WO2021193613A1 - 共重合体、樹脂組成物、成形体、フィルム状成形体、及び共重合体の製造方法 - Google Patents

共重合体、樹脂組成物、成形体、フィルム状成形体、及び共重合体の製造方法 Download PDF

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Publication number
WO2021193613A1
WO2021193613A1 PCT/JP2021/011946 JP2021011946W WO2021193613A1 WO 2021193613 A1 WO2021193613 A1 WO 2021193613A1 JP 2021011946 W JP2021011946 W JP 2021011946W WO 2021193613 A1 WO2021193613 A1 WO 2021193613A1
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WIPO (PCT)
Prior art keywords
mass
copolymer
macromonomer
acrylate
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2021/011946
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English (en)
French (fr)
Japanese (ja)
Inventor
大谷　剛
優 都倉
晃 山内
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Filing date
Publication date
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Priority to CN202180016416.0A priority Critical patent/CN115210279A/zh
Priority to JP2021519905A priority patent/JPWO2021193613A1/ja
Priority to KR1020227032182A priority patent/KR102814981B1/ko
Priority to EP21777178.1A priority patent/EP4130068A4/en
Priority to MX2022011520A priority patent/MX2022011520A/es
Publication of WO2021193613A1 publication Critical patent/WO2021193613A1/ja
Priority to JP2022028528A priority patent/JP7302685B2/ja
Priority to US17/896,844 priority patent/US20230002528A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
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    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
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    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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    • B29C48/873—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the nozzle zone characterised by differential heating or cooling in the direction of the stream of the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Definitions

  • the present invention relates to a copolymer, a resin composition, a molded product, a film-shaped molded product, and a method for producing a copolymer.
  • Acrylic resin has excellent transparency, weather resistance, high elasticity, surface hardness, etc., so it is used for display front panels such as liquid crystal displays and organic EL, signboard supplies, lighting supplies, home appliances, vehicle interior / exterior materials, industrial materials, and construction. It is widely used in materials, lenses, light guide plates, light collecting members, optical films used for displays such as liquid crystals and organic EL.
  • acrylic resin products are required to have improved impact resistance while maintaining a high elastic modulus. Further, it is required that the acrylic resin can be formed into a thin shape or a complicated shape by using a melt molding method such as injection molding or extrusion molding. That is, an acrylic resin having excellent melt moldability is required.
  • Patent Document 1 describes a core portion made of crosslinked rubber and a shell portion that ensures compatibility and dispersibility between a matrix (meth) acrylic polymer.
  • a resin composition in which a rubber having a core-shell structure having a core-shell structure (core-shell rubber) is blended with a (meth) acrylic resin is disclosed.
  • the resin composition described in Patent Document 1 tends to increase the melt viscosity and decrease the melt moldability due to the inclusion of the core-shell rubber, the resin composition is used for a thicker purpose. There is a problem that it is limited to large resin products and resin products having a simple shape.
  • the molded product using the resin composition is transparent near room temperature, there is a problem that the transparency is lowered in a high temperature environment. Further, when an acrylic resin containing core-shell rubber is molded into a film, there is a problem that the film is whitened when it is bent.
  • a block / graft copolymer is a resin composition in which a block / graft copolymer having a poly (meth) acrylate chain is blended with an acrylic resin because two or more kinds of polymer segments are chemically bonded to each other.
  • the phase-separated structure is nanometer-sized (called a "microphase-separated structure").
  • the resin composition and the molded product obtained by molding the resin composition it is possible to express both the characteristics of the acrylic resin as a matrix and the block / graft copolymer, and further block / graft.
  • the characteristics of each polymer segment of the copolymer can be exhibited.
  • Acrylic resin has excellent transparency, but has the problem of being hard and brittle.
  • the resin composition in which the block / graft copolymer is blended with the acrylic resin a microphase-separated structure is formed. Therefore, in the molded body obtained by molding the resin composition, the transparent resin has. Good properties can be maintained, and the characteristics (for example, impact resistance, etc.) of each polymer segment of the block / graft copolymer can be exhibited.
  • Patent Document 2 obtains a block copolymer by a method of performing controlled radical polymerization in the presence of nitroxide. Specifically, a technique for obtaining a sheet-shaped molded product containing a block copolymer is disclosed by a method of producing a cast sheet by placing a syrup in a mold and polymerizing it. It is described that the obtained sheet-shaped molded product contains an acrylic resin and a block copolymer having a polymethyl methacrylate chain and an n-butyl acrylate / styrene copolymer chain, and is excellent in impact resistance and transparency. Has been done.
  • an acrylic macromonomer (hereinafter referred to as "macromonomer”) is produced in advance using a very small amount of a cobalt complex having an extremely high chain transfer constant, and the macro is produced.
  • a method for producing a block / graft copolymer by copolymerizing a monomer with another monomer is known.
  • a method for producing an acrylic macromonomer using a cobalt complex is known as a catalytic chain transfer polymerization method (CCTP).
  • the macromonomer is a polymer having a polymerizable functional group in its molecular structure, and is sometimes called a macromolecule.
  • Patent Document 3 CCTP is applied to an emulsification polymerization method to produce a macromonomer, and then a graft copolymer (comb) is obtained by copolymerizing the obtained macromonomer with another acrylic monomer using an emulsification polymerization method.
  • a technique for producing a copolymer) (corresponding to the "block / graft copolymer" of the present application) and then adding the obtained graft copolymer to a thermoplastic resin to improve impact resistance is disclosed. ..
  • Patent Document 4 CCTP is applied to a suspension polymerization method to produce a macromonomer, and then the obtained macromonomer is copolymerized with another acrylic monomer by a solution polymerization method to obtain a macromonomer.
  • a technique for producing a copolymer and then adding the obtained macromonomer copolymer to an acrylic resin to achieve both impact resistance and transparency is disclosed.
  • Patent Document 2 cannot be applied to the melt molding method because the synthesis of the block copolymer, the synthesis of the polymethylmethacrylate as the matrix, and the production of the molded product are performed at the same time, and the shape and thickness are thin. There is a problem that it cannot be molded into a complicated shape.
  • the molded product using the obtained thermoplastic resin composition is not transparent because the refractive index of the graft polymer and the refractive index of the acrylic resin as the matrix are different.
  • an object of the present invention is to solve these problems. That is, an object of the present invention is to provide a molded product having excellent impact resistance and transparency in a wide operating temperature range, and a resin composition having excellent melt moldability for molding the molded product. Further, the present invention provides a resin composition capable of suppressing bending and whitening of a film. Another object of the present invention is to obtain a film-shaped molded product having excellent impact resistance and transparency in a wide operating temperature range and capable of suppressing bending and whitening of the film, and a resin composition for molding the film-shaped molded product. To provide. Furthermore, an object of the present invention is to provide a copolymer which is a constituent component of the resin composition and a method for producing the copolymer.
  • the mass average molecular weight (Mw) is 240,000 or more and 3,500,000 or less.
  • Copolymer contains a structural unit derived from the macromonomer (A).
  • R and R 1 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 indicates a terminal group.
  • n represents a natural number from 2 to 10,000.
  • the structural unit derived from the macromonomer (A) contains 80% by mass or more of the repeating unit derived from methyl methacrylate with respect to 100% by mass of the total mass of the structural unit derived from the macromonomer (A).
  • a copolymer in which the structural unit derived from the comonomer (B) includes a structural unit derived from acrylate (B1) and a structural unit derived from aromatic vinyl (B2).
  • R and R 1 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 indicates a terminal group.
  • n represents a natural number from 2 to 10,000.
  • the structural unit derived from the macromonomer (A) contains 80% by mass or more of the repeating unit derived from methyl methacrylate with respect to 100% by mass of the total mass of the structural unit derived from the macromonomer (A).
  • the copolymer according to any one of [4] to [6].
  • the mass average molecular weight (Mw) of the copolymer is preferably 300,000 or more and 3,000,000 or less, more preferably 600,000 or more and 2,000,000 or less, [1] to [10].
  • the content ratio of the macromonomer (A) unit contained in the copolymer is preferably 35% by mass or more and 75% by mass or less, preferably 40% by mass, based on 100% by mass of the total mass of the copolymer.
  • the mass average molecular weight (Mw) of the macromonomer (A) is preferably 10,000 or more and 100,000 or less, more preferably 12,000 or more and 80,000 or less, and 15,000 or more and 60,000 or less.
  • the content ratio of the structural unit of the acrylate (B1) contained in the structural unit derived from the comonomer (B) is 70% by mass or more and 100% by mass with respect to 100% by mass of the total mass of the comonomer (B). % Or less, more preferably 79% by mass or more and 95% by mass or less, still more preferably 81% by mass or more and 90% by mass or less, the copolymer according to [6].
  • the content ratio of the structural unit of the aromatic vinyl (B2) contained in the structural unit derived from the copolymer (B) is 10 to 30 mass by mass with respect to 100% by mass of the total mass of the copolymer (B).
  • the acrylate (B1) is at least one selected from the group consisting of 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, n-butyl acrylate, n-propyl acrylate, ethyl acrylate, and 2-hydroxyethyl acrylate.
  • the aromatic vinyl (B2) is styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene and pt-butylstyrene, vinylethylbenzene, vinyl.
  • the copolymer according to any one of [1] to [17] which is at least one selected from the group consisting of toluene, vinylxylene, vinylnaphthalene, diphenylethylene, and divinylbenzene.
  • a method for producing a copolymer which comprises a step of polymerizing a mixture containing the polymerizable composition (X) and a polymerization initiator.
  • the polymerizable composition (X) is composed of a macromonomer (A) represented by the following general formula (1) and a comonomer (B) copolymerizable with the macromonomer (A).
  • R and R 1 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 indicates a terminal group.
  • n represents a natural number from 2 to 10,000.
  • the syrup preparation step The method for producing a copolymer according to any one of [19] to [24], which comprises a step of dissolving a radical polymerization initiator and a step of preparing an aqueous solution.
  • the content ratio of the acrylate (B1) contained in the comonomer (B) is preferably 70% by mass or more and 100% by mass or less, preferably 79% by mass, based on 100% by mass of the total mass of the comonomer (B).
  • the acrylate (B1) is at least one selected from the group consisting of 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, n-butyl acrylate, n-propyl acrylate, ethyl acrylate, and 2-hydroxyethyl acrylate.
  • the content ratio of the aromatic vinyl (B2) contained in the copolymer (B) is preferably 10 to 30% by mass, preferably 13 to 21% by mass, based on 100% by mass of the total mass of the copolymer (B).
  • the aromatic vinyl (B2) is styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene and pt-butylstyrene, vinylethylbenzene, vinyl.
  • the (meth) acrylic polymer (M) is 10% by mass or more and 99% by mass or less, and the copolymer is 1% by mass or more and 90% by mass with respect to 100% by mass of the total mass of the resin composition.
  • the resin composition according to [30] which is contained below.
  • the content ratio of the (meth) acrylic polymer (M) is preferably 10 to 99% by mass, more preferably 20 to 98% by mass or less, based on 100% by mass of the total mass of the resin composition. , 50 to 90%, more preferably, the resin composition according to any one of [30] to [33].
  • the content ratio of the copolymer is preferably 1 to 90% by mass, more preferably 2 to 80% by mass, further preferably 10 to 50% by mass, based on 100% by mass of the total mass of the resin composition.
  • the mass average molecular weight (Mw) of the (meth) acrylic polymer (M) is preferably 30,000 or more and 1,000,000 or less, more preferably 50,000 or more and 500,000 or less, 80, The resin composition according to any one of [30] to [35], more preferably 000 or more and 200,000 or less.
  • the mass ratio represented by the (meth) acrylic polymer (M): copolymer is preferably 40:60 to 90:20, more preferably 50:50 to 80:20, and 60:40 to 60:40.
  • the resin composition of the present invention contains the copolymer of the present invention as a constituent component, it is excellent in melt moldability. Further, since the molded product of the present invention is formed by molding the resin composition, it is excellent in impact resistance and transparency in a wide operating temperature range.
  • the present embodiment is not limited to the following description and varies within the scope of the gist thereof. It can be transformed into.
  • “(meth) acrylic acid” means at least one selected from “acrylic acid” and “methacrylic acid”. Further, the (meth) acrylate indicates methacrylate or acrylate.
  • the "monomer” means an unpolymerized compound, and the "repeating unit” and the “structural unit” constitute a polymer derived from the monomer formed by polymerizing the monomer. Means the structural unit to be used.
  • the structural unit constituting the polymer is referred to as "-monomer unit".
  • the "repeating unit” or “structural unit” may be a unit directly formed by a polymerization reaction, or a part of the unit may be converted into another structure by processing a polymer. ..
  • “% by mass” indicates the content of a specific component contained in 100% by mass of the total amount.
  • the numerical range represented by using “-” in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • “AB” means that it is A or more and B or less.
  • the first embodiment of the copolymer of the present invention has a mass average molecular weight (Mw) of 240,000 or more and 3,500,000 or less, a structural unit derived from acrylate (B1), and aromatic vinyl ( It is a copolymer (1) containing a structural unit derived from B2) and having a branched structure.
  • the lower limit of the mass average molecular weight (Mw) of the copolymer (1) of the present invention is a resin composition obtained by mixing the copolymer (1) and a (meth) acrylic polymer (M) described later (hereinafter,).
  • Mw mass average molecular weight
  • the upper limit of Mw of the copolymer (1) of the present invention is 3.5 million or less because the handleability as a resin composition is good.
  • the Mw of the copolymer (1) of the present invention is 240,000 or more and 3,500,000 or less, preferably 300,000 or more and 3,000,000 or less, and 600,000 or more and 2,000, More preferably, it is 000 or less.
  • the mass average molecular weight (Mw) of the copolymer (1) and the copolymer (2) described later is the mass average molecular weight determined as the relative molecular weight of the copolymer, and is gel permeation chromatography. Obtained using graphics (GPC).
  • the calibration curve used to determine the relative molecular weight is made using a standard polymer with a known peak molecular weight.
  • the standard polymer it is preferable to use a type close to the properties of the polymer to be measured, and when measuring the copolymer, it is possible to prepare a calibration curve using 5 to 10 types of polymethylmethacrylate having a known peak molecular weight. preferable.
  • As the detector it is preferable to use a differential refractometer (RI).
  • the copolymer (1) of the present invention contains a structural unit derived from the acrylate (B1) and a structural unit derived from the aromatic vinyl (B2), whereby the impact resistance of the obtained molded product is impact-resistant.
  • the sex can be further improved. The details of the acrylate (B1) and the aromatic vinyl (B2) will be described later.
  • the copolymer (1) of the present invention has a branched structure in the molecule, so that the impact resistance of the obtained molded product can be further improved.
  • the branched structure in the copolymer (1) includes, for example, a macromonomer (A) and a comonomer, as described in the report by Yamada et al. (Prog. Polymer. Sci. 31 (2006) p835-877).
  • the terminal double-bonding group of the macromonomer (A) is copolymerized with the acrylate (B1) or the aromatic vinyl (B2) according to the reaction mechanism at the time of copolymerization. It is formed. That is, by reacting the terminal double bond group of the macromonomer (A) with acrylate (B1) or aromatic vinyl (B2), a trifurcation connected to a branched chain (branched structure) in the main chain (main chain structure).
  • the copolymer (1) of the present invention having a branch point can be obtained. Further, in the copolymer (1) of the present invention, a branched structure is generated from the macromonomer (A), and the main component is derived from the acrylate (B1) or aromatic vinyl (B2) that reacts with the macromonomer. A chain will be formed.
  • the structural unit derived from acrylate (B1) and the structural unit derived from aromatic vinyl (B2) may be contained in the main chain or the branched chain. However, it may be contained in both the main chain and the branched chain.
  • the branched structure may include a structural unit derived from the acrylate (B1) and a structural unit derived from the aromatic vinyl (B2). ..
  • the structural unit derived from the acrylate (B1) and the structural unit derived from the aromatic vinyl (B2) in the branched structure the impact resistance of the obtained molded product and a wide operating temperature range can be obtained. The transparency can be further improved.
  • the impact resistance of the obtained molded product and the transparency in a wide operating temperature range can be further improved, so that the copolymer is bonded to the three-pronged branch point 3
  • at least one structural unit is a structural unit derived from acrylate (B1) or a structural unit derived from aromatic vinyl (B2).
  • two structural units are more preferably structural units derived from acrylate (B1) or aromatic vinyl (B2), and all of the three structural units are all. More preferably, it is a structural unit derived from acrylate (B1) or a structural unit derived from aromatic vinyl (B2).
  • the three-pronged branch point is formed from a structural unit derived from methacrylate.
  • the copolymer (1) of the present invention can contain a structural unit derived from the macromonomer (A) represented by the following general formula (1).
  • R and R 1 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 indicates a terminal group.
  • n represents a natural number from 2 to 10,000.
  • the copolymer (1) of the present invention contains the macromonomer (A) unit represented by the general formula (1), the impact resistance and transparency of the obtained molded product can be further improved. .. The details of the macromonomer (A) will be described later.
  • the copolymer (1) of the present invention contains a structural unit derived from the macromonomer (A) represented by the general formula (1), the copolymer (1) of the present invention has the same weight.
  • the unreacted macromonomer (A) at the time of production of the coalescence (1), the polymer consisting only of the acrylate (B1) unit, or the polymer consisting only of the aromatic vinyl (B2) unit may be contained.
  • the copolymer (1) of the present invention can be obtained by polymerizing the polymerizable composition (X) described later, which contains the macromonomer (A), the acrylate (B1) and the aromatic vinyl (B2). can.
  • the second embodiment of the copolymer of the present invention is referred to as a structural unit derived from the macromonomer (A) described later, which is represented by the following general formula (1) (hereinafter, referred to as "macromonomer (A) unit”. ) And a structural unit (hereinafter, referred to as “comonomer (B) unit”) derived from the comonomer (B), which will be described later, which is copolymerizable with the macromonomer (A).
  • R and R 1 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 indicates a terminal group.
  • n represents a natural number from 2 to 10,000.
  • the copolymer (2) of the present invention contains the macromonomer (A) unit, the impact resistance and transparency of the obtained molded product can be further improved.
  • the details of the macromonomer (A) will be described later.
  • the copolymer (2) of the present invention contains the comonomer (B) unit, the impact resistance of the obtained molded product can be further improved.
  • the details of the comonomer (B) will be described later.
  • the copolymer (2) of the present invention may contain an unreacted macromonomer (A) at the time of production of the copolymer (2) or a polymer composed of only comonomer (B) units.
  • the copolymer (2) of the present invention can be obtained by polymerizing the polymerizable composition (X) described later, which contains the macromonomer (A) and the comonomer (B).
  • the lower limit of the mass average molecular weight (Mw) of the copolymer (2) of the present invention is a resin composition obtained by mixing the copolymer (2) and a (meth) acrylic polymer (M) described later (hereinafter,).
  • Mw mass average molecular weight
  • the upper limit of Mw of the copolymer (2) of the present invention is 3.5 million or less because the handleability as a resin composition is good.
  • the Mw of the copolymer (2) of the present invention is 240,000 or more and 3,500,000 or less, preferably 300,000 or more and 3,000,000 or less, and 600,000 or more and 2,000, More preferably, it is 000 or less.
  • the resin composition of the present invention is the (meth) acrylic polymer (M) described later, and the copolymer (1) or copolymer (2) of the present invention "hereinafter, simply referred to as” copolymer ". Is a resin composition containing.
  • the resin composition of the present invention can contain other components (Q) described later, if necessary.
  • the content ratio of the (meth) acrylic polymer (M) contained in the resin composition is preferably 10 to 99% by mass, preferably 20 to 98% by mass, based on 100% by mass of the total mass of the resin composition. The following is more preferable, and 50 to 90% is further preferable.
  • the lower limit of the content ratio of the (meth) acrylic polymer (M) contained in the resin composition is 10% by mass or more, the acrylic resin has a molded product obtained by molding the resin composition. Properties such as transparency, weather resistance, high elasticity, and surface hardness are good.
  • the melt moldability of the resin composition is good, and further, the molded product obtained by molding the resin composition , Impact resistance and transparency in a wide operating temperature range are improved.
  • the content ratio of the copolymer contained in the resin composition is preferably 1 to 90% by mass, more preferably 2 to 80% by mass, and 10 to 50% by mass with respect to 100% by mass of the total mass of the resin composition. Mass% is more preferred.
  • the lower limit of the content ratio of the copolymer contained in the resin composition is 1% by mass or more, the melt moldability of the resin composition is good, and further, a molded product obtained by molding the resin composition. The characteristics such as impact resistance and transparency in a wide operating temperature range are improved.
  • the upper limit of the content ratio of the copolymer is 90% by mass or less, the molded product obtained by molding the resin composition has the original transparency, weather resistance, high elasticity, and surface hardness of the acrylic resin. Etc. can be maintained well.
  • the content ratio of the copolymer can be appropriately optimized depending on the elastic modulus and impact resistance required for the molded product.
  • the mass ratio represented by the (meth) acrylic polymer (M): copolymer is preferably 10:90 to 99: 1, more preferably 20:80 to 98: 2, and 50:50 to 90:10. Is even more preferable.
  • the resin composition of the present invention can contain, if necessary, another component (Q) described later within a range that does not impair the effects of the present invention.
  • the content ratio of the other component (Q) is not particularly limited as long as the effect of the present invention is not impaired. Usually, 0 to 20% by mass is preferable, and 0.1 to 5% by mass is more preferable with respect to 100% by mass of the total mass of the resin composition.
  • the MFR melt flow rate
  • the resin composition of the present invention has the above-mentioned structure, the MFR (melt flow rate) at a temperature of 230 ° C. and a load of 37.3 N is larger than that of the (meth) acrylic polymer (M) alone. It has an excellent fluidity of over 0.0 g / 10 min and is excellent in melt moldability. As a result, it is suitable as a molding material for producing a thin molded body or a molded body having a complicated shape.
  • the resin composition of the present invention is suitable as a molding material used for known melt molding such as injection molding, extrusion molding, compression molding, and hollow molding.
  • the resin composition of the present invention is suitable as a molding material used for injection molding or extrusion molding. Further, it is suitable as a molding material used for extrusion molding of a film-shaped molded product.
  • the (meth) acrylic polymer (M), the copolymer, and other components (Q) added as needed are added to known physical materials such as a Henschel mixer and a blender. It can be obtained by a method of kneading to obtain a resin composition by a mixing method and a known melt-mixing method such as an extruder. By obtaining the obtained resin composition in the form of pellets, workability is improved when the molded product is subsequently melt-molded to obtain a molded product.
  • Such a resin composition can be produced, for example, by mixing the above-mentioned copolymer of the present invention with the above-mentioned (meth) acrylic polymer (M).
  • the (meth) acrylic polymer (M) is one of the constituents of the resin composition of the present invention.
  • the (meth) acrylic polymer (M) is in MMA units (hereinafter, methyl methacrylate may be abbreviated as MMA) with respect to 100% by mass of the total weight of the (meth) acrylic polymer (M). Is contained in an amount of 80% by mass or more.
  • the upper limit of the content ratio of MMA units is not particularly limited, and may be a homopolymer of MMA (content ratio of MMA units is 100% by mass).
  • the (meth) acrylic polymer (M) is a repeating unit derived from another comonomer capable of copolymerizing with MMA for various purposes in addition to the MMA unit (hereinafter, referred to as "comonomer unit"). Can be included.
  • the above-mentioned acrylate unit as the comonomer unit in the (meth) acrylic polymer (M)
  • depolymerization of the (meth) acrylic polymer (M) when exposed to high temperature conditions is suppressed. Therefore, the heat-resistant decomposition property can be improved.
  • the glass transition temperature (Tg) processability, heat resistance, refractive index, weather resistance, releasability, and moldability of the (meth) acrylic polymer (M) can be adjusted. Functions such as heat resistance can be controlled.
  • the upper limit of the content ratio of the comonomer unit of the (meth) acrylic polymer (M) is the performance of the (meth) acrylic polymer such as heat resistance, hardness, scratch resistance, weather resistance, transparency, and workability. 20% by mass or less is preferable with respect to 100% by mass of the total mass of the (meth) acrylic polymer (M).
  • the lower limit of the content ratio of the comonomer unit is not particularly limited, and may be a homopolymer of MMA that does not contain the comonomer unit.
  • Examples of the comonomer forming the comonomer unit of the (meth) acrylic polymer (M) include the following a) to i). a) 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 -A (meth) acrylate ester monomer other than methyl methacrylate
  • a hydroxyl group-containing (meth) acrylate monomer such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate.
  • An acid anhydride group-containing vinyl monomer such as maleic anhydride and itaconic anhydride.
  • Epoxy group-containing vinyl-based monomers such as glycisyl (meth) acrylate, glycisyl ⁇ -ethyl acrylate, and 3,4-epoxybutyl (meth) acrylate.
  • Amino group-containing (meth) acrylate-based vinyl monomer such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
  • Vinyl-based monomers such as styrene, ⁇ -methylstyrene, vinyltoluene, (meth) acrylonitrile, vinyl chloride, vinyl acetate, vinyl propionate
  • 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, trimerol propane
  • Polyfunctional vinyl-based monomers such as tri (meth) acrylate, allyl (meth) acrylate, and N, N'-methylenebis (meth) acrylamide.
  • methyl acrylate, ethyl (meth) acrylate, and n-butyl (meth) acrylate are used in terms of easy availability of monomers.
  • 2-Ethylhexyl (meth) acrylate is preferable, and methyl acrylate is more preferable.
  • the mass average molecular weight (Mw) of the (meth) acrylic polymer (M) in the present invention is not particularly limited, and is preferably 30,000 or more and 1,000,000 or less, and 50,000 or more and 500,000. The following is more preferable, and 80,000 or more and 200,000 or less is further preferable.
  • Mw of the (meth) acrylic polymer (M) is 30,000 or more, the performance of the (meth) acrylic polymer such as heat resistance, hardness, scratch resistance, weather resistance, transparency, etc. Is more likely to be demonstrated.
  • the upper limit of Mw of the (meth) acrylic polymer (M) is 1,000,000 or less, the melt viscosity is within an appropriate range, and the melt kneadability and processability are good.
  • the macromonomer (A) is one of the monomer raw materials forming the copolymer of the present invention, is represented by the following general formula (1), and can be radically polymerized at one end of the poly (meth) acrylate segment. Has an unsaturated double bond group.
  • R and R 1 to R n are independently hydrogen atoms, alkyl groups, cycloalkyl groups, aryl groups or heterocyclic groups.
  • X 1 to X n are independent of each other. It is a hydrogen atom or a methyl group.
  • Z is a terminal group.
  • N is a natural number of 2 to 10,000.
  • the copolymer of the present invention contains the macromonomer (A) unit to produce the resin composition of the present invention
  • the copolymer and the (meth) acrylic polymer (M) are combined. Good compatibility. As a result, the impact resistance and transparency of the obtained molded product are excellent.
  • the types of the monomer units constituting each of the macromonomer (A) and the (meth) acrylic polymer (M) and the composition ratio of each of the monomer units in a similar manner, the above-mentioned The compatibility between the copolymer and the (meth) acrylic polymer (M) can be improved.
  • alkyl group of R and R 1 to R n examples include a branched or linear alkyl group 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 and nonyl 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 selected from the viewpoint of availability.
  • a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a t-butyl group are more preferable, and a methyl group is particularly preferable.
  • Examples of the cycloalkyl group of R and R 1 to R n include a cycloalkyl group having 3 to 20 carbon atoms. Specific examples thereof 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 and the like.
  • a cyclopropyl group, a cyclobutyl group, and an adamantyl group are preferable because of their availability.
  • Examples of the aryl group of R and R 1 to R n include an aryl group having 6 to 18 carbon atoms. Specific examples include, for example, a phenyl group, a benzyl group, a naphthyl group and the like.
  • heterocyclic groups of R and R 1 to R n include heterocyclic groups having 5 to 18 carbon atoms. Specific examples include, for example, a ⁇ -lactone group, an ⁇ -caprolactone group, a morpholin group, and the like. Examples of the hetero atom contained in the heterocycle include an oxygen atom, a nitrogen atom, a sulfur atom and the like.
  • R or R 1 to R n are independently an alkyl group, an aryl group, a carboxy group, an alkoxycarbonyl group (-COOR'), a carbamoyl group (-CONR'R''), a cyano group, and the like. Selected from the group consisting of 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. Groups or atoms can be mentioned. Examples of R'or R'' include independent groups similar to R (excluding heterocyclic groups).
  • Examples of the alkoxycarbonyl group as a substituent of R or R 1 to R n include a methoxycarbonyl group.
  • Examples of the carbamoyl group as a substituent of R or R 1 to R n include an N-methylcarbamoyl group and an N, N-dimethylcarbamoyl group.
  • Examples of the amide group as a substituent of R or R 1 to R n include a dimethylamide group.
  • Examples of the halogen atom as a substituent of R or R 1 to R n include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkoxy group as the substituent of R or R 1 to R n include an alkoxy group having 1 to 12 carbon atoms. Specific examples include a methoxy group.
  • Examples of the group exhibiting hydrophilicity or ionicity as a substituent of R or R 1 to R n include an alkali salt of a carboxy group or an alkali salt of a sulfoxyl group, a polyethylene oxide group, a poly (alkylene oxide) such as a polypropylene oxide group. ) Groups and cationic substituents such as quaternary ammonium bases.
  • R and R 1 to R n are preferably at least one selected from an alkyl group and a cycloalkyl group, and more preferably an alkyl group.
  • an alkyl group a methyl group, an ethyl group, an n-propyl group or an i-propyl group is preferable, and a methyl group is more preferable from the viewpoint of availability.
  • X 1 to X n in equation (1) [X 1 to X n in equation (1)]
  • X 1 ⁇ X n n from the viewpoint of ease of synthesis of the macromonomer (A), relative to the total mole number 100 mol% of X 1 ⁇ X n, methyl least 80 mol% It is preferably a group.
  • Z is a terminal group of the macromonomer (A).
  • the terminal group of the macromonomer (A) include a group derived from a hydrogen atom and a radical polymerization initiator, similarly to the terminal group of a polymer obtained by known radical polymerization.
  • the lower limit of the content ratio of the MMA unit contained in the macromonomer (A) is not particularly limited, and is 80% by mass or more based on 100% by mass of the total mass of the macromonomer (A).
  • the impact resistance and transparency of the molded product obtained by molding the resin composition (hereinafter, referred to as "the obtained molded product” or simply "molded product") are improved.
  • the lower limit of the content ratio of the MMA unit is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more.
  • the upper limit of the content ratio of the MMA unit is not particularly limited and may be 100% by mass of the MMA unit, or 99 with respect to 100% by mass of the total mass of the macromonomer (A). It can also be mass% or less.
  • the lower limit of the content ratio of the macromonomer (A) unit contained in the copolymer of the present invention is not particularly limited, and the handleability of the copolymer is improved. With respect to the total mass of 100% by mass, 35% by mass or more is preferable, 40% by mass or more is more preferable, 45% by mass or more is further preferable, 50% by mass or more is particularly preferable, and 55% by mass or more is most preferable.
  • the upper limit of the content ratio of the macromonomer (A) unit is not particularly limited, and the amount of the copolymer used can be suppressed and the modifying effect can be obtained with a small amount of addition.
  • the content ratio of the macromonomer (A) unit contained in the copolymer of the present invention may be 35% by mass or more and 75% by mass or less with respect to 100% by mass of the total mass of the copolymer. can. It is more preferably 40% by mass or more and 70% by mass or less, further preferably 45% by mass or more and 70% by mass or less, particularly preferably 50% by mass or more and 65% by mass or less, and most preferably 55% by mass or more and 65% by mass or less.
  • the macromonomer (A) is a repeating unit derived from methacrylate other than the MMA unit in order to adjust the compatibility of the copolymer with the (meth) acrylic polymer (M).
  • it may include "methacrylate unit”).
  • the macromonomer (A) contains a repeating unit derived from acrylate (hereinafter, referred to as "acrylate unit") in order to improve the thermal decomposition property of the copolymer. Can be done. Details of the methacrylate unit and the acrylate unit will be described later.
  • the lower limit of the content ratio of the acrylate unit contained in the macromonomer (A) is such that the heat-resistant decomposition property of the copolymer is good, so that the total mass of the macromonomer (A) is 100% by mass with respect to 100% by mass. 0.5% by mass or more is preferable, 2% by mass or more is more preferable, and 4% by mass or more is further preferable.
  • the upper limit of the content ratio of the acrylate unit is preferably 20% by mass or less with respect to 100% by mass of the total mass of the macromonomer (A) because the heat-resistant decomposition property of the resin composition can be maintained satisfactorily. 10% by mass or less is more preferable, and 5% by mass or less is further preferable.
  • the monomer constituting the methacrylate unit or the acrylate unit is not particularly limited as long as it is a monomer copolymerizable with methyl methacrylate.
  • the above-mentioned "(meth) acrylic polymer” A monomer similar to the monomer described in "M) Comonomer forming a copolymer unit” can be used. These can be used alone or in combination of two or more.
  • the monomer constituting the methacrylate unit n-butyl methacrylate and 2-ethylhexyl methacrylate are more preferable.
  • the monomer constituting the acrylate unit methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferable from the viewpoint of easy availability.
  • the copolymer of the present invention and the (meth) acrylic polymer (M) are mixed to produce the resin composition of the present invention, it is composed of the macromonomer (A) unit in the copolymer.
  • the molecular weight of the polymer chain By adjusting the molecular weight of the polymer chain to such an extent that the polymer chain and the (meth) acrylic polymer (M) are entangled with each other, the impact resistance of the obtained molded product can be further improved.
  • the molecular weight Me between the entangled points of polymethylmethacrylate is known to be about 9,200 g / mol (report by Wu et al .: POLYMER ENGINEERING AND SCIENCE, JUNE 1992, Vol.32, No.12. p823).
  • the lower limit of the mass average molecular weight (Mw) of the macromonomer (A) is such that the polymer chain composed of the macromonomer (A) unit and the (meth) acrylic polymer (M) are entangled, and the copolymer Since the interfacial strength between the polymer (M) and the matrix phase formed by the (meth) acrylic polymer (M) is improved, the impact resistance of the obtained molded product can be improved to 10,000 or more. can do. 12,000 or more is more preferable, 15,000 or more is further preferable, and 20,000 or more is particularly preferable.
  • the upper limit of the mass average molecular weight (Mw) of the macromonomer (A) is such that the copolymerization between the macromonomer (A) and the comonomer (B) becomes good, and the impact resistance of the obtained molded product is maintained well. Since it can be done, it can be set to 1,000,000 or less. 80,000 or less is more preferable, 60,000 or less is further preferable, and 40,000 or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. Alternatively, the mass average molecular weight (Mw) of the macromonomer (A) can be 10,000 or more and 100,000 or less.
  • the mass average molecular weight (Mw) of the macromonomer (A) means the mass average molecular weight which is a relative molecular weight obtained in terms of polymethylmethacrylate (PMMA) by using gel permeation chromatography (GPC). do.
  • the macromonomer (A) in the present invention may be a mixture of two or more types of macromonomers. In that case, the mass average molecular weight Mw is calculated as the value of the entire macromonomer (A).
  • the lower molecular weight macromonomer (A) plays a role of reducing the syrup viscosity and preventing the copolymer from cross-linking, and has a larger molecular weight.
  • the macromonomer (A) is used as an additive, it plays a role of ensuring compatibility with the matrix resin.
  • the raw material monomer for producing the macromonomer (A) in the present invention contains methyl methacrylate as an essential component and contains a monomer copolymerizable with methyl methacrylate as another component.
  • Examples of the monomer copolymerizable with methyl methacrylate include the same monomers as those mentioned in the above-mentioned "Comonomer forming a comonomer unit of (meth) acrylic polymer (M)". Can be used. These can be used alone or in combination of two or more.
  • Acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferred, methyl acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Are more preferred.
  • the copolymer of the present invention which is a product
  • the resin composition of the present invention containing the copolymer, and the resin composition are used.
  • the molded product of the present invention molded by the above-mentioned product contains acrylate in a part from the viewpoint of excellent heat-decomposability.
  • the acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate and t-butyl acrylate. Of these, methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferable in terms of availability.
  • the comonomer (B) is one of the monomer raw materials forming the copolymer (2) of the present invention, and is a monomer having copolymerizability with the macromonomer (A) in the present invention.
  • the copolymer of the present invention has the comonomer (B) unit, the impact resistance of the obtained molded product and the transparency in a wide operating temperature range are improved.
  • the comonomer (B) unit in the present invention includes a repeating unit derived from the acrylate (B1) described later.
  • the acrylate (B1) unit By including the acrylate (B1) unit, the impact resistance of the obtained molded product becomes good. Further, by including the acrylate (B1) unit, when the obtained molded product has a film shape, flexibility is imparted to the film, and the film is less likely to break when repeatedly bent.
  • the comonomer (B) unit in the present invention includes a repeating unit derived from aromatic vinyl (B2) described later (hereinafter, referred to as "aromatic vinyl (B2) unit").
  • aromatic vinyl (B2) unit By including the aromatic vinyl (B2) unit, the refractive index of the polymer chain containing the comonomer (B) unit is changed to the refractive index of the (meth) acrylic copolymer (M) blended with the copolymer. It can be combined, and the obtained polymer has good transparency in a wide operating temperature range.
  • the comonomer (B) in the present invention is a repeating unit derived from methacrylate (B3) described later (hereinafter referred to as “methacrylate (B3) unit”) or another monomer described later (hereinafter referred to as “methacrylate (B3) unit”), if necessary.
  • a repeating unit derived from B4) (hereinafter, referred to as “other monomer (B4) unit”) can be included.
  • the copolymerization reaction mechanism between the macromonomer (A) and the comonomer (B) is described in detail in a report by Yamada et al. (Prog. Polymer. Sci. 31 (2006) p835-877) and the like.
  • the comonomer (B) a monomer having a double bond and having radical polymerization property can be used alone or in combination of two or more.
  • the polymer chain containing the comonomer (B) unit contained in the copolymer can improve the impact resistance of the obtained molded product, so that the glass transition temperature (Tg) is less than 0 ° C. It is preferably ⁇ 20 ° C. or lower, more preferably ⁇ 30 ° C. or lower, and particularly preferably ⁇ 35 ° C. or lower.
  • the Tg of the polymer chain containing the comonomer (B) unit is known as the Tg of the homopolymer of the monomer used as the comonomer (B) in the Polymer Handbook (POLYMER HANDBOOK FOURTH EDITION 2003) and the like. It can be calculated by adopting the numerical values described in the above document and using the Fox formula. Alternatively, the dynamic viscoelasticity of the obtained molded product can be measured and the value of tan ⁇ can be adopted as Tg.
  • the content ratio (unit: mass%) of the comonomer (B) unit contained in the copolymer of the present invention is preferably 25% by mass or more and 65% by mass or less with respect to 100% by mass of the total mass of the copolymer. ..
  • the lower limit of the content ratio of the comonomer (B) is preferably 25% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass or more.
  • the upper limit of the content ratio of the comonomer (B) is 65% by mass or less, the haze of the molded product when the copolymer is blended in the resin composition becomes good.
  • the upper limit of the content ratio of the comonomer (B) is preferably 65% by mass or less, more preferably 60% by mass or less, further preferably 55% by mass or less, particularly preferably 50% by mass or less, and most preferably 45% by mass or less.
  • the comonomer (B) is not particularly limited as long as it can be copolymerized with the macromonomer (A), and various polymerizable monomers can be used as needed. Specifically, acrylate (B1) described later and aromatic vinyl (B2) described later are mainly used in terms of reactivity with the macromonomer (A), formation of a branched structure, and adjustment of the refractive index. Is preferable. Further, if necessary, methacrylate (B3) described later and other monomers (B4) described later can be used.
  • the comonomer (B) contains an acrylate (B1) having good copolymerizability with the macromonomer (A).
  • the impact resistance of the obtained molded product becomes good.
  • the lower limit of the content ratio of the acrylate (B1) contained in the comonomer (B) is preferably 70% by mass or more, more preferably 79% by mass or more, based on 100% by mass of the total mass of the comonomer (B). 81% by mass or more is more preferable.
  • the lower limit of the content ratio of the acrylate (B1) is 70% by mass or more, the reactivity between the macromonomer (A) and the comonomer (B) is ensured, and the ratio of the block polymer or graft polymer contained in the copolymer is increased. Can be sufficiently enhanced.
  • the content ratio of the acrylate (B1) is small, the macromonomer (A) does not react sufficiently and remains unreacted, or the molecular weight of the copolymer of the present invention does not sufficiently increase. The reaction time until the copolymer of the present invention is obtained may become too long.
  • the upper limit of the content ratio of the acrylate (B1) contained in the comonomer (B) is not particularly limited, but is preferably less than 100% by mass, preferably 95% by mass, based on 100% by mass of the total mass of the comonomer (B). The following is more preferable, and 90% by mass or less is further preferable.
  • the glass transition temperature (Tg) of the homopolymer of the acrylate (B1) is less than 0 ° C. preferable.
  • the Tg of the acrylate (B1) homopolymer can be calculated by adopting the numerical values described in known documents such as the Polymer Handbook (POLYMER HANDBOOK FOURTH EDITION 2003) and using the Fox formula. ..
  • Examples of the acrylate (B1) include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and n-lauryl acrylate.
  • Acrylate such as n-stearyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, phenoxyethyl acrylate; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, Hydroxylate-containing acrylates such as 4-hydroxybutyl acrylate and glycerol acrylate; 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxypropyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxypropylphthalic acid, Carboxy group-containing acrylates such as 2-acryloyloxyethyl maleic acid, 2-acryloyloxypropyl maleic acid, 2-acryloyloxyethyl succinic acid, 2-
  • Examples thereof include acrylates, triethylene glycol diacrylates, tetraethylene glycol diacrylates, tripropylene glycol diacrylates, trimethylolpropane triacrylates, allyl acrylates, and polyfunctional acrylates such as N, N'-methylenebisacrylamide. These can be used alone or in combination of two or more.
  • the Tg of the homopolymer is less than 0 ° C.
  • 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, n-butyl acrylate, n-propyl acrylate, ethyl acrylate, 2-hydroxyethyl Acrylate is preferred.
  • the compatibility between the macromonomer (A) and the comonomer (B) is improved and the transparency and impact resistance of the obtained molded product can be improved, methyl acrylate, ethyl acrylate, and n-butyl acrylate can be used. preferable.
  • the comonomer (B) in the present invention contains aromatic vinyl (B2) as an essential component.
  • the present inventors have combined acrylate (B1) and aromatic vinyl (B2) to optimize the conditions of the polymerization reaction, so that the copolymerization with the macromonomer (A) is good. We found that it progressed at a speed. Further, by adjusting the composition ratio of the acrylate (B1) and the aromatic vinyl (B2), a polymer chain composed of a macromonomer (A), a (meth) acrylic polymer (M), and a comonomer (B) can be obtained. It became possible to match the refractive indexes of. As a result, the molded product made of the resin composition has good transparency in a wide operating temperature range.
  • the copolymer is crosslinked when the polymerizable composition (X) is polymerized to obtain a copolymer.
  • aromatic vinyl (B2) it is necessary to prevent cross-linking of the copolymer by the chain transfer effect of the macromonomer (A), and it is necessary to use a low molecular weight macromonomer (A) in order to increase the mol% of the macromonomer (A) to be used. there were. Therefore, by using aromatic vinyl (B2), it has become possible to use a higher molecular weight macromonomer (A). It has been found that by using a higher molecular weight macromonomer (A), the molded product using the resin composition is further improved in transparency in a wide temperature range.
  • the content ratio of the aromatic vinyl (B2) contained in the comonomer (B) is preferably 10 to 30% by mass, more preferably 13 to 21% by mass, based on 100% by mass of the total mass of the comonomer (B). It is preferable, and 15 to 19% by mass is more preferable.
  • the content ratio of the aromatic vinyl (B1) contained in the comonomer (B) is 10% by mass or more, the macromonomer (A) having a large molecular weight can be used, and a molded product using the resin composition. However, good transparency can be exhibited in a wide temperature range.
  • the content ratio of the aromatic vinyl (B1) contained in the comonomer (B) is 30% by mass or less, the polymerization reaction rate of the polymerizable composition (X) becomes sufficiently high.
  • aromatic vinyl (B2) examples include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene and pt-butylstyrene, vinylethylbenzene and vinyltoluene. , Vinylxylene, vinylnaphthalene, diphenylethylene, divinylbenzene and the like. Among these, styrene is preferable from the viewpoint of practical physical properties and productivity. These can be used alone or in combination of two or more.
  • the comonomer (B) of the present invention can contain a methacrylate (B3) having good copolymerizability with the macromonomer (A) and the aromatic vinyl (B2).
  • the methacrylate (B3) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate.
  • Epyl group-containing methacrylate such as butyl methacrylate
  • Amino group-containing methacrylate such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate
  • Polyfunctional methacrylates such as dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylpropantrimethacrylate, and allyl methacrylate; and the like can be mentioned. One or more of these can be appropriately selected and used.
  • methacrylate (B3) suppresses the copolymerization reaction between the macromonomer (A) and the comonomer (B) and hinders the formation of branched products, it is preferable that the amount used is small.
  • the content of methacrylate (B3) is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and may not be used with respect to the total 100% by mass of the comonomer (B).
  • the comonomer (B) of the present invention may contain, if necessary, another monomer (B4) having good copolymerizability with the macromonomer (A) and the aromatic vinyl (B2).
  • the other monomer (B4) include carboxy group-containing vinyl monomers such as (meth) acrylate, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, and monomethyl itacone; maleic anhydride.
  • An acid anhydride group-containing vinyl monomer such as itaconic anhydride; (meth) acrylamide, Nt-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N -Vinyl-based monomers containing amide groups such as butoxymethyl (meth) acrylamide, diacetoneacrylamide, maleic acid amide, and maleimide; vinyl-based monomers such as (meth) acrylonitrile, vinyl chloride, vinyl acetate, and vinyl propionate. Body; etc. One or more of these can be appropriately selected and used.
  • the content of the other monomer (B4) is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and not used with respect to the total 100% by mass of the comonomer (B). Is also good.
  • the macromonomer (A) in the present invention can be produced by a known method.
  • a method for producing the macromonomer (A) for example, a method for producing the macromonomer (A) using a cobalt chain transfer agent (US Pat. No. 4,680,352), or an ⁇ -substituted unsaturated compound such as ⁇ -bromomethylstyrene is used as the chain transfer agent.
  • Method International Publication No. 88/04304
  • method for chemically bonding polymerizable groups Japanese Patent Laid-Open No. 60-133007, US Pat. No.
  • Examples of the method for producing the macromonomer (A) using the cobalt chain transfer agent include a massive polymerization method, a solution polymerization method, and an aqueous dispersion polymerization method such as a suspension polymerization method and an emulsion polymerization method.
  • the aqueous dispersion polymerization method is preferable, and the suspension polymerization method is particularly preferable, from the viewpoint of simplifying the recovery step of the macromonomer (A).
  • the solution polymerization method it is also possible to obtain the copolymer of the present invention by a copolymerization reaction by adding the comonomer (B) and the thermal polymerization initiator as they are without recovering the macromonomer (A). be.
  • the cobalt chain transfer agent used in the present invention represented by the following general formula (2) can be used.
  • 35411 Public Relations US Patent No. 45269945, No. 4694054, No. 48334326, No. 4886861, No. 5324879, International Publication No. 95/17435, Special Table Those described in the public relations, etc. of Heisei 9-510499 can be used.
  • R 1 to R 4 are independent alkyl groups, cycloalkyl groups and aryl groups, respectively; X is independently F atom, Cl atom, Br atom, OH group and alkoxy. Groups, aryloxy groups, alkyl groups and aryl groups. ]
  • the method for producing a copolymer of the present invention includes a step of polymerizing a polymerizable mixture containing the polymerizable composition (X) described later and a polymerization initiator.
  • the polymerizable composition (X) contains a macromonomer (A) represented by the following general formula (1) and a comonomer (B) copolymerizable with the macromonomer (A).
  • the comonomer (B) contains an acrylate (B1) and an aromatic vinyl (B2).
  • the comonomer (B) can contain methacrylate (B3) and other monomers (B4), if necessary.
  • R and R 1 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 indicates a terminal group.
  • n represents a natural number from 2 to 10,000.
  • the polymerization reaction is carried out by using a radical polymerization method.
  • the radical polymerization method include a bulk polymerization method such as a bulk polymerization method and a cast polymerization method, a solution polymerization method, and an aqueous dispersion polymerization method such as a suspension polymerization method and an emulsion polymerization method. Since the recovery step of the copolymer can be simplified, an aqueous dispersion polymerization method such as a suspension polymerization method and an emulsion polymerization method is preferable, and the suspension polymerization method is preferable because the obtained polymer particles are easy to handle. More preferred.
  • the copolymer is obtained as spherical particles having an average particle diameter of about 5 ⁇ m to 1 mm.
  • the obtained spherical particles have good handleability and are suitable as a resin composition because there is little concern about dust scattering when used in processing operations such as extrusion and molding. Further, it is preferable because the moldability of the resin composition obtained by the suspension polymerization method is improved. The reason is not clear, but it is speculated that the suspension polymerization method is superior to the emulsion polymerization method as a result of the trace amount of abnormal polymer produced by emulsion polymerization and the remaining emulsifier causing foreign matter and thickening. Will be done. Details of the suspension polymerization method will be described later.
  • the polymerization reaction is carried out by using a bulk polymerization method such as a bulk polymerization method or a cast polymerization method, and can include a step of heating and polymerizing the polymerizable mixture.
  • a bulk polymerization method such as a bulk polymerization method or a cast polymerization method
  • the macromonomer (A) is produced by solution polymerization, and the comonomer (B) and the thermal polymerization initiator are added to the solution as it is and a copolymerization reaction is carried out to carry out the copolymerization reaction of the present invention. It is also possible to obtain coalescence.
  • the upper limit of the content of the sulfur-containing chain transfer agent contained in the polymerizable mixture is less than 0.01 parts by mass with respect to 100 parts by mass of the polymerizable composition (X). Is preferable.
  • the upper limit of the content of the sulfur-containing chain transfer agent is less than 0.01 parts by mass, it is possible to suppress the widening of the composition distribution of the copolymer, so that 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, and it is more preferable that the sulfur-containing chain transfer agent is not contained.
  • the sulfur-containing chain transfer agent 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 obtained copolymer can be polymerized so that the mass average molecular weight (Mw) of the obtained copolymer is 240,000 or more and 3,500,000 or less.
  • the lower limit of the mass average molecular weight (Mw) of the copolymer is preferably 240,000 or more, more preferably 300,000 or more, and 600, for the same reason as described in the section of the copolymer of the present invention. More than 000 is more preferable.
  • the upper limit of Mw of the copolymer is preferably 3.5 million or less, more preferably 3,000,000 or less, for the same reason as described in the section of the copolymer of the present invention.
  • the above upper limit value and lower limit value can be arbitrarily combined.
  • the method for controlling the mass average molecular weight (Mw) of the copolymer to 240,000 or more is not particularly limited. It can be controlled by adjusting the addition amount of the above, the polymerization temperature, and the like.
  • the polymerizable composition (X) is one of the raw materials for the resin composition of the present invention.
  • the content ratio (A, unit: mass%) of the macromonomer (A) and the content ratio (B, unit: mass%) of the comonomer (B) contained in the polymerizable composition (X) are the above-mentioned polymerizable composition (A, unit: mass%).
  • A: B 35 to 75% by mass: 65 to 25% by mass is preferable
  • the content ratio (A, unit: mass%) of the macromonomer (A) and the content ratio (B, unit: mass%) of the comonomer (B) contained in the polymerizable composition (X) are the above-mentioned polymerizable composition (B, unit: mass%).
  • the lower limit of the content ratio of the macromonomer (A) contained in the polymerizable composition (X) is 35% by mass or more or 35% by mass or more of the comonomer (B) with respect to the total mass of 100% by mass of the polymerizable composition (X).
  • the content ratio is 65% by mass or less, the handleability of the copolymer is good.
  • the lower limit of the content ratio of the comonomer (B) contained in the polymerizable composition (X) is 25% by mass or more or macromonomer (A) with respect to the total mass of 100% by mass of the polymerizable composition (X). ) Is 75% by mass or less, the impact resistance of the resin composition containing the copolymer and the obtained molded product can be satisfactorily maintained.
  • the macromonomer (A) in the present invention includes the following steps i) to v).
  • the production and the method for producing the copolymer of the present invention are separately performed, and among the steps i) to v) below, the steps I) to II) below are included instead of the steps i) to ii) below.
  • the method of continuously producing the macromonomer (A) in the present invention and the copolymer of the present invention can be mentioned.
  • Syrup preparation step A syrup prepared by dissolving a beaded macromonomer (A) produced by suspension polymerization in a solution containing a comonomer (B) is used as a polymerizable composition (X).
  • the mixture containing the macromonomer (A) and the comonomer (B) is heated at a temperature equal to or lower than the boiling point of the comonomer (B) to dissolve the macromonomer (A).
  • 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.
  • the radical polymerization initiator used does not react at the temperature at which the polymerizable composition (X) is prepared, the radical polymerization initiator is mixed with the polymerizable composition (X) to obtain a polymerizable mixture. After that, the polymerizable mixture can be heated.
  • ii) Radical polymerization initiator dissolution step When 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 lower. After that, a 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 not more than a temperature obtained by subtracting 15 ° C. from the 10-hour half-life temperature of the radical polymerization initiator.
  • Step of preparing an aqueous solution The polymerizable mixture and the aqueous solution are mixed and then stirred to prepare a suspension in which droplets of the polymerizable mixture are dispersed in the aqueous solution.
  • the aqueous solution is an aqueous solution for dispersing the polymerizable mixture, and may contain a dispersant, an electrolyte, and other auxiliaries. By appropriately selecting the combination of the dispersant and the electrolyte, the dispersibility of the droplets of the polymerizable mixture formed in the aqueous solution when the polymerizable mixture is dispersed in the aqueous solution can be controlled.
  • deionized water is preferably used because the dispersibility of the droplets of the polymerizable mixture is good.
  • the dispersant 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, and an alkali metal salt of sulfoalkyl (meth) acrylic acid.
  • acrylic acid ester copolymer polystyrene sulfonic acid alkali metal salt, styrene sulfonic acid alkali metal salt and (meth) acrylic acid ester copolymer, or a combination of these monomers.
  • Coalescence Polyvinyl alcohol, methyl cellulose, starch and hydroxyapatite having a saponification degree of 70 to 100% can be mentioned. These can be used alone or in combination of two or more. Among these, a copolymer of an alkali metal salt of sulfoalkyl (meth) acrylate and an alkali metal ester of (meth) acrylic acid having good dispersion stability during suspension polymerization, and an alkali metal salt of (meth) acrylate and (meth). ) A copolymer of acrylic acid ester is preferable.
  • the amount of the dispersant added is, 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, manganese sulfate and the like.
  • the amount of the electrolyte added is, for example, in the range of 0.01 to 1.0 parts by mass with respect to 100 parts by mass of the polymerizable composition (X).
  • the macromonomer (A) on the beads produced by suspension polymerization is dispersed in an aqueous solution, and a solution containing the comonomer (B) is added to the polymerizable composition (X). To prepare.
  • the temperature at which the macromonomer (A) is dissolved in the solution containing the comonomer (B) is preferably in the range of 20 ° C to 100 ° C, more preferably in the range of 40 ° C to 90 ° C, and in the range of 50 ° C to 80 ° C. Is even more preferable.
  • 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 lower. After that, a 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 not more than a temperature obtained by subtracting 15 ° C. from the 10-hour half-life temperature of the radical polymerization initiator.
  • the polymerization temperature at the time of carrying out the polymerization reaction is an important condition for obtaining the copolymer (block / graft copolymer) of the present invention in a 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.
  • the temperature of the suspension can be raised for the purpose of increasing the reaction rate of the polymerizable composition (X) and eliminating the unreacted radical polymerization initiator.
  • the temperature for raising the temperature of the suspension is preferably 80 ° C. or higher, more preferably 85 ° C. or higher.
  • the temperature rising time may be determined by calculating the time until the radical polymerization initiator disappears, and is usually about 30 minutes to 2 hours.
  • the suspension is cooled to room temperature or lower, and then the produced beaded copolymer is recovered by using a known method such as filtration. If necessary, a cleaning step for removing impurities such as a dispersant and an electrolyte, a step for removing beads mixed with air bubbles, a drying step, and the like can be performed.
  • the finally obtained bead-shaped copolymer (block / graft copolymer) is used as the copolymer of the present invention.
  • the radical polymerization initiator When the polymerization reaction is carried out in the presence of a radical polymerization initiator, the radical polymerization initiator includes known organic peroxides such as 2,4-dichlorobenzoyl peroxide and t-butylperoxypivalate, and 2,2. Known azo compounds such as'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) can be used.
  • the amount of the radical polymerization initiator to be blended can be appropriately selected by those skilled in the art according to a well-known technique. The usual blending amount is 0.0001 to 10 parts by mass of the radical polymerization initiator with respect to 100 parts by mass of the total amount of the polymerizable composition (X).
  • the other component (Q) is added to the resin composition as needed.
  • Other components (Q) include, for example, mold release agents, antioxidants, heat stabilizers, impact resistance improvers, flexibility imparting agents, weather resistance improvers, colorants, inorganic pigments, organic pigments, and carbon black.
  • Ferrites conductivity-imparting agents, UV absorbers, infrared absorbers, lubricants, inorganic fillers, strengthening agents, plasticizers, reverse plasticizers, neutralizers, cross-linking agents, flame retardants, preservatives, insect repellents, fragrances , Radical catching agent, sound absorbing material, core shell rubber, etc.
  • the molded product of the present invention can be obtained by molding pellets of the resin composition of the present invention by a known melt molding method such as extrusion molding, injection molding, compression molding, or hollow molding.
  • the shape of the molded product of the present invention is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, a substantially box shape, and a three-dimensional shape having a curved surface portion. Since the molded body of the present invention is excellent in impact resistance and transparency in a wide operating temperature range, display front panels such as liquid crystals and organic EL, signboard supplies, lighting supplies, home appliances, vehicle interior / exterior materials.
  • the film-shaped molded product of the present invention is not only excellent in impact resistance and transparency in a wide operating temperature range, but also is less likely to cause whitening when the film-shaped molded product is bent. In addition, the film-shaped molded product of the present invention is less likely to break when repeatedly bent, and thus can be suitably used for a foldable display or the like.
  • the molded article of the present invention preferably has a Charpy impact strength (without notch) of 30 kJ / m 2 or more and 100 kJ / m 2 or less, and preferably 50 kJ / m 2 or more and 100 kJ / m 2 or less.
  • the molded product of the present invention preferably has a flexural modulus of 1500 MPa or more and 5000 MPa or less, and more preferably 2000 MPa or more and 3000 MPa or less.
  • the molded product of the present invention preferably has an MFR of 2.0 g / 10 minutes or more and 50 g / 10 minutes or less, and more preferably an MFR of 15 g / 10 minutes or more and 40 g / 10 minutes or less.
  • the molded product of the present invention preferably has a haze value of less than 15%, preferably 10% or less, more preferably 5% or less, and further preferably 2% or less at room temperature of 23 ° C. preferable.
  • the molded product of the present invention preferably has a haze value of less than 15%, preferably 10% or less, and more preferably 5% or less at room temperature of 80 ° C.
  • the film-shaped molded article of the present invention of the present invention preferably has an elastic modulus of 1000 to 5000 MPa, more preferably 1500 to 3000 MPa.
  • the film-shaped molded product of the present invention preferably has a maximum point strength of 30 to 90 MPa, more preferably 40 to 80 MPa.
  • the film-shaped molded product of the present invention preferably has a breaking elongation of 1 to 30%, more preferably 2 to 20%.
  • Mass average molecular weight (Mw) and number average molecular weight (Mn) of macromonomer (A) The mass average molecular weight (Mw) and number average molecular weight (Mn) of the macromonomers (A) obtained in Examples and Comparative Examples were measured by 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.
  • the measurement was carried out under the conditions of a separation column temperature: 40 ° C., a moving layer: tetrahydrofuran, a flow rate of the moving layer: 0.6 mL / min, and a sample injection amount: 10 ⁇ l.
  • a calibration curve was prepared using several types of polymethylmethacrylates having known molecular weights (manufactured by Polymer Laboratories, peak molecular weight (Mp) 1,560 to 19,500,000) as standard polymers, and Mw and Mn were determined.
  • Mass average molecular weight (Mw) and number average molecular weight (Mn) of copolymer The mass average molecular weight (Mw) and number average molecular weight (Mn) of the copolymers obtained in Examples and Comparative Examples were measured by 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.
  • a high-performance liquid chromatography measuring device manufactured by Tosoh Corporation, model name: HLC-8320 type
  • a polymer measurement guard column manufactured by Tosoh Co., Ltd., trade name: TSK-GUARD COLUMN SUPER H
  • -H high-performance liquid chromatography measuring device
  • TSK-GUARD COLUMN SUPER H polymer measurement guard column
  • TSK-GEL GMHHR-H ultrapolymer measurement column
  • the measurement was carried out under the conditions of a separation column temperature: 40 ° C., a moving layer: tetrahydrofuran, a flow rate of the moving layer: 0.6 mL / min, and a sample injection amount: 10 ⁇ l.
  • a calibration curve was prepared using several types of polymethylmethacrylate known molecular weights (manufactured by Polymer Laboratories, peak molecular weight (Mp) 1,560 to 19,500,000) as standard polymers, and the mass average molecular weight, which is the relative molecular weight in terms of polymethylmethacrylate. (Mw) and number average molecular weight (Mn) were determined.
  • a plate-shaped molded body (width 50 mm, length 100 mm, thickness 3 mm) and a rod-shaped molded body (width 8 mm, length 80 mm, thickness 4 mm) were obtained. These molded products were used as test pieces for evaluation.
  • Charpy impact strength is 50 kJ / m 2 or more
  • melt flow rate (unit: g / 10 minutes) measured under the conditions of a temperature of 230 ° C. and a load of 37.3 N was measured.
  • the heating time of the resin composition was 4 minutes, and the sample cutting time interval was 10 seconds to 120 seconds depending on the MFR value of the sample.
  • a three-stage evaluation was performed according to the following criteria. AA: MFR is 15 g / 10 minutes or more A: MFR is 2.0 g / 10 minutes or more and less than 15 g / 10 minutes B: MFR is 2.0 g / 10 minutes or less
  • Haze evaluation As an index of the transparency of the molded product obtained in Examples and Comparative Examples, a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., device name: NDH2020) was used to obtain the plate-shaped molded product in accordance with JIS K7316. The haze (unit:%) of the test piece was measured at room temperature of 23 ° C. and 80 ° C. ° C. In the measurement at 80 ° C., the plate-shaped molded product was allowed to stand in an environment of 80 ° C. for 1 hour, and then the measurement was carried out promptly. A three-stage evaluation was performed according to the following criteria. AA: Haze is less than 10% A: Haze is 10% or more and less than 15% B: Haze is 15% or more
  • Glass transition temperature of copolymer comonomer homopolymer The glass transition temperature (Tg) of the comonomer homopolymer of the copolymer was calculated from the Tg of the comonomer homopolymer using the Fox formula.
  • Tg value of the homopolymer of the comonomer the literature value described in the Polymer Handbook (POLYMER HANDBOOK FOURTH EDITION 2003) was adopted.
  • the obtained film was cut into 150 mm ⁇ 15 mm with the film forming direction as the long side, and used with a Tensilon universal testing machine (manufactured by Orientec Co., Ltd., trade name: RTC-1250A) in accordance with JIS K7127.
  • a tensile test was carried out at a distance between chucks of 100 mm and a tensile speed of 100 mm / min, and the elastic modulus, maximum point strength, and fracture elongation of the film were measured.
  • V-50 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 2,2'-azobis (2-methylpropion amidine) dihydrochloride, trade name
  • the temperature of the liquid in the reactor was raised to 60 ° C.
  • 1.4 parts of MMA was added in portions every 15 minutes 5 times in total (7 parts in total of MMA).
  • the liquid in the polymerization apparatus was held at 60 ° C. for 6 hours with stirring, and then cooled to room temperature to obtain a dispersant (1) having a solid content of 8% by mass, which is a transparent aqueous solution.
  • the inside of the polymerization apparatus was sufficiently replaced with nitrogen, and the aqueous dispersion was heated to 80 ° C. and then held for 3 hours, then heated to 90 ° C. and held for 2 hours. Then, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension of macromonomers.
  • the aqueous suspension was filtered through a filter cloth, the filtrate was washed with deionized water and dried at 40 ° C. for 16 hours to give the macromonomer (A-1).
  • the evaluation results of the obtained macromonomer are shown in Table 1.
  • Example 1 Synthesis of copolymer (1)
  • 40 parts of macromonomer (A-11), 49.8 parts of BA, and 10.2 parts of St were added to a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer to start stirring.
  • the polymerization apparatus was heated with warm water at 65 ° C., and the macromonomer (A-1) was dissolved in BA and St to obtain a uniform syrup.
  • 0.5 part of the polymerization initiator (3) was added and stirred to dissolve.
  • a mixed solution of 150 parts of deionized water, 0.26 part of dispersant (1), and 0.3 part of sodium sulfate was prepared as an aqueous solution, added to the syrup and stirred to obtain a dispersion liquid. Then, the inside of the polymerization apparatus was replaced with nitrogen. The dispersion was heated to 80 ° C. and held for 5 hours, then heated to 90 ° C. and held for 1 hour. After cooling to 40 ° C. or lower, the mixture was filtered through a filter cloth, and the filtered material was washed with deionized water. Then, the filtrate was dried under reduced pressure at 40 ° C. for 12 hours to obtain a bead-shaped copolymer (1).
  • 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 homopolymer (B) unit of the copolymer (1) was -37.5 ° C. when calculated using the Fox formula. Table 2 shows the charged composition and the evaluation results of the obtained bead-shaped copolymer.
  • Example 2 Synthesis of copolymer (2)
  • a bead-shaped copolymer (2) was obtained in the same manner as in Example 1 except that the charged composition was changed to the conditions shown in Table 2.
  • Table 2 shows the charged composition and the evaluation results of the obtained bead-shaped copolymer.
  • Example 3 Synthesis of copolymer (3)
  • the charged composition was changed to the amount shown in Table 1 to obtain an aqueous suspension containing 60 parts by mass of macromonomer (A-2).
  • A-2 macromonomer
  • aqueous dispersion 57 parts of MMA, 3 parts of MA, 0.0015 parts of the chain transfer agent (1) produced in Production Example 2, and 0.15 of the polymerization initiator (1) as a polymerization initiator were added to prepare an aqueous dispersion.
  • the inside of the polymerization apparatus was sufficiently replaced with nitrogen, and the aqueous dispersion was heated to 80 ° C. and then held for 3 hours, then heated to 90 ° C. and held for 2 hours to obtain the macromonomer (A-2). An aqueous suspension was obtained.
  • Example 4 Synthesis of copolymer (4)
  • a bead-shaped copolymer (4) was obtained in the same manner as in Example 1 except that the charged composition was changed to the conditions shown in Table 2.
  • Table 2 shows the charged composition and the evaluation results of the obtained bead-shaped copolymer.
  • Example 9 Synthesis of copolymer (10)] 60 parts of macromonomer (A-7) obtained in Production Example 9, 150 parts of deionized water, 0.26 part of dispersant (1), sodium sulfate in a polymerization apparatus equipped with a stirrer, a cooling tube and a thermometer. 0.3 part was added and stirred to obtain an aqueous suspension. Next, the temperature inside the polymerization apparatus was raised to 70 ° C., and then 33.2 parts of BA and 6.8 parts of St were slowly added. Then, the mixture was kept at 70 ° C. for 1 hour with stirring to dissolve the macromonomer (A-7) in BA and St to obtain a dispersion liquid.
  • Example 10 Synthesis of copolymer (11)
  • a bead-shaped copolymer (11) was obtained in the same manner as in Example 9 except that the charging composition was changed to the conditions shown in Table 2.
  • Table 2 shows the charged composition and the evaluation results of the obtained bead-shaped copolymer.
  • the obtained polymer solution was diluted with toluene so as to have a solid content concentration of 10% by mass, and the solution was added dropwise to methanol in an amount 10 times the diluted polymer solution to form a precipitate.
  • the obtained precipitate was recovered and dried to obtain a copolymer (7).
  • Table 3 shows the charged composition and the evaluation results of the obtained bead-shaped copolymer.
  • the solid content concentration of the obtained latex was 40.8% by mass, and the volume average particle size measured by a laser diffraction / scattering type particle size distribution meter (LA-960S, manufactured by Horiba, Ltd.) was 96 nm.
  • the Mn measured by GPC was 125,200, and the Mw was 3,670,300.
  • the charged composition and evaluation results are shown in Table 3.
  • a 5% aqueous solution of calcium acetate was added to coagulate and recover the copolymer (8) obtained as latex.
  • the copolymer (8) produced a white paste-like high-viscosity liquid precipitate, which could not be recovered. It was difficult to remove the water contained in the highly viscous liquid precipitate, and it was also difficult to handle because it was a liquid.
  • the resin compositions of Examples 5 to 8 and Examples 11 to 12 had good melt moldability. Further, the obtained molded product had good impact resistance and elastic modulus, and had good transparency at room temperature and 80 ° C. That is, as shown in Examples 5 to 8 and Examples 11 to 12, the resin composition of the present invention has an MFR (melt flow rate) of more than 2.0 g / 10 min at a temperature of 230 ° C. and a load of 37.3 N. It has better fluidity than the (meth) acrylic polymer (M1) alone, and is excellent in melt moldability. As a result, the resin composition of the present invention can be subjected to injection molding or extrusion molding to produce a thin molded body or a molded body having a complicated shape.
  • MFR melt flow rate
  • the molded product of the present invention can have a Charpy impact test (without notch) of 30 kJ / m 2 or more and a flexural modulus of 1500 MPa or more.
  • the impact resistance of a molded product tends to decrease as the elastic modulus increases, which is a so-called trade-off relationship. That is, the molded product of the present invention is a molded product having a remarkable characteristic that both impact resistance and elastic modulus, which are contradictory characteristics, are compatible with each other.
  • the molded product of the present invention has excellent transparency with a haze of less than 15% at room temperature (23 ° C.) and 80 ° C., and can be said to be usable as a transparent material in a wide temperature range.
  • the molded product obtained in Comparative Example 6 had insufficient transparency at room temperature and 80 ° C. because the comonomer (B) did not contain aromatic vinyl (B1). Further, since the molecular weight of the macromonomer (A) used for the synthesis of the copolymer (5) was small, the obtained molded product had insufficient impact resistance.
  • the molded product obtained in Comparative Example 7 had insufficient transparency at 80 ° C. because the comonomer (B) did not contain aromatic vinyl (B1). Further, since the comonomer (B) used for the synthesis of the copolymer (6) contains MMA and the Tg of the polymer chain containing the comonomer (B) unit is relatively high, the obtained molded product has impact resistance. Was inadequate.
  • the Tg of the copolymer of methyl methacrylate (MMA) was 105 ° C (POLYMER HANDBOOK FOURTH EDITION 2003), and the Tg of the copolymer of n-butyl acrylate (BA) was -54 ° C (POLYMER HANDBOOK FOURTH EDITION 2003). Therefore, the Tg of the polymer chain containing the comonomer (B) unit of the copolymer (6) calculated from the FOX formula is ⁇ 9.7 ° C.
  • the molded product obtained in Comparative Example 8 had insufficient transparency at 80 ° C. because the comonomer (B) did not contain aromatic vinyl (B1). Further, since the molecular weight of the copolymer (7) is low, the obtained molded product has insufficient impact resistance.
  • the resin composition of Comparative Example 9 had insufficient melt moldability. Further, the obtained molded product had good impact resistance and elastic modulus, but was insufficiently transparent at 80 ° C. because it did not contain the copolymer of the present invention.
  • the resin composition of Reference Example 1 had lower melt moldability as compared with Examples 5 to 8. Further, the obtained molded product had lower impact resistance as compared with Examples 5 to 8.
  • Example 13 to 14 A film was formed using a resin composition in which the (meth) acrylic polymer (M1) and the copolymer (11) were blended as shown in Table 6. Specifically, the resin composition was plasticized with a 40 mm ⁇ extruder in which the cylinder temperature was set to 240 ° C. Next, a film having a thickness of 50 ⁇ m was formed with a T-die set at 240 ° C. The obtained film had no unevenness on the surface and had a good appearance quality. Furthermore, the creases did not whiten when the film was bent. The tensile test results of the film are shown in Table 6.
  • Examples 15 to 16 Similar to Examples 5 to 8, melt-kneading with a twin-screw extruder except that the (meth) acrylic polymer (M1) and the copolymer (10) were blended as shown in Table 6 to form pellets. A resin composition was obtained. Then, a film having a thickness of 50 ⁇ m was obtained in the same manner as in Examples 13 to 14. The obtained film had no unevenness on the surface and had a good appearance quality. Furthermore, the creases did not whiten when the film was bent. The tensile test results of the film are shown in Table 6.
  • the resin composition of the present invention contains the copolymer of the present invention as a constituent component, it is excellent in melt moldability. Further, since the molded product of the present invention is formed by molding the resin composition, it is excellent in impact resistance and transparency in a wide operating temperature range.

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