight (Mn) of 75,000 and a mass average molecular weight (Mw) of 1,300,000.
• 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).
• the Tg of the polymer (B2) contained in the (meth)acrylic copolymer (B) was calculated to be -37.5°C using the Fox formula.
• a mixture of 22.0 parts of MMA, 16.0 parts of BA, 2.0 parts of ST, 1.2 parts of 1,3BD, 0.15 parts of AMA, 0.07 parts of TBHP, and 1.44 parts of emulsifier (1) was added as the composition for the inner layer over a period of 2 hours, and the mixture was maintained at 80°C for 1 hour to complete the polymerization of the inner layer.
• the polymerization rate of the obtained latex was 99% or more, and the mass average particle size of the polymer for the inner layer was 190 nm.
• an aqueous solution of 0.2 parts of SFS dissolved in 3.0 parts of deionized water was added to the latex and held for 15 minutes, after which a mixture of 49.0 parts of BA, 11.0 parts of ST, 0.15 parts of 1,3BD, 1.0 part of AMA, 0.17 parts of CHP, and 0.96 parts of emulsifier (1) was added dropwise over 3 hours as a composition for the intermediate layer, and the mixture was held for 2 hours to complete the polymerization of the intermediate layer.
• the polymerization rate of the obtained latex was 99% or more, and the mass average particle diameter of the polymer formed up to the intermediate layer was 260 nm.
• aqueous solution of 0.2 parts of SFS dissolved in 3.0 parts of deionized water was added to the latex and held for 15 minutes, after which a mixture of 57.0 parts of MMA, 3.0 parts of MA, 0.1 parts of TBHP, and 0.18 parts of nOM was added dropwise over 2 hours as a composition for the graft layer, and the mixture was held for 1 hour to complete the polymerization of the graft layer.
• the polymerization rate of the final latex obtained was 99% or more.
• the mass average particle diameter of the polymer was 280 nm.
• the emulsion was placed in a separable flask equipped with a cooling condenser, and then a mixture of 0.20 parts of sulfuric acid and 49.8 parts of distilled water was added over a period of 3 minutes. The temperature was then maintained at 80° C. for 7 hours, and then cooled. The resulting reaction product was then kept at room temperature for 6 hours, and then neutralized with an aqueous caustic soda solution to obtain a polyorganosiloxane latex.
• the atmosphere inside the separable flask was replaced with nitrogen by passing a nitrogen stream through it, and the temperature was raised to 50°C.
• an aqueous solution of 0.001 parts of ferrous sulfate, 0.003 parts of disodium salt of ethylenediaminetetraacetic acid, and 0.24 parts of Rongalit in 10 parts of distilled water was added to initiate radical polymerization. This state was maintained for one hour to complete the polymerization of the acrylate component, and a composite rubber latex of polyorganosiloxane rubber and butyl acrylate was obtained.
• Example 1 A pellet-shaped resin composition was prepared using a twin-screw extruder (product name: TEM-26SX, 26 mm ⁇ , L/D ⁇ 48) manufactured by Shibaura Machine Co., Ltd. 52.5 parts of ACRYPET VH were used as the (meth)acrylic polymer (A), 37.5 parts of the macromonomer copolymer obtained in Production Example 4 as the (meth)acrylic copolymer (B), and 10.0 parts of the rubber-like graft polymer (C) having a crosslinked structure obtained in Production Example 5 were used, and the mixture was melt-kneaded under conditions of a cylinder temperature of 200 to 230° C.
• test pieces for evaluation were prepared using the obtained resin composition under conditions of a cylinder temperature of 250°C and a mold temperature of 60°C.
• the obtained injection molded pieces were used for bending tests and Charpy impact tests.
• the melt flow rate was measured using dried pellet-shaped resin compositions.
• the resin composition and the evaluation results of the obtained test pieces are shown in Table 1.
• Example 1 [Examples I-2 to I-5, Comparative Examples I-1 to I-5, Reference Example I-1]
• pellet-shaped resin compositions were prepared from the resin compositions shown in Table 1, and test pieces were prepared by injection molding and evaluated. The resin compositions and the evaluation results of the obtained test pieces are shown in Table 1.
• Example I-4 the rubber portion is a silicone-acrylic composite rubber, and due to the effect of the rubber graft polymer (C-2) having a crosslinked structure, the notched Charpy impact test value at -30°C is good, and the toughness and impact resistance at low temperatures are improved.
• Comparative Example I-5 did not contain the (meth)acrylic copolymer (B), had a low melt flow rate, and was poor in moldability.
• Example I-5 further contains a (meth)acrylic polymer (D), and it is clear that, compared with Reference Example I-1, the haze value is reduced, and the transparency and surface appearance can be improved. As described above, in Examples I-1 to I-5, high toughness and impact resistance are achieved in combination with good moldability.
• Example II-1 A pellet-shaped resin composition was prepared using a twin-screw extruder (product name: TEM-26SX, 26 mm ⁇ , L/D ⁇ 48) manufactured by Shibaura Machine Co., Ltd.
• test pieces for evaluation were prepared using the obtained resin composition under conditions of a cylinder temperature of 250°C and a mold temperature of 60°C.
• the obtained injection molded pieces were used to measure the haze value, and were subjected to a bending test and a Charpy impact test.
• the melt flow rate was measured using a dried pellet-shaped resin composition.
• the resin composition and the evaluation results of the obtained test pieces are shown in Table 2.
• Example II-2 to II-6 Comparative Examples II-1 to II-3, Reference Example II-1
• pellet-shaped resin compositions were prepared from the resin compositions shown in Table 2, and test pieces were prepared by injection molding and evaluated. The resin compositions and the evaluation results of the obtained test pieces are shown in Table 2.
• Example II-6 and Comparative Example II-2 show that the haze value is reduced and the transparency and surface appearance are improved by adding the (meth)acrylic polymer (D) to a resin composition containing the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B).
• a comparison of Example II-6 and Comparative Example II-2 shows that, due to the effect of the (meth)acrylic polymer (B), the flexural modulus is low, flexibility and impact resistance are imparted, and the melt flow rate is high, resulting in excellent moldability.
• Example II-1 to II-5 the rubber-like graft polymer (C) having a crosslinked structure is contained in addition to the (meth)acrylic copolymer (B), which provides further excellent flexibility and impact resistance. Comparing Examples II-1 to II-5 with Comparative Example II-1, it can be seen that the effect of the (meth)acrylic copolymer (B) provides flexibility and impact resistance with a low flexural modulus, and provides excellent moldability with a high melt flow rate. In addition, comparing Example II-1 with Examples II-2 and II-3, it is found that P530A has a higher effect of suppressing haze than P551A.
• Examples II-4 and II-5 which use MF as the (meth)acrylic polymer (A2), are able to further suppress haze and improve moldability.
• Examples II-1 to II-6 contain the (meth)acrylic polymer (D) to suppress haze to a low level, and have excellent transparency and good appearance quality.
• Reference Example II-1 does not contain the (meth)acrylic polymer (D), so the transparency is insufficient, but it is excellent in impact resistance and moldability.
• Comparative Example II-3 which contains only the (meth)acrylic polymer (A), is excellent in transparency, but has a high flexural modulus, is poor in flexibility, and is also poor in impact resistance.
• the resin composition of the first invention contains, as constituent components, a (meth)acrylic polymer (A), a specific (meth)acrylic copolymer (B), and a rubber-like graft polymer (C) having a crosslinked structure, and therefore has excellent toughness, impact resistance, and moldability.
• the molding material and molded article of the first invention are obtained by molding the resin composition, and therefore have excellent toughness, impact resistance and moldability.
• the resin composition of the second invention contains the (meth)acrylic polymer (A), the specific (meth)acrylic copolymer (B) and the (meth)acrylic polymer (D) as constituent components, and is therefore excellent in flexibility, moldability and transparency.
• the molding material and molded article of the second invention are obtained by molding the above-mentioned resin composition, and therefore it is possible to obtain a molded article having excellent flexibility, impact resistance and transparency and exhibiting good appearance quality.

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