WO2023136275A1 - (meth)acrylic resin composition and molded article using same, and method for producing (meth)acrylic resin composition - Google Patents

(meth)acrylic resin composition and molded article using same, and method for producing (meth)acrylic resin composition Download PDF

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WO2023136275A1
WO2023136275A1 PCT/JP2023/000535 JP2023000535W WO2023136275A1 WO 2023136275 A1 WO2023136275 A1 WO 2023136275A1 JP 2023000535 W JP2023000535 W JP 2023000535W WO 2023136275 A1 WO2023136275 A1 WO 2023136275A1
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meth
resin composition
acrylic resin
acrylic
mass
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PCT/JP2023/000535
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French (fr)
Japanese (ja)
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彩 阿部
倫明 北村
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株式会社日本触媒
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C08F8/16—Lactonisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a (meth)acrylic resin composition, a molded article using the same, and a method for producing a (meth)acrylic resin composition.
  • (Meth)acrylic resins are suitable for use in optical members because they have an excellent balance of properties such as optical properties, mechanical strength, molding processability, and surface hardness.
  • (meth)acrylic resins generally have a low glass transition temperature (Tg) and are not excellent in heat resistance. Therefore, in order to improve the heat resistance of (meth)acrylic resins, there are known (meth)acrylic resins in which a ring structure such as a lactone ring structure is introduced into the main chain.
  • Patent Documents 1 and 2 As a method for producing a (meth)acrylic resin having a lactone ring structure, for example, a polymer having a hydroxy group and an ester group in the molecular chain is condensed and cyclized by heating using an organic phosphorus compound as a catalyst. A method of forming a lactone ring structure in a molecular chain has been proposed (Patent Documents 1 and 2).
  • the specifically used catalysts are methyl phosphate and phenyl phosphonous acid.
  • Patent Document 2 the specifically used catalyst is stearyl phosphate.
  • Methyl phosphate and the like specifically used in Patent Document 1 had low cyclization efficiency. Therefore, it was necessary to use a large amount of catalyst in order to form a desired ratio of ring structures in the polymer.
  • a large amount of catalyst is used, there is a risk that a large amount of components (compounds containing phosphorus atoms) derived from the catalyst may remain in the resulting (meth)acrylic resin composition.
  • Phosphorus atoms are corrosive, so there was concern about the stability of (meth)acrylic resins.
  • the amount of catalyst is reduced, there is a possibility that silver streaks may occur in the (meth)acrylic resin composition.
  • Patent Document 2 discloses controlling the content of elemental phosphorus and a hindered phenol compound having a molecular weight of less than 300 in a resin composition, that is, controlling the amount of a phosphorus-based antioxidant having a hindered phenol site ( It was studied to suppress the contamination of the roll surface by not adding excessively. However, even if the amount of the phosphorus antioxidant having a hindered phenol moiety is suppressed, there is still a contamination source on the roll surface, and stearyl phosphate is used in the specific example, so contamination of the roll surface is suppressed. was thought to have limits.
  • the present invention has been made in view of the above circumstances, and its object is to reduce roll contamination, further suppress the generation of silver streaks, and provide a (meth)acrylic (meth)acrylic roll with excellent stability.
  • An object of the present invention is to provide a resin composition.
  • Another object of the present invention is to provide a molded article using the (meth)acrylic resin composition and a method for producing the (meth)acrylic resin composition.
  • the present inventors found that the contamination was caused by the adhesion of stearyl phosphate used as a cyclization catalyst or a component derived therefrom (stearyl alcohol, etc.) to the surface of the roll.
  • stearyl alcohol a component derived therefrom
  • the cyclization step In the catalyst is stable, the amount of catalyst used can be reduced, the generation of silver streaks is suppressed, and a (meth)acrylic resin composition with excellent stability can be obtained.
  • the catalyst When an ester obtained from phosphorous acid or the like and a lower or intermediate aliphatic alcohol is used as a cyclization catalyst, the catalyst is easily volatilized and removed in the devolatilization process, and furthermore, the lower or intermediate aliphatic alcohol generated by decomposition Since the alcohol is also removed in the devolatilization step, the inventors have found that the contamination of the rolls by the cyclization catalyst can be reduced, and completed the present invention. That is, the present invention is specified by the following constituent requirements.
  • a (meth)acrylic resin composition comprising a (meth)acrylic polymer having a ring structure that is at least one of a lactone ring structure and a glutaric anhydride structure in the main chain,
  • the content of phosphorus atoms in the (meth)acrylic resin composition is 1.0 ppm or more and 50 ppm or less
  • R 1 represents an aliphatic hydrocarbon group having 13 or more carbon atoms or an aromatic hydrocarbon group having 6 or more carbon atoms.
  • a method for producing a (meth)acrylic resin composition comprising a cyclization step of forming, (i) a cyclization reaction to form a lactone ring structure between a hydroxy group and an ester group or a carboxyl group; (ii) a glutaric anhydride structure between a carboxyl group and an ester group or another carboxyl group; Cyclization reaction to form In the cyclization reaction, at least one selected from the group consisting of C 3-12 alkyl phosphate, C 3-12 alkyl phosphite, and C 3-12 hypophosphite As a catalyst, a method for producing a (meth)acrylic resin composition.
  • the catalyst used in the cyclization reaction is selected from the group consisting of C 3-7 alkyl phosphate, C 3-7 alkyl phosphite and C 3-7 hypophosphite.
  • a method for producing a (meth)acrylic resin composition is selected from the group consisting of C 3-7 alkyl phosphate, C 3-7 alkyl phosphite and C 3-7 hypophosphite.
  • a method for producing an acrylic resin composition [14] The method for producing a (meth)acrylic resin composition according to any one of [10] to [13], wherein the decomposition temperature of the catalyst is 160°C or higher.
  • an additive is added in one or more steps selected from the polymerization step, the cyclization step, and a step after the cyclization step;
  • the (meth)acrylic resin composition of the present invention contains a (meth)acrylic polymer having a ring structure that is at least one of a lactone ring structure and a glutaric anhydride structure in the main chain. , the content of phosphorus atoms in the composition is 1.0 ppm or more and 50 ppm or less, and the content of the compound represented by the following formula (I) in the composition is 95 ppm or less. . Since the (meth)acrylic resin composition of the present invention has the above constituent elements, it is possible to reduce roll contamination, suppress the generation of silver streaks, and have excellent stability.
  • R 1 represents an aliphatic hydrocarbon group having 13 or more carbon atoms or an aromatic hydrocarbon group having 6 or more carbon atoms.
  • ppm means a value calculated in terms of mass (for example, 10,000 ppm corresponds to 1% by mass).
  • C3-12 means “3 or more and 12 or less carbon atoms.”
  • the (meth)acrylic polymer is (meth)acrylic acid, (meth)acrylic acid ester, or derivatives thereof (hereinafter collectively referred to as (meth)acrylic monomer (sometimes referred to as ) as a monomer unit (that is, a structural unit).
  • (meth)acrylic acid includes both acrylic acid and methacrylic acid.
  • Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, t-(meth)acrylate, Alkyl (meth)acrylates such as butyl, n-hexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate (preferably C 2- methacrylate); 20 aralkyl); (meth)acrylic acid such as cyclohexyl (meth)acrylate and dicyclopentanyl (meth)acrylate and hydroxy cyclic saturated hydrocarbon (preferably hydroxy cyclic saturated hydrocarbon having 5 to 20 carbon atoms) and the like.
  • the (meth)acrylic acid ester is preferably a methacrylic acid ester, more preferably an alkyl methacrylate, still more preferably a C 1-10 alkyl methacrylate, still more preferably a C 1-7 alkyl methacrylate and more preferably C 1-4 alkyl methacrylate, particularly preferably C 1-2 alkyl methacrylate.
  • (Meth)acrylic acid ester derivatives include hydroxy group-introduced derivatives such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3,4,5 (meth)acrylate, Hydroxyalkyl (meth)acrylates such as 6-pentahydroxyhexyl and 2,3,4,5-tetrahydroxypentyl (meth)acrylate; and ⁇ -(1-hydroxyalkyl)alkyl acrylates.
  • the hydroxyalkyl (meth)acrylate is preferably hydroxyC 1-20 alkyl (meth)acrylate, more preferably hydroxyC 1-15 alkyl (meth)acrylate, and hydroxyC 1-10 alkyl (meth)acrylate. is more preferred, and hydroxy C 1-5 alkyl (meth)acrylate is even more preferred.
  • the alkyl ⁇ -(1-hydroxyalkyl) acrylate is preferably C 1-20 alkyl ⁇ -(1 - hydroxyC 1-20 alkyl) acrylate, and ⁇ -(1-hydroxyC 1-20 alkyl) acrylate.
  • C 1-20 alkyl includes methyl ⁇ -(hydroxymethyl)acrylate, ethyl ⁇ -(hydroxymethyl)acrylate, isopropyl ⁇ -(hydroxymethyl)acrylate, n-butyl ⁇ -(hydroxymethyl)acrylate, C 1-20 alkyl ⁇ -(hydroxymethyl)acrylate such as t-butyl ⁇ -(hydroxymethyl)acrylate; ⁇ -(1-hydroxyC 2-20 alkyl such as methyl ⁇ -(1-hydroxyethyl)acrylate alkyl) C 1-20 alkyl acrylates and the like are included.
  • (Meth)acrylic acid ester derivatives include ⁇ -C 1-10 alkyl acrylate such as methyl crotonate; halogens such as chloromethyl (meth)acrylate and 2-chloroethyl (meth)acrylate; Introduced derivatives: Also included are ether bond-introduced derivatives such as dicyclopentanyloxyethyl (meth)acrylate.
  • the (meth)acrylic acid ester derivative is preferably a hydroxy group-introduced derivative, more preferably ⁇ -(1-hydroxyalkyl) alkyl acrylate, still more preferably ⁇ -(1-hydroxyC 1-20 alkyl ) C 1-20 alkyl acrylate, more preferably C 1-20 alkyl ⁇ -(hydroxymethyl)acrylate.
  • (Meth)acrylic acid derivatives include compounds obtained by hydrolyzing the ester bond of the methacrylic acid ester derivative, such as crotonic acid, ⁇ -(hydroxymethyl)acrylic acid, 2-(1-hydroxyethyl)acrylic acid, and the like. - hydroxyalkyl acrylic acid and the like.
  • the (meth)acrylic monomer that the (meth)acrylic polymer has as a monomer unit may be used alone or in combination of two or more.
  • (meth)acrylic monomers it preferably contains (meth)acrylic acid or (meth)acrylic acid ester as an essential unit, and more preferably contains (meth)acrylic acid ester (especially methacrylic acid ester) as an essential unit. .
  • the content of the essential unit in the (meth)acrylic polymer is, for example, 30% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, and even more preferably is 70% by mass or more, particularly preferably 75% by mass or more, and is, for example, 100% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.
  • the proportion of (meth)acrylic monomer units in the above content ratio does not include the unit derived from the (meth)acrylic monomer that has become the different unit.
  • the (meth)acrylic polymer may have a structural unit introduced by copolymerizing the (meth)acrylic monomer with another monomer.
  • Such other monomers are not particularly limited as long as they are compounds having a polymerizable double bond. Examples include styrene, vinyltoluene, ⁇ -methylstyrene, ⁇ -hydroxymethylstyrene, ⁇ -hydroxyethylstyrene, and the like.
  • Styrenic monomers nitrogen-containing heterocyclic vinyl compounds such as N-vinylpyrrolidone and N-vinylcarbazole; vinyl nitriles such as acrylonitrile and methacrylonitrile; vinyl alcohols such as methallyl alcohol and allyl alcohol; ethylene, propylene, Olefins such as 4-methyl-1-pentene; Maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, monomethyl maleate, monobutyl maleate, monomethyl itaconate, monobutyl itaconate, etc.
  • nitrogen-containing heterocyclic vinyl compounds such as N-vinylpyrrolidone and N-vinylcarbazole
  • vinyl nitriles such as acrylonitrile and methacrylonitrile
  • vinyl alcohols such as methallyl alcohol and allyl alcohol
  • ethylene, propylene, Olefins such as 4-methyl-1-pentene
  • carboxyl group-containing ethylenic monofunctional monomer vinyl acetate; 2-hydroxymethyl-1-butene; methyl vinyl ketone;
  • styrene-based monomers, nitrogen-containing heterocyclic vinyl compounds, and carboxyl group-containing ethylenic monofunctional monomers are preferred, styrene-based monomers and carboxyl group-containing ethylenic monofunctional monomers are more preferred, and styrene-based monomers are further preferred. preferable.
  • These other monomers (constituent units) may have only one type or may have two or more types.
  • Other monomers (constituent units) in the (meth)acrylic polymer are, for example, 0% by mass or more, preferably 1% by mass or more, for example, 30% by mass or less, preferably 20% by mass or less, more preferably is 10% by mass or less, more preferably 5% by mass or less.
  • Structural units derived from (meth)acrylic monomers in all structural units of the (meth)acrylic polymer is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and even more preferably 75% by mass or more, from the viewpoint of transparency of the molded article. . There is no particular upper limit, and it may be 100% by mass.
  • the total content of structural units derived from (meth)acrylic monomers in all structural units of the (meth)acrylic polymer having a structure is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably is 60% by mass or more, more preferably 70% by mass or more, particularly preferably 75% by mass or more, preferably 99% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less. Yes, more preferably 85% by mass or less.
  • the total content of structural units derived from a hydroxy group-introduced derivative of a (meth)acrylic acid ester (preferably ⁇ -(1-hydroxyalkyl) alkyl acrylate) in all structural units of the (meth)acrylic polymer is It is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, even more preferably 10% by mass or more, preferably 70% by mass or less, more preferably 50% by mass. % or less, more preferably 30 mass % or less.
  • the total content of structural units derived from a hydroxy group-introduced derivative of a (meth)acrylic acid ester in all structural units of the (meth)acrylic polymer having a structure may be 0% by mass or 10% by mass. The following is preferable, more preferably 8% by mass or less, and even more preferably 5% by mass or less.
  • a (meth)acrylic polymer having a ring structure that is at least one of a lactone ring structure and a glutaric anhydride structure in the main chain is, for example, a (meth)acrylic polymer having a hydroxy group, an ester group, and/or a carboxyl group. In coalescence, it can be formed by performing a cyclization reaction, which will be described later.
  • the lactone ring structure for example, a 4- to 8-membered ring is preferable because the lactone ring structure is easily formed, and a 5- or 6-membered ring is more preferable because the stability of the ring structure is excellent. , is more preferably a 6-membered ring.
  • Examples of the six-membered lactone ring structure include structures represented by the following formula (1).
  • R 1a , R 2a and R 3a are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue contains an oxygen atom. good too.
  • the organic residue in formula (1) include a hydrocarbon group optionally having a substituent and having 1 to 20 carbon atoms.
  • the hydrocarbon group include saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbon groups and aromatic hydrocarbon groups.
  • the aliphatic hydrocarbon group include alkyl groups having 1 to 20 carbon atoms (preferably alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, etc.).
  • an alkyl group having 1 to 6 carbon atoms preferably an alkyl group having 1 to 6 carbon atoms
  • an alkenyl group having 2 to 20 carbon atoms such as an ethenyl group and a propenyl group
  • an alkenyl group having 2 to 10 carbon atoms preferably an alkenyl group having 2 to 10 carbon atoms, more preferably 2 cycloalkyl group having 3 to 20 carbon atoms (preferably a cycloalkyl group having 4 to 12 carbon atoms, more preferably 5 to 8 carbon atoms, such as a cyclopentyl group and a cyclohexyl group); cycloalkyl group); and the like.
  • aromatic hydrocarbon group examples include aryl groups having 6 to 20 carbon atoms (preferably aryl groups having 6 to 14 carbon atoms, such as phenyl, tolyl, xylyl, naphthyl, and biphenyl groups, more preferably an aryl group having 6 to 10 carbon atoms); an aralkyl group having 7 to 20 carbon atoms such as a benzyl group and a phenylethyl group (preferably an aralkyl group having 7 to 15 carbon atoms; an aralkyl group having a number of 7 or more and 11 or less); These hydrocarbon groups may contain an oxygen atom or a halogen atom. Specifically, one or more hydrogen atoms of the hydrocarbon group are selected from hydroxy, carboxyl, ether and ester may be substituted by at least one group represented by
  • R 1a and R 2a each independently have a hydrogen atom or a carbon number It is preferably an alkyl group of 1 to 20, more preferably a hydrogen atom or a methyl group, and R 3a is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
  • the (meth)acrylic polymer may have only one type of lactone ring structure, or may have two or more types.
  • the content of the lactone ring structure in the polymer is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass.
  • it is 70% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.
  • the content ratio of the lactone ring structure in the (meth)acrylic polymer is determined by the monomers involved in lactone cyclization (hydroxy group-containing (meth)acrylic monomer A and It can be calculated by the following formula from the polymerization amount of the (meth)acrylic monomer B) and the lactone cyclization rate.
  • Z 1 is a raw material monomer involved in lactone cyclization in the polymer before lactone cyclization (hydroxy group-containing (meth)acrylic monomer A in the case of cyclization reaction (i) described later and the mass content ratio of structural units derived from (meth)acrylic monomer B)
  • MR is the formula weight of the lactone ring structural unit to be produced (the lactone ring-forming element and the number of groups other than the main chain bonded to the lactone ring is the meaning of the total formula weight)
  • M m is a raw material monomer involved in lactone cyclization (hydroxy group-containing (meth)acrylic monomer A and (meth)acrylic monomer in the case of the cyclization reaction (i) described later. is the molecular weight (total) of the system monomer B), and Z2 is the lactone cyclization rate)
  • the content of the lactone ring structure in the (meth)acrylic polymer can be evaluated by known methods such as nuclear magnetic resonance ( 1 H-NMR) method and/or infrared spectroscopy (IR) method.
  • 1 H-NMR nuclear magnetic resonance
  • IR infrared spectroscopy
  • Examples of glutaric anhydride structures include structures represented by the following formula (2).
  • R 4a and R 5a are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group having 1 to 8 carbon atoms in formula (2) is preferably a linear or branched alkyl group, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, and the like.
  • R 4a and R 5a each independently represent a hydrogen atom or a carbon It is preferably an alkyl group having a number of 1 or more and 4 or less, more preferably a hydrogen atom or a methyl group.
  • the (meth)acrylic polymer may have only one type of glutaric anhydride structure, or may have two or more types.
  • the content of the glutaric anhydride structure in the polymer is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more. % by mass or more, for example, 70% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.
  • the content of the glutaric anhydride structure in the (meth)acrylic polymer can be determined, for example, by the method described in JP-A-2006-131689.
  • the content of the ring structural unit in the (meth)acrylic polymer is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, preferably 70% by mass or less, and 50% by mass. The following is more preferable, 45% by mass or less is even more preferable, and 30% by mass or less is even more preferable.
  • a (meth)acrylic resin composition having excellent heat resistance and mechanical strength can be obtained by setting the content of the ring structural unit within the above range.
  • the cyclic structural unit in the content ratio of the cyclic structural unit means a unit having a cyclic structure in the main chain of the (meth)acrylic polymer.
  • the cyclization rate in the (meth)acrylic polymer is preferably 95.0% by mass or more, more preferably 95.5% by mass or more, and even more preferably 96.0% by mass or more, from the viewpoint of suppressing foaming during molding. , 96.5% by mass or more is even more preferable. There is no particular upper limit, and it may be 100% by mass.
  • the cyclization rate is, for example, based on the amount of mass reduction that occurs when all hydroxy groups are dealcoholized or dehydrated as alcohol or water from the polymer composition obtained by polymerization, and the amount before the mass reduction starts in dynamic TG measurement. It can be determined from the mass reduction due to the dealcoholization reaction or dehydration reaction from 150° C. to 300° C. before decomposition of the polymer begins. That is, the mass reduction rate is measured from 150° C. to 300° C. in the dynamic TG measurement of a polymer having a ring structure, and the measured mass reduction rate obtained is defined as (X).
  • the theoretical mass reduction rate when assuming dealcoholization or dehydration because all hydroxyl groups contained in the polymer composition participate in ring formation is the mass reduction rate calculated on the assumption that a reaction or dehydration reaction has occurred.
  • the theoretical mass reduction rate (Y) is, more specifically, the molar ratio of the raw material monomer having a structure (hydroxy group) involved in the dealcoholization reaction or dehydration reaction in the polymer, that is, the polymer composition It can be calculated from the content of the raw material monomer in.
  • the total content of structural units derived from (meth)acrylic monomers (preferably units derived from (meth)acrylic acid esters) and ring structural units in all structural units of the (meth)acrylic polymer is 90 mass. % or more is preferred, 93 mass % or more is more preferred, and 95 mass % or more is even more preferred. This facilitates enhancing the transparency and heat resistance of the (meth)acrylic polymer.
  • the (meth)acrylic polymer may have at least one of a lactone ring structure and a glutaric anhydride structure as a ring structure. Therefore, it is more preferable to have a lactone ring structure.
  • the weight average molecular weight (Mw) of the (meth)acrylic polymer is, for example, 80,000 or more, preferably 100,000 or more, more preferably 105,000 or more, and still more preferably 110,000 or more. Yes, for example, 300,000 or less, preferably 250,000 or less, more preferably 200,000 or less.
  • Mw weight average molecular weight
  • the content of the (meth)acrylic polymer having a ring structure in the (meth)acrylic resin composition is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably is 95% by mass or more.
  • the upper limit of the content of the (meth)acrylic polymer having a ring structure in the (meth)acrylic resin composition is less than 100% by mass.
  • the (meth)acrylic resin composition of the present invention contains a phosphorus atom.
  • the phosphorus atom is preferably derived from the catalyst used for the cyclization reaction of the (meth)acrylic polymer.
  • the content of phosphorus atoms in the (meth)acrylic resin composition is 1.0 ppm or more and 50 ppm or less, preferably 1.5 ppm or more and 45 ppm or less, more preferably 2.0 ppm or more and 40 ppm or less, and 20 ppm or more and 34 ppm or less. More preferred.
  • the cyclization rate can be increased and the content of the ring structural units of the (meth)acrylic polymer can be set within an appropriate range.
  • a (meth)acrylic resin composition having excellent mechanical strength can be obtained.
  • the content of phosphorus atoms is 50 ppm or less, it is possible to obtain a (meth)acrylic resin composition that suppresses the generation of silver streaks and has excellent stability. Specifically, when the content of phosphorus atoms is 50 ppm or less, the number of corrosive phosphorus atoms is sufficiently small, and the stability is excellent. In addition, the content of phosphorus atoms shall be specified with two significant digits.
  • the (meth)acrylic resin composition of the present invention may contain a compound represented by the following formula (I), but preferably does not contain it as much as possible.
  • the content of the compound represented by formula (I) in the (meth)acrylic resin composition is 95 ppm or less, preferably 90 ppm or less, more preferably 80 ppm or less, and even more preferably 60 ppm or less. , 0 ppm (that is, not detected by the method described in the Examples).
  • the identification and content of the compound represented by the formula (I) can be obtained by the method described in Examples below. In addition, it shall be specified by rounding off to the first decimal place when expressed in ppm.
  • R 1 represents an aliphatic hydrocarbon group having 13 or more carbon atoms or an aromatic hydrocarbon group having 6 or more carbon atoms.
  • the aliphatic hydrocarbon group represented by R 1 in formula (I) may be saturated or unsaturated, and may be chain or cyclic.
  • Examples of aliphatic hydrocarbon groups having 13 or more carbon atoms represented by R 1 include tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups having 13 or more carbon atoms.
  • Alkyl groups tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, octadecenyl group, alkenyl groups having 13 or more carbon atoms such as octadecadienyl group; cyclotridecyl group, cyclotetradecyl group, cyclopentadecyl group, cyclohexyl a cycloalkyl group having 13 or more carbon atoms such as a sadecyl group, a cycloheptadecyl group, a cyclooctadecyl group; and the like.
  • aromatic hydrocarbon groups having 6 or more carbon atoms represented by R 1 include aryl groups having 6 or more carbon atoms such as phenyl, tolyl, xylyl, naphthyl, and biphenyl; benzyl, phenylethyl; an aralkyl group having 7 or more carbon atoms such as a group;
  • the (meth)acrylic resin composition of the present invention may contain a compound represented by the following formula (II), but preferably does not contain it as much as possible.
  • the content of the compound represented by formula (II) in the (meth)acrylic resin composition is 95 ppm or less, preferably 90 ppm or less, more preferably 80 ppm or less, and even more preferably 60 ppm or less. , 0 ppm (that is, not detected by the method described in the Examples).
  • the identification and content of the compound represented by formula (II) can be determined by the same method as for the compound represented by formula (I). In addition, it shall be specified by rounding off to the first decimal place when expressed in ppm.
  • R 2 represents an aliphatic hydrocarbon group having 3 or more and 12 or less carbon atoms.
  • the aliphatic hydrocarbon group represented by R 2 in formula (II) may be saturated or unsaturated, and may be linear or cyclic.
  • Examples of the aliphatic hydrocarbon group having 3 to 12 carbon atoms represented by R 2 include n-propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, alkyl groups having 3 to 12 carbon atoms such as hexyl group, heptyl group and octyl group; alkenyl groups having 3 to 12 carbon atoms such as propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group and octenyl group; Cycloalkyl groups having 3 to 12 carbon atoms such as propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cycl
  • R 2 is preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, more preferably an aliphatic hydrocarbon group having 3 to 8 carbon atoms, and further an aliphatic hydrocarbon group having 3 to 7 carbon atoms. preferable.
  • the (meth)acrylic resin composition of the present invention contains alcohols (referred to as other alcohols) other than the compounds represented by formula (I) and formula (II). You can stay.
  • the other alcohol is a low-molecular-weight alcohol such as methanol or ethanol, it will volatilize and be removed by heating during molding, so that it will not cause contamination of the rolls.
  • the content of other alcohols is as small as possible.
  • the (meth)acrylic resin composition of the present invention may optionally contain other components in addition to the (meth)acrylic polymer having a ring structure and the phosphorus atom described above. good.
  • the (meth)acrylic resin composition of the present invention contains, as the other component, for example, a (meth)acrylic polymer having no ring structure or a polymer other than the (meth)acrylic polymer.
  • a (meth)acrylic polymer having no ring structure or a polymer other than the (meth)acrylic polymer.
  • polymers other than (meth)acrylic polymers include olefin polymers such as polyethylene, polypropylene, ethylene-propylene polymer, and poly(4-methyl-1-pentene); vinyl chloride and chlorinated vinyl resins.
  • halogen-containing polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer; polyesters such as phthalates; polyamides such as nylon 6, nylon 66, nylon 610; polyacetals; polycarbonates; polyphenylene oxides; polyphenylene sulfides; cellulose derivatives; rubbery polymers such as ABS resins and ASA resins blended with polybutadiene rubbers and (meth)acrylic rubbers;
  • the content of the polymer other than the (meth)acrylic polymer having a ring structure is 100 parts by mass with respect to 100 parts by mass of the (meth)acrylic polymer having a ring structure.
  • the amount is preferably 40 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and may
  • the (meth)acrylic resin composition of the present invention may contain various additives as long as they do not impair the effects of the present invention.
  • Additives include, for example, ultraviolet absorbers; phenolic antioxidants (eg, hydroquinone, 2,6-di-t-butyl-p-cresol, tocopherol, 1,3,5-trimethyl-2,4,6 -tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, etc.), phosphorus-based antioxidants (e.g., triphenylphosphite, tris(2,4-di-t-butylphenyl)phosphite etc.), antioxidants such as sulfur-based antioxidants (e.g., 2-mercaptobenzimidazole, dilauryl 3,3'-thiodipropionate, etc.); stabilizers such as light stabilizers, weather stabilizers, heat stabilizers, etc.
  • phenolic antioxidants eg, hydroquinone
  • each additive in 100% by mass of the solid content of the resin composition is preferably 0% by mass or more and 5% by mass or less, more preferably 0% by mass or more and 2% by mass or less.
  • Examples of the ultraviolet absorber include benzophenone-based compounds, salicylate-based compounds, benzoate-based compounds, triazole-based compounds, triazine-based compounds, and the like, and known ultraviolet absorbers can be used.
  • Benzophenone compounds include 2,4-dihydroxybenzophenone, 4-n-octyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and the like.
  • Salicylate-based compounds include pt-butylphenyl salicylate and the like.
  • Benzoate compounds include 2,4-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate and the like.
  • Triazole compounds include 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(3,5 -di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4 ,6-bis(1-methyl-1-phenylethyl)phenol, 2-benzotriazol-2-yl-4,6-di-tert-butylphenol, 2-[5-chloro(2H)-benzotriazole-2- yl]-4-methyl-6-t-butylphenol, 2-(2H-benzotriazol-2-yl)-4,6-di-t-butylphenol, 2-(2H-benzotriazol-2-yl)-4 -(1,1,3,3-tetramethyl
  • Triazine compounds include 2-[4,6-bis(biphenyl-4-yl)-1,3,6-triazi-2-yl]-5-[(2-ethylhexyl)oxy]phenol, 2-mono (Hydroxyphenyl)-1,3,5-triazine compound, 2,4-bis(hydroxyphenyl)-1,3,5-triazine compound, 2,4,6-tris(hydroxyphenyl)-1,3,5 - triazine compounds and the like.
  • UV absorbers include, for example, triazine-based UV absorbers Tinuvin (registered trademark) 1577, Tinuvin (registered trademark) 460, Tinuvin (registered trademark) 477 (manufactured by BASF Japan), Adekastab (registered trademark) LA. -F70 (manufactured by ADEKA), Adekastab (registered trademark) LA-31 (manufactured by ADEKA), which is a triazole-based UV absorber, and the like. Only one type of ultraviolet absorber may be used, or two or more types may be used in combination.
  • the (meth)acrylic resin composition of the present invention preferably does not contain a hindered phenol compound and/or a compound that is a source of hindered phenol compounds, in order to more effectively suppress roll contamination.
  • a hindered phenol compound preferably does not contain a hindered phenol compound and/or a compound that is a source of hindered phenol compounds, in order to more effectively suppress roll contamination.
  • hindered phenol compounds cause roll contamination.
  • Hindered phenol compounds include, for example, 2,6-di-t-butyl-p-cresol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4 -hydroxybenzyl) benzene and other hindered phenol-based antioxidants.
  • the compound that is the source of the hindered phenol compound examples include organic phosphorus compounds having a hindered phenol moiety, specifically tris(2,4-di-t-butylphenyl) phosphite and the like. Phosphorus-based antioxidants having hindered phenol moieties and the like can be mentioned.
  • the hindered phenol compound is a phenolic compound having at least one or more sterically bulky substituents, for example, a tertiary alkyl group such as a t-butyl group, and at least one tertiary alkyl group. Phenolic compounds with
  • the (meth)acrylic resin composition of the present invention has a phosphorus atom content of 1.0 ppm or more and 50 ppm or less, and a content of the compound represented by the above formula (I) of 95 ppm or less. and preferably the content of the compound represented by the above formula (II) is 95 ppm or less, so that roll contamination can be reduced, silver streak generation is suppressed, and stability is excellent.
  • the weight average molecular weight (Mw) of the (meth)acrylic resin composition is, for example, 50,000 or more, preferably 80,000 or more, more preferably 100,000 or more, and still more preferably 115,000 or more. , more preferably 120,000 or more, for example, 300,000 or less, preferably 250,000 or less, and more preferably 200,000 or less.
  • Mw weight average molecular weight
  • the number average molecular weight (Mn) of the (meth)acrylic resin composition is, for example, 30,000 or more, preferably 35,000 or more, more preferably 40,000 or more, for example, 250,000 or less, It is preferably 200,000 or less, more preferably 150,000 or less.
  • Mn number average molecular weight of the (meth)acrylic resin composition
  • Mw represents the weight average molecular weight of the (meth)acrylic resin composition
  • Mn represents the number average molecular weight of the (meth)acrylic resin composition
  • it is 3.5 or less, preferably 3.0 or less, more preferably 2.5 or less, and there is no particular lower limit.
  • it may be 1.1 or more.
  • the (meth)acrylic resin composition preferably has a glass transition temperature of 110°C or higher. Having a glass transition temperature of 110° C. or higher increases the heat resistance of the resin composition.
  • the (meth)acrylic resin composition may have multiple glass transition temperatures of 110° C. or higher.
  • the glass transition temperature of the (meth)acrylic resin composition is more preferably 120° C. or higher, still more preferably 123° C. or higher. From the viewpoint of enhancing workability during molding, the glass transition temperature of the (meth)acrylic resin composition is preferably less than 300°C, more preferably 200°C or less, and even more preferably 180°C or less.
  • the (meth)acrylic resin composition has good adhesion because the content of the compound represented by formula (I) is 95 ppm or less.
  • the (meth)acrylic resin composition Since the (meth)acrylic resin composition has good adhesion, contamination of rolls during molding is suppressed. If the rolls become contaminated during molding, there is a risk that the appearance (smoothness) of the molded product will be impaired, and production efficiency will be reduced by stopping the line to remove the contamination on the roll surface.
  • Method for producing a (meth)acrylic resin composition In the method for producing a (meth)acrylic resin composition of the present invention, a (meth)acrylic polymer is subjected to a cyclization reaction, and the (meth)acrylic polymer is The method is characterized by including a cyclization step of forming at least one of a lactone ring structure and a glutaric anhydride structure on the main chain, and using a specific cyclization catalyst as a catalyst for the cyclization reaction.
  • the method for producing the (meth)acrylic resin composition of the present invention preferably includes a polymerization step of polymerizing the (meth)acrylic monomer to form the (meth)acrylic polymer.
  • the (meth)acrylic monomer is a polymerizable component, and examples of the (meth)acrylic monomer include the same monomers as the (meth)acrylic monomers described above, which are preferred. Aspects are also the same.
  • the (meth)acrylic monomer used for polymerization may be used alone or in combination of two or more.
  • the (meth)acrylic monomer used for polymerization preferably contains at least (meth)acrylic acid or (meth)acrylic acid ester, and more preferably contains at least (meth)acrylic acid ester.
  • the (meth)acrylic monomer used for polymerization preferably further contains a (meth)acrylic acid ester derivative.
  • (meth)acrylic monomers used for polymerization preferably include (meth)acrylic acid esters and hydroxy group-introduced derivatives of (meth)acrylic acid esters.
  • the ratio of the total amount of the (meth)acrylic monomer to the total amount of the monomer components used for polymerization is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass, from the viewpoint of the transparency of the molded article. % or more, more preferably 75% by mass or more, and there is no particular upper limit, and it may be 100% by mass.
  • the content of (meth)acrylic acid and/or (meth)acrylic acid ester in the (meth)acrylic monomer used for polymerization is, for example, 30% by mass or more, preferably 50% by mass or more, more preferably 60% by mass.
  • the content of the (meth)acrylic acid ester derivative (preferably ⁇ -(1-hydroxyalkyl) alkyl acrylate) relative to the total amount of monomer components used for polymerization is, for example, 1% by mass or more, preferably 5% by mass or more. , More preferably 8% by mass or more, still more preferably 10% by mass or more, for example, 70% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less .
  • the monomer component which is a polymerization component, may contain other monomers other than the (meth)acrylic monomers, and examples of the other monomers include the same monomers as the other monomers described above. , and preferred embodiments thereof are also the same.
  • the other monomers used for polymerization may be of only one type, or may be of two or more types.
  • the ratio of the total amount of other monomers to the total amount of monomer components is, for example, 0% by mass or more, preferably 1% by mass or more, for example, 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass. % by mass or less.
  • a polymerization initiator In the polymerization reaction using the (meth)acrylic monomer, a polymerization initiator may be used as necessary.
  • polymerization initiators examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, dimethyl-2,2'-azobis(2-methylpropane).
  • azo compounds such as 4,4′-azobis (4-cyanopentanoic acid); persulfates such as potassium persulfate; cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, t-amylperoxyoctoate, t-amylperoxyisononanoate, t-amylper Organic peroxides such as oxyisopropyl carbonate and t-amylperoxy 2-ethylhexyl carbonate can be used
  • the amount of the polymerization initiator used is, for example, 500 ppm or more, preferably 1000 ppm or more, or more, relative to the total amount of the monomer components. Preferably it is 1500 ppm or more.
  • the amount of the polymerization initiator used is, for example, 2% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, relative to the total amount of the monomer components.
  • a reducing agent such as sodium hydrogen sulfite
  • a transition metal salt such as ferrous sulfate
  • a chain transfer agent may be added to the reaction system in order to adjust the weight average molecular weight of the (meth)acrylic polymer.
  • a chain transfer agent By adding a chain transfer agent to the reaction system, the (meth)acrylic polymer can be made to have a low molecular weight.
  • chain transfer agents include organic thiol compounds; halogen compounds such as carbon tetrachloride, carbon tetrabromide, methylene chloride, bromoform, and bromotrichloroethane; Examples include unsaturated hydrocarbon compounds. These chain transfer agents may be used alone or in combination of two or more. Among these, an organic thiol compound is preferable because it can suppress a decrease in conversion rate.
  • Examples of the organic thiol compound include monofunctional thiol compounds and polyfunctional thiol compounds.
  • Examples of the monofunctional thiol compound include aromatics such as thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, and octyl thioglycolate.
  • aliphatic monofunctional thiol compound examples include aliphatic hydrocarbons such as octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, and 2-mercaptoethyl octanoate.
  • polyfunctional thiol compound examples include polyfunctional thiol compounds having an aromatic ring such as 1,4-dimethylmercaptobenzene and 1,3,5-triazine-2,4,6-trithiol; 1,8-dimercapto -3,6-dioxaoctane, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhiobutanate, pentaerythritol tetrakisthioglycolate, pentaerythritol Having an aromatic ring such as tetrakisthiopropionate, pentaerythritol tetrakis (4-mercaptobutanate), pentaerythritol tetrakis (6-mercaptohexanate), dipentaerythritol hexakis (3-mer
  • organic thiol compound monofunctional thiol compounds are preferred, aliphatic monofunctional thiol compounds are more preferred, and alkylthiol compounds are even more preferred.
  • the amount of the chain transfer agent used is, for example, 200 ppm or more, preferably 400 ppm or more, more preferably 500 ppm or more, for example, 5% by mass or less, preferably 1% by mass or less, relative to the total amount of the monomer components. More preferably, it is 0.5% by mass or less.
  • the ratio of the amount of the chain transfer agent and the polymerization initiator used is preferably 0.10 or more, more preferably 0.15 or more, and still more preferably 0. 0.20 or more, preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.0 or less.
  • amount ratio of the chain transfer agent and the polymerization initiator is within the above range, the polymerization rate can be appropriately maintained and the molecular weight distribution can be narrowed.
  • the polymerization form of the (meth)acrylic monomer may be batch polymerization or continuous polymerization. When a chain transfer agent is used, the residual amount of unreacted chain transfer agent can be reduced. Batch polymerization is preferred. Polymerization of the (meth)acrylic monomer may be bulk polymerization, solution polymerization, emulsion polymerization, or suspension polymerization, but solution polymerization is preferred because of its high safety and low risk of foreign matter contamination.
  • Solvents usable in solution polymerization include aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Ether solvents such as anisole; Ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; Cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve; methanol, ethanol, isopropanol, n alcohol solvents such as butanol; nitrile solvents such as acetonitrile, propionitrile, butyronitrile and benz
  • the total concentration of the monomers (monomer components) in the polymerization reaction solution is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less.
  • the amount of solvent used in the polymerization reaction is not particularly limited as long as the total concentration of the monomers in the polymerization reaction solution is within the above range.
  • the total amount of each may be initially charged, or a fixed amount may be initially charged and the remainder may be added all at once or continuously to the reaction system during the polymerization reaction.
  • the continuation may be continuous or intermittent such as divided addition, preferably continuous or intermittent at intervals of 10 minutes or less, more preferably continuous.
  • the method of adding the polymerization initiator and the chain transfer agent, which are used as necessary is not particularly limited.
  • the total amount of each may be initially charged, or a fixed amount may be initially charged and the remainder may be added all at once or continuously to the reaction system during the polymerization reaction, or the total amount may be added to the reaction system by addition.
  • the continuation may be continuous or intermittent such as divided addition, preferably continuous or intermittent at intervals of 10 minutes or less, more preferably continuous.
  • the polymerization initiator can narrow the molecular weight distribution of the obtained (meth)acrylic polymer, the total amount is continuously added to the reaction system during the polymerization reaction, or a certain amount is initially charged and the rest is polymerized. It is preferable to continuously add to the reaction system during the reaction.
  • the atmosphere in which the (meth)acrylic monomer is polymerized is not particularly limited, it is preferably an inert gas such as nitrogen gas from the viewpoint of increasing the efficiency of the polymerization reaction.
  • the polymerization temperature for polymerizing the (meth)acrylic monomer is, for example, 40° C. or higher, preferably 60° C. or higher, more preferably 80° C. or higher.
  • the 10-hour half-life temperature means the temperature at which the half-life of the polymerization initiator is 10 hours.
  • the polymerization temperature is, for example, 180° C. or lower, preferably 150° C. or lower, more preferably 120° C. or lower, and when a solvent is used, it is preferably not higher than the reflux temperature of the solvent used.
  • the polymerization time for polymerizing the (meth)acrylic monomer is not particularly limited, and may be appropriately set according to the progress of the polymerization reaction, but is usually about 2 to 8 hours.
  • aging may be performed as necessary. Aging further improves monomer conversion.
  • the aging time is, for example, 0 hours or more and 10 hours or less, preferably 1 hour or more and 5 hours or less.
  • the conversion rate of the monomer at the end of the reaction is, for example, 80% or higher, preferably 85% or higher, and more preferably 88% or higher.
  • the total content of structural units derived from (meth)acrylic monomers in all structural units of the (meth)acrylic polymer obtained by the polymerization reaction is preferably 50% by mass or more from the viewpoint of the transparency of the molded product. , more preferably 60% by mass or more, still more preferably 70% by mass or more, and even more preferably 75% by mass or more. There is no particular upper limit, and it may be 100% by mass.
  • the total content of structural units derived from (meth)acrylic acid ester derivatives (preferably ⁇ -(1-hydroxyalkyl)alkyl acrylate) in all structural units of the (meth)acrylic polymer obtained by the polymerization reaction is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, for example, 70% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less, and further Preferably, it is 20% by mass or less.
  • the cyclization catalyst is selected from the group consisting of C 3-12 alkyl phosphate, C 3-12 alkyl phosphite, and C 3-12 hypophosphite. By using at least one of them, it is possible to efficiently perform the cyclization reaction and to suppress deterioration of adhesion of the obtained (meth)acrylic resin composition.
  • C 3-12 alkyl phosphate examples include monopropyl phosphate, dipropyl phosphate, tripropyl phosphate, monoisopropyl phosphate, diisopropyl phosphate, triisopropyl phosphate, monobutyl phosphate, dibutyl phosphate, phosphorus tributyl acid, mono-tert-butyl phosphate, di-tert-butyl phosphate, tri-tert-butyl phosphate, monopentyl phosphate, dipentyl phosphate, tripentyl phosphate, monohexyl phosphate, dihexyl phosphate, trihexyl phosphate, phosphorus monoheptyl phosphate, diheptyl phosphate, triheptyl phosphate, monooctyl phosphate, dioctyl phosphate, trioctyl phosphate and the like.
  • the C 3-12 alkyl phosphate is preferably a C 3-10 alkyl phosphate, more preferably a C 3-8 alkyl phosphate, and even more preferably a C 3-7 alkyl phosphate.
  • the C 3-8 alkyl phosphate is preferably a C 3-8 straight-chain alkyl phosphate, more preferably a C 3-8 mono-straight-chain alkyl phosphate and a C 3-8 di-straight-chain alkyl phosphate.
  • the C 3-7 alkyl phosphate is preferably a C 3-7 straight-chain alkyl phosphate, more preferably a C 3-7 mono-straight-chain alkyl phosphate and a C 3-7 di-straight-chain alkyl phosphate.
  • monobutyl phosphate and dibutyl phosphate are particularly preferred.
  • C 3-12 alkyl phosphite examples include monopropyl phosphite, dipropyl phosphite, tripropyl phosphite, monoisopropyl phosphite, diisopropyl phosphite, triisopropyl phosphite, phosphite monobutyl acid, dibutyl phosphite, tributyl phosphite, mono-tert-butyl phosphite, di-tert-butyl phosphite, tri-tert-butyl phosphite, monopentyl phosphite, dipentyl phosphite, phosphorous tripentyl phosphite, monohexyl phosphite, dihexyl phosphite, trihexyl phosphite, monoheptyl phosphite, dihept
  • the C 3-12 alkyl phosphite is preferably a C 3-10 alkyl phosphite, more preferably a C 3-8 alkyl phosphite, and even more preferably a C 3-7 alkyl phosphite.
  • the C 3-8 alkyl phosphite is more preferably C 3-8 straight-chain alkyl phosphite, C 3-8 mono-straight-chain alkyl phosphite, C 3-8 di-straight-chain alkyl phosphite Esters are even more preferred.
  • the C 3-7 alkyl phosphite is preferably C 3-7 straight-chain alkyl phosphite, C 3-7 mono-straight-chain alkyl phosphite, C 3-7 di-straight-chain alkyl phosphite Esters are more preferred.
  • C 3-12 alkyl phosphites monobutyl phosphite and dibutyl phosphite are particularly preferred.
  • Hypophosphite C 3-12 alkyl esters include, for example, monopropyl hypophosphite, dipropyl hypophosphite, tripropyl hypophosphite, monoisopropyl hypophosphite, diisopropyl hypophosphite, hypophosphite triisopropyl phosphate, monobutyl hypophosphite, dibutyl hypophosphite, tributyl hypophosphite, mono-tert-butyl hypophosphite, di-tert-butyl hypophosphite, tri-tert-butyl hypophosphite, monopentyl hypophosphite, dipentyl hypophosphite, tripentyl hypophosphite, monohexyl hypophosphite, dihexyl hypophosphite, trihexyl hypophosphite, monoheptyl hypophosphite
  • the C 3-12 alkyl hypophosphite is preferably a C 3-10 alkyl hypophosphite, more preferably a C 3-8 alkyl hypophosphite, and a C 3-7 alkyl hypophosphite. is more preferred.
  • the C 3-8 alkyl hypophosphite is more preferably C 3-8 linear alkyl hypophosphite, C 3-8 mono linear alkyl hypophosphite, C 3-8 hypophosphite Dilinear alkyl esters are even more preferred.
  • the C 3-7 alkyl hypophosphite is more preferably C 3-7 linear alkyl hypophosphite, C 3-7 mono linear alkyl hypophosphite, C 3-7 hypophosphite Dilinear alkyl esters are even more preferred.
  • C 3-12 alkyl hypophosphite monobutyl hypophosphite and dibutyl hypophosphite are particularly preferred.
  • cyclization catalyst Only one kind of the cyclization catalyst may be used, or two or more kinds thereof may be used in combination. When two or more types are used together, one of them may be stearyl phosphate. This is because one of the ideas of the present invention is to make the proportion of stearyl phosphate in the total amount of the cyclization catalyst smaller than before.
  • a phosphoric acid C 3-12 alkyl ester is preferable because of its high catalytic activity.
  • the decomposition temperature of the cyclization catalyst is preferably 160°C or higher, more preferably 180°C or higher, and still more preferably 200°C or higher.
  • the decomposition temperature of butyl phosphate is 220°C and the decomposition temperature of octyl phosphate is 247°C.
  • cyclization reaction to form a lactone ring structure between a hydroxy group and an ester group or a carboxyl group;
  • a glutaric anhydride structure between a carboxyl group and an ester group or another carboxyl group; cyclization reaction to form
  • a hydroxy group-containing (meth)acrylic monomer A such as alkyl ⁇ -(1-hydroxyalkyl)acrylate is homopolymerized, or the hydroxy A group-containing (meth)acrylic monomer A and a (meth)acrylic monomer B such as (meth)acrylic acid or (meth)acrylic acid ester are copolymerized to form a (meth)acrylic polymer molecular chain.
  • a hydroxy group and an ester group or a carboxyl group are introduced.
  • a lactone ring structure can be formed by dealcoholization or dehydration cyclocondensation between a hydroxy group and an ester group or a carboxyl group.
  • the hydroxy group-containing (meth)acrylic monomer A in the cyclization reaction (i) include hydroxy group-introduced derivatives of the aforementioned (meth)acrylic acid esters, and preferred embodiments thereof are the same.
  • the (meth)acrylic monomer B includes the above-described (meth)acrylic acid and (meth)acrylic acid ester, and preferred embodiments thereof are also the same.
  • (meth)acrylic acid is homopolymerized to introduce a carboxyl group into the molecular chain of the (meth)acrylic polymer, or (meth)acrylic acid A (meth)acrylic monomer B such as a (meth)acrylic acid ester is polymerized (preferably copolymerized) to introduce a carboxyl group and an ester group into the molecular chain of the (meth)acrylic polymer.
  • a glutaric anhydride structure can be formed by dehydration cyclocondensation between two carboxyl groups or by dealcoholization between a carboxyl group and an ester group.
  • the (meth)acrylic monomer B in the cyclization reaction (ii) include the above-mentioned (meth)acrylic acid and (meth)acrylic acid esters, and preferred embodiments thereof are also the same.
  • addition reaction of a hydroxy group to the double bond portion, ester A hydroxy group, an ester group, or a carboxyl group that reacts in a cyclization reaction may be subsequently introduced into the (meth)acrylic polymer by hydrolysis of the group, esterification reaction of the carboxyl group or acid anhydride group, or the like.
  • the reaction may be carried out so as to be within the ranges of the content ratio of the units and the cyclization rate.
  • the cyclization reaction may be carried out in the presence of a solvent, and the solvents that can be used in the cyclization reaction include the same types of solvents that can be used in the polymerization reaction described above, and preferred embodiments are also the same.
  • a new solvent may be added after removing the solvent used in the solution polymerization, or the solvent used in the solution polymerization may be used as a solvent in the cyclization reaction.
  • the concentration of the (meth)acrylic polymer in the cyclization reaction solution is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less.
  • the amount of solvent used in the cyclization reaction is not particularly limited as long as the concentration of the (meth)acrylic polymer in the cyclization reaction solution is within the above range.
  • the amount of the cyclization catalyst used is, for example, preferably 100 ppm or more and 1000 ppm or less, more preferably 110 ppm or more, still more preferably 120 ppm or more, and more It is more preferably 150 ppm or more, more preferably 900 ppm or less, still more preferably 800 ppm or less, and even more preferably 700 ppm or less.
  • the amount of the cyclization catalyst used is within the above range, the cyclization rate is increased, and the generation of silver streaks is suppressed and stabilized while forming the desired ratio of ring structural units in the (meth)acrylic polymer.
  • a (meth)acrylic resin composition having excellent properties can be obtained.
  • the entire amount may be initially charged, or a fixed amount may be initially charged and the remainder may be added all at once or continuously to the reaction system during the cyclization reaction.
  • the entire amount may be introduced into the reaction system by addition.
  • the continuation may be continuous or intermittent such as divided addition, preferably continuous or intermittent at intervals of 10 minutes or less, more preferably continuous.
  • the reaction temperature for the cyclization reaction is, for example, 50°C to 300°C, preferably 70°C to 150°C.
  • the reaction time for the cyclization reaction is, for example, about 5 minutes to 6 hours, preferably 30 minutes to 3 hours. According to the cyclization catalyst of the present invention, since the cyclization reaction can be performed efficiently, even if the reaction time is less than 3 hours, the cyclization rate is high, and the above-mentioned ring structural unit in the (meth)acrylic polymer can achieve cyclization within the range of the content ratio of
  • the cyclization reaction is carried out in a reaction vessel in which the polymerization reaction is carried out, and further progressed in an autoclave, multitubular heat exchanger, or the like.
  • the devolatilization step is a treatment step for removing volatile matter such as solvent and residual monomers, and alcohol by-produced by the cyclization reaction. If at least one selected from the group consisting of C 3-12 alkyl phosphate, C 3-12 alkyl phosphite, and C 3-12 hypophosphite is used as a cyclization catalyst, devolatilization Easy to volatilize and be removed in the process. Furthermore, by performing the devolatilization step under heating conditions, the cyclization catalyst is decomposed to generate alcohol, and it is preferable that the alcohol is also removed.
  • the (meth)acrylic resin composition has a large amount of residual volatile matter, and foaming occurs during molding, resulting in poor molding.
  • alkyl phosphates, alkyl phosphites, or alkyl hypophosphites having 13 or more carbon atoms are used as the cyclization catalyst, higher alcohols (carbon atoms alcohol of 13 or more) is difficult to volatilize, so it remains in the (meth)acrylic resin composition and reduces the adhesion of the (meth)acrylic resin composition.
  • the device used for devolatilization is not particularly limited, but for example, an autoclave, a kettle-type reactor, a device consisting of a heat exchanger and a devolatilization tank, a vented extruder, etc. can be used, and a dryer may be used. .
  • the extruder When using a vented extruder for devolatilization, the extruder preferably has a cylinder, a screw provided in the cylinder, and heating means. It is preferable that the cylinder is provided with one or more vents, and the vent is more preferably provided at least downstream of the raw material charging section with respect to the transfer direction in the extruder, and upstream of the raw material charging section. It may also be provided on the side. Volatilization progresses in the process in which the polymer fed into the extruder is conveyed from the upstream side to the downstream side of the extruder while being kneaded by a screw.
  • a die is preferably provided on the downstream side of the extruder, and the polymer can be molded into a predetermined shape by discharging the polymer from the die.
  • pellets can be produced by finely cutting a rod-shaped polymer.
  • the die part of the extruder is provided with a polymer filter.
  • the devolatilization treatment temperature is preferably in the range of 150°C to 350°C, more preferably in the range of 200°C to 300°C. When the devolatilization treatment temperature is lower than 150°C, the devolatilization becomes insufficient and the remaining volatile matter increases.
  • the degree of pressure reduction during the devolatilization treatment is preferably 13.3 hPa or more (for example, about 13.3 hPa to 800 hPa).
  • the additive may be added in one or more steps selected from the polymerization step, the cyclization step, and the steps after the cyclization step. However, it is preferable that the additive does not contain the hindered phenol compound and/or the compound that is the source of the hindered phenol compound.
  • the (meth)acrylic resin composition can be molded into various shapes and used as various products or parts.
  • the shape of the molded article may be appropriately set according to the application, and examples thereof include plate-like, granular, powdery, lumpy, particle aggregate, spherical, ellipsoidal, lens-like, cubic, columnar, rod-like, cone-like, Cylindrical, acicular, fibrous, hollow fiber, porous and the like can be mentioned.
  • Molded bodies of these (meth)acrylic resin compositions can be formed by, for example, injection molding, extrusion molding, blow molding, or other processes in which (meth)acrylic resin particles are thermally melted, or the primary molded body is further subjected to secondary molding (vacuum molding).
  • the shape of the (meth)acrylic resin particles is preferably, for example, powder with a particle diameter of 1 ⁇ m to 1000 ⁇ m, cylindrical or spherical pellets with a major diameter of about 1 mm to 10 mm, or a mixture thereof.
  • the (meth)acrylic resin particles may be further formed into a film to form an optical film.
  • optical films include polarizer protective films, retardation films, viewing angle compensation films, light diffusion films, reflective films, antireflection films, antiglare films, brightness enhancement films, and conductive films for touch panels.
  • These optical films generally have a (meth)acrylic resin layer made of a (meth)acrylic resin composition and a primer layer provided on the surface of the (meth)acrylic resin layer. Contains particles.
  • the primer layer is, for example, a layer made of at least one resin selected from urethane resin, cellulose resin, polyol resin, polycarboxylic acid resin, and polyester resin.
  • the particles may be organic particles or inorganic particles.
  • the organic particles are, for example, particles containing an organic polymer such as a (meth)acrylic polymer having a (meth)acrylic monomer as a structural unit or a styrene polymer having a styrene monomer as a structural unit.
  • the constituent units ((meth)acrylic monomer, styrene monomer, etc.) of the organic polymer may be those prepared through recycling such as chemical recycling.
  • examples of inorganic particles include silica particles, alumina particles, titania particles, zirconia particles, vitreous particles, and the like. These particles may also be prepared through recycling.
  • the molding temperature of the (meth)acrylic resin composition is not particularly limited, but is preferably in the range of 150°C to 350°C, more preferably in the range of 200°C to 300°C.
  • the (meth)acrylic resin composition of the present invention can reduce roll contamination, further suppresses the generation of silver streaks and has excellent stability, so the (meth)acrylic resin composition is used. Molded products with excellent appearance can be produced with high efficiency.
  • Weight average molecular weight, number average molecular weight, molecular weight distribution The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the (meth)acrylic resin in the polymerization solution and after polymerization are It calculated
  • GPC gel permeation chromatography
  • Measurement system Tosoh GPC system HLC-8220 Measurement side column configuration: ⁇ Guard column (manufactured by Tosoh, TSK guardcolumn SuperHZ-L) ⁇ Separation column (manufactured by Tosoh, TSK Gel Super HZM-M), two columns connected in series Reference side column configuration: ⁇ Reference column (manufactured by Tosoh, TSK gel SuperH-RC) Developing solvent: Chloroform (manufactured by Wako Pure Chemical Industries, special grade) Flow rate of developing solvent: 0.6 mL / min Standard sample: TSK standard polystyrene (manufactured by Tosoh, PS-oligomer kit)
  • the glass transition temperature (Tg) of the (meth)acrylic resin composition was determined by the starting point method in accordance with JIS K7121. Specifically, using a differential scanning calorimeter (Thermo plus EVO DSC-8230 manufactured by Rigaku Co., Ltd.), a sample of about 10 mg was heated from room temperature to 200 ° C. under nitrogen gas flow (100 ml / min) (heating The evaluation was made from the DSC curve obtained at a speed of 20°C/min). ⁇ -alumina was used as a reference.
  • Lactone Cyclization Rate Two parts of the (meth)acrylic resin composition were dissolved in 20 parts of chloroform, and the resulting solution was added dropwise to 200 parts of methanol to obtain a solution containing precipitates. A sample was obtained by filtering the solution containing the precipitate, extracting the precipitate, and drying it in a vacuum dryer at 80° C. for 4 hours. The obtained sample was analyzed by the following method (dynamic TG method), and the lactone cyclization rate (%) was calculated from the formula (B).
  • Alcohol component measurement Sample preparation 2 parts of the (meth)acrylic resin composition was dissolved in 20 parts of chloroform, and the obtained solution was dropped into 200 parts of methanol to obtain a solution containing precipitates.
  • the obtained sample solution was measured using GC-MS to identify detected alcohol components other than methanol.
  • the sample solution was measured using gas chromatography (manufactured by Shimadzu Corporation, device name: GC17A) to quantify the alcohol component content (ppm) other than methanol in the (meth)acrylic resin composition.
  • Adhesion evaluation A (meth)acrylic resin composition is sandwiched between aluminum thin plates (manufactured by Nippon Test Panel, film thickness 0.1 mm), and further sandwiched between aluminum thin plates with SUS plates. It was melt press molded at 250° C. for 5 minutes using IMC-180C type manufactured by Imoto Seisakusho. After that, it was removed from the press while sandwiched between the SUS plates, cooled for 1 minute, and when the aluminum thin plate was peeled off, if the resin composition adhered to the entire surface of the aluminum thin plate, the adhesion was "good", and the resin composition was evaluated as "good”. The adhesion was judged to be "Normal” when the resin composition partially adhered, and the adhesion was judged to be "Poor” when the resin composition could be peeled off without adhering.
  • the pellets were melted with a single screw while being sucked from the vent port at 25 Torr, and passed through a leaf disk type polymer filter with a filtration accuracy of 5 ⁇ m using a gear pump. Then, the molten resin was extruded from a T-die with a width of 600 mm and cast on a hard chromium-plated cooling roll temperature-controlled at 115° C. to obtain a raw film with a thickness of 145 ⁇ m. After the above-mentioned melt film formation, the surface of the cast cooling roll was visually observed. If white turbidity was also observed in the central portion in the width direction of the film, it was determined as "defective".
  • Example 1 83.5 parts of methyl methacrylate (MMA), methyl 2-(hydroxymethyl) acrylate (MHMA; ⁇ -(hydroxymethyl) acrylic 12 parts of methyl acid) and 88.7 parts of toluene were charged, and the temperature was raised to 105° C. while nitrogen was passed through. When refluxing with temperature rise started, 0.535 parts of a 20% by weight toluene solution of t-amylperoxyisononanoate (manufactured by Arkema Yoshitomi Co., Ltd., Luperox (registered trademark) 570T20) was added as a polymerization initiator.
  • MMA methyl methacrylate
  • MHMA methyl 2-(hydroxymethyl) acrylate
  • ⁇ -(hydroxymethyl) acrylic 12 parts of methyl acid 88.7 parts
  • the extruder has one rear vent, four fore vents (hereinafter referred to as first, second, third, and fourth vents from the upstream side), and side vents between the third and fourth vents. Equipped with a feeder, the number of revolutions was 80 rpm, the degree of pressure reduction was 25 to 800 hPa, and the barrel temperature was 255° C. (heated with a heat medium of 255° C.).
  • the extruder has a leaf disk-shaped polymer filter (filtration accuracy of 10 ⁇ m) at the tip, and the extrusion die provided at the tip of the polymer filter has pores formed around the circumference of the resin ejection surface.
  • a large number of water ring cut type cutters are installed along the ridge. After cutting and water-cooling solidification, a dehydration facility using a centrifugal dryer is provided, and the material is transported to a storage silo by gas transportation.
  • ion-exchanged water is introduced at a rate of 1.5 parts/hour from the upstream of the second and third vents, and ion-exchanged water is introduced at a rate of 3 parts/hour from the upstream of the fourth vent.
  • the molten (meth)acrylic resin composition is extruded from the die (pore) of the extrusion die, cut, and water cooled. After solidification, it was dehydrated using a centrifugal dryer, transported, and then cooled in a storage silo to obtain a (meth)acrylic resin composition (A-1).
  • Table 1 shows the composition of the obtained (meth)acrylic resin composition (A-1), and Table 2 shows its physical properties.
  • Example 2 As a catalyst (cyclization catalyst) for the cyclization condensation reaction, (meth)acrylic A system resin composition (A-2) was obtained.
  • Table 1 shows the compounding composition of the obtained (meth)acrylic resin composition (A-2), and Table 2 shows each physical property.
  • Example 3 (Meth)acrylic (meth)acrylic A system resin composition (A-3) was obtained.
  • Table 1 shows the composition of the obtained (meth)acrylic resin composition (A-3), and Table 2 shows its physical properties.
  • ADEKA Co., Ltd., ADEKA STAB (registered trademark) LA-F70 ultraviolet absorber
  • Example 5 (Meth)acrylic (meth)acrylic A system resin composition (A-5) was obtained.
  • Table 1 shows the formulation of the obtained (meth)acrylic resin (A-5) composition, and Table 2 shows each physical property.
  • Comparative example 1 83.5 parts of MMA, 12 parts of MHMA, 0.07 parts of nDM, and 88.7 parts of toluene were charged into a reactor equipped with a stirrer, temperature sensor, cooling condenser, and nitrogen inlet tube, and heated to 105°C while passing nitrogen through the reactor. The temperature was raised to When the reflux started with the temperature rise, 0.451 part of a 20% by weight toluene solution of t-amylperoxyisononanoate (manufactured by Arkema Yoshitomi Co., Ltd., Luperox (registered trademark) 570T20) was added as a polymerization initiator.
  • t-amylperoxyisononanoate manufactured by Arkema Yoshitomi Co., Ltd., Luperox (registered trademark) 570T20
  • stearyl phosphate Phoslex A-18, manufactured by SC Organic Chemical Co., Ltd.
  • cyclization catalyst a catalyst for the cyclization condensation reaction
  • the cyclization condensation reaction to form the lactone ring structure was allowed to proceed for 2 hours under reflux at °C.
  • the resulting polymerization solution was passed through a shell and tube heat exchanger heated to 235° C. to complete the cyclization condensation reaction.
  • the obtained polymerization solution was introduced at a processing rate of 100 parts / hour in terms of resin amount and devolatilized. processed.
  • a toluene solution consisting of 74:1:1 was charged upstream of the third vent at a rate of 0.165 parts/hour.
  • the molten (meth)acrylic resin composition is extruded from the die (pore) of the extrusion die, cut, and water cooled. After solidification, it was dehydrated using a centrifugal dryer, transported, and then cooled in a storage silo to obtain a (meth)acrylic resin composition (A-6).
  • Table 1 shows the composition of the obtained (meth)acrylic resin (A-6) composition
  • Table 2 shows each physical property.
  • Comparative example 2 (Meth)acrylic (meth)acrylic A system resin composition (A-7) was obtained.
  • Table 1 shows the formulation of the obtained (meth)acrylic resin (A-7) composition, and Table 2 shows each physical property.

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Abstract

The present invention addresses the problem of providing a (meth)acrylic resin composition which makes it possible to reduce the contamination of a roll and prevent the occurrence of silver streaks, and which has excellent stability. The present invention also addresses the problem of providing: a molded article using the (meth)acrylic resin composition; and a method for producing the (meth)acrylic resin composition. Provided is a (meth)acrylic resin composition that contains a (meth)acrylic polymer having, in a main chain thereof, a ring structure that is at least one of a lactone ring structure and a glutaric anhydride structure, the (meth)acrylic resin composition being characterized in that the content of phosphorus atoms in the (meth)acrylic resin composition is 1.0 ppm to 50 ppm inclusive and the content of a compound represented by formula (I) in the (meth)acrylic resin composition is 95 ppm or less. (I): HO―R1 [In formula (I), R1 represents an aliphatic hydrocarbon group having 13 or more carbon atoms or an aromatic hydrocarbon group having 6 or more carbon atoms.]

Description

（メタ）アクリル系樹脂組成物及びそれを用いた成形体、並びに（メタ）アクリル系樹脂組成物の製造方法(Meth)acrylic resin composition, molded article using the same, and method for producing (meth)acrylic resin composition
　本発明は、（メタ）アクリル系樹脂組成物及びそれを用いた成形体、並びに（メタ）アクリル系樹脂組成物の製造方法に関するものである。 The present invention relates to a (meth)acrylic resin composition, a molded article using the same, and a method for producing a (meth)acrylic resin composition.
　（メタ）アクリル系樹脂は、光学特性、機械的強度、成型加工性、表面硬度等の諸特性のバランスに優れるため、光学部材への使用に好適である。しかし、一般に、（メタ）アクリル系樹脂はガラス転移温度（Ｔｇ）が低く、耐熱性に優れない。そこで、（メタ）アクリル系樹脂の耐熱性向上のために、主鎖にラクトン環構造等の環構造を導入した（メタ）アクリル系樹脂が知られている。ラクトン環構造を有する（メタ）アクリル系樹脂の製造方法としては、例えば、分子鎖中にヒドロキシ基とエステル基とを有する重合体において、有機リン化合物を触媒として用いて、加熱により縮合環化してラクトン環構造を分子鎖中に形成する方法が提案されている（特許文献１、２）。特許文献１では、具体的に用いられる触媒はリン酸メチルやフェニル亜ホスホン酸である。特許文献２では、具体的に用いられる触媒はリン酸ステアリルである。 (Meth)acrylic resins are suitable for use in optical members because they have an excellent balance of properties such as optical properties, mechanical strength, molding processability, and surface hardness. However, (meth)acrylic resins generally have a low glass transition temperature (Tg) and are not excellent in heat resistance. Therefore, in order to improve the heat resistance of (meth)acrylic resins, there are known (meth)acrylic resins in which a ring structure such as a lactone ring structure is introduced into the main chain. As a method for producing a (meth)acrylic resin having a lactone ring structure, for example, a polymer having a hydroxy group and an ester group in the molecular chain is condensed and cyclized by heating using an organic phosphorus compound as a catalyst. A method of forming a lactone ring structure in a molecular chain has been proposed (Patent Documents 1 and 2). In Patent Document 1, the specifically used catalysts are methyl phosphate and phenyl phosphonous acid. In Patent Document 2, the specifically used catalyst is stearyl phosphate.
特開２００１－１５１８１４号公報JP 2001-151814 A 特開２０１７－１４５３８７号公報JP 2017-145387 A
　特許文献１で具体的に用いられるリン酸メチル等は、環化効率が低かった。そのため、重合体において所望の割合の環構造を形成するためには、触媒を多く使用する必要があった。触媒を多く使用すると、得られる（メタ）アクリル系樹脂組成物中に触媒に由来する成分（リン原子を含む化合物）が多く残る恐れがあった。リン原子は腐食性を有するので、（メタ）アクリル系樹脂の安定性が懸念された。他方、触媒量を少なくすると、（メタ）アクリル系樹脂組成物にシルバーストリークが発生する恐れがあった。また、特許文献２で具体的に用いられるリン酸ステアリルを環化触媒として使用した場合には、樹脂をフィルムにするときに、フィルムの製造に用いられるロールの表面が汚染されやすい問題があった。ロールの表面が汚染されると、得られるフィルムの外観が損なわれたり、生産効率が低下したりする恐れがあった。 Methyl phosphate and the like specifically used in Patent Document 1 had low cyclization efficiency. Therefore, it was necessary to use a large amount of catalyst in order to form a desired ratio of ring structures in the polymer. When a large amount of catalyst is used, there is a risk that a large amount of components (compounds containing phosphorus atoms) derived from the catalyst may remain in the resulting (meth)acrylic resin composition. Phosphorus atoms are corrosive, so there was concern about the stability of (meth)acrylic resins. On the other hand, if the amount of catalyst is reduced, there is a possibility that silver streaks may occur in the (meth)acrylic resin composition. In addition, when stearyl phosphate specifically used in Patent Document 2 is used as a cyclization catalyst, when the resin is made into a film, there is a problem that the surface of the roll used for film production is easily contaminated. . If the surface of the roll is contaminated, there is a possibility that the appearance of the resulting film will be spoiled or the production efficiency will be lowered.
　この問題に関し、特許文献２では樹脂組成物におけるリン元素や分子量３００未満のヒンダードフェノール化合物の含有量を制御すること、つまりヒンダードフェノール部位を有するリン系酸化防止剤の使用量を制御する（過剰添加をしない）ことにより、ロール表面の汚染を抑制することが検討された。しかしながら、ヒンダードフェノール部位を有するリン系酸化防止剤の使用量を抑制してもなおロール表面の汚染源が存在しており、具体例でリン酸ステアリルが使用されているためロール表面の汚染の抑制には限界があるように考えられた。 Regarding this problem, Patent Document 2 discloses controlling the content of elemental phosphorus and a hindered phenol compound having a molecular weight of less than 300 in a resin composition, that is, controlling the amount of a phosphorus-based antioxidant having a hindered phenol site ( It was studied to suppress the contamination of the roll surface by not adding excessively. However, even if the amount of the phosphorus antioxidant having a hindered phenol moiety is suppressed, there is still a contamination source on the roll surface, and stearyl phosphate is used in the specific example, so contamination of the roll surface is suppressed. was thought to have limits.
　本発明は上記のような事情に着目してなされたものであって、その目的は、ロール汚染を低減でき、さらにはシルバーストリークの発生が抑制されるとともに安定性に優れた（メタ）アクリル系樹脂組成物を提供することにある。また本発明は、前記（メタ）アクリル系樹脂組成物を用いた成形体、並びに前記（メタ）アクリル系樹脂組成物の製造方法を提供することも目的とする。 The present invention has been made in view of the above circumstances, and its object is to reduce roll contamination, further suppress the generation of silver streaks, and provide a (meth)acrylic (meth)acrylic roll with excellent stability. An object of the present invention is to provide a resin composition. Another object of the present invention is to provide a molded article using the (meth)acrylic resin composition and a method for producing the (meth)acrylic resin composition.
　本発明者らは、前記課題を解決するために鋭意検討した結果、環化触媒として使用したリン酸ステアリル又はその由来成分（ステアリルアルコール等）のロール表面への付着が汚染の原因であったこと、そしてリン酸、亜リン酸、次亜リン酸等と低級又は中級の脂肪族アルコール（特に炭素数３以上１２以下の脂肪族アルコール）とから得られるエステルを環化触媒とすると、環化工程では触媒が安定であって触媒使用量を低減でき、シルバーストリークの発生が抑制されるとともに安定性に優れた（メタ）アクリル系樹脂組成物を得られること、またリン酸、亜リン酸、次亜リン酸等と低級又は中級の脂肪族アルコールとから得られるエステルを環化触媒とすると、脱揮工程で触媒が揮散して除去されやすく、さらには分解して発生する低級又は中級の脂肪族アルコールについても脱揮工程で除去されるため環化触媒によるロール汚染が低減されることを見出し、本発明を完成した。
　すなわち本発明は、以下の構成要件によって特定される。
［１］　主鎖にラクトン環構造及び無水グルタル酸構造の少なくとも一方である環構造を有する（メタ）アクリル系重合体を含む（メタ）アクリル系樹脂組成物であって、
　（メタ）アクリル系樹脂組成物中のリン原子の含有量が、１．０ｐｐｍ以上５０ｐｐｍ以下であり、
　（メタ）アクリル系樹脂組成物中の下記式（Ｉ）で表される化合物の含有量が、９５ｐｐｍ以下であることを特徴とする（メタ）アクリル系樹脂組成物。
Figure JPOXMLDOC01-appb-C000003
［式（Ｉ）中、Ｒ1は炭素数１３以上の脂肪族炭化水素基、又は炭素数６以上の芳香族炭化水素基を表す。］
［２］　（メタ）アクリル系樹脂組成物中の下記式（ＩＩ）で表される化合物の含有量が、９５ｐｐｍ以下である［１］に記載の（メタ）アクリル系樹脂組成物。
Figure JPOXMLDOC01-appb-C000004
［式（ＩＩ）中、Ｒ2は炭素数３以上１２以下の脂肪族炭化水素基を表す。］
［３］　環構造を有する（メタ）アクリル系重合体における環構造単位の含有割合が、５質量％以上７０質量％以下である［１］又は［２］に記載の（メタ）アクリル系樹脂組成物。
［４］　（メタ）アクリル系樹脂組成物中の環構造を有する（メタ）アクリル系重合体の含有量が、５０質量％以上である［１］～［３］のいずれかに記載の（メタ）アクリル系樹脂組成物。
［５］　ガラス転移温度が１２０℃以上である［１］～［４］のいずれかに記載の（メタ）アクリル系樹脂組成物。
［６］　ヒンダードフェノール化合物を含まない［１］～［５］のいずれかにに記載の（メタ）アクリル系樹脂組成物。
［７］　ヒンダードフェノール部位を有する有機リン化合物を含まない［１］～［６］のいずれかに記載の（メタ）アクリル系樹脂組成物。
［８］　［１］～［７］のいずれかに記載の（メタ）アクリル系樹脂組成物を含む成形体。
［９］　シート、フィルム又はレンズ状である［８］に記載の成形体。
［１０］　（メタ）アクリル系重合体において、下記（ｉ）及び（ｉｉ）の環化反応のうち少なくとも片方の環化反応を行い、前記（メタ）アクリル系重合体の主鎖に環構造を形成する環化工程を含む（メタ）アクリル系樹脂組成物の製造方法であって、
　（ｉ）ヒドロキシ基と、エステル基又はカルボキシル基との間で、ラクトン環構造を形成する環化反応
　（ｉｉ）カルボキシル基と、エステル基又は他のカルボキシル基との間で、無水グルタル酸構造を形成する環化反応
　前記環化反応において、リン酸Ｃ3-12アルキルエステル、亜リン酸Ｃ3-12アルキルエステル、及び次亜リン酸Ｃ3-12アルキルエステルからなる群から選ばれる少なくとも１種を触媒として用いることを特徴とする（メタ）アクリル系樹脂組成物の製造方法。
［１１］　前記環化反応で用いられる前記触媒が、リン酸Ｃ3-７アルキルエステル、亜リン酸Ｃ3-７アルキルエステル、及び次亜リン酸Ｃ3-７アルキルエステルからなる群から選ばれる少なくとも１種である［１０］に記載の（メタ）アクリル系樹脂組成物の製造方法。
［１２］　前記環化反応で用いられる前記触媒が、リン酸ブチル、亜リン酸ブチル、及び次亜リン酸ブチルからなる群から選ばれる少なくとも１種である［１０］又は［１１］に記載の（メタ）アクリル系樹脂組成物の製造方法。
［１３］　前記触媒の使用量が、前記（メタ）アクリル系重合体を構成する単量体成分の全量に対して１０００ｐｐｍ以下である［１０］～［１２］のいずれかに記載の（メタ）アクリル系樹脂組成物の製造方法。
［１４］　前記触媒の分解温度が１６０℃以上である［１０］～［１３］のいずれかに記載の（メタ）アクリル系樹脂組成物の製造方法。
［１５］　（メタ）アクリル系モノマーを重合して前記（メタ）アクリル系重合体を形成する重合工程をさらに含む［１０］～［１４］のいずれかに記載の（メタ）アクリル系樹脂組成物の製造方法。
［１６］　前記（メタ）アクリル系重合体の全構成単位における前記（メタ）アクリル系モノマーに由来する構成単位の合計含有割合が、５０質量％以上である［１５］に記載の（メタ）アクリル系樹脂組成物の製造方法。
［１７］　前記（メタ）アクリル系モノマーとしてα－（１－ヒドロキシアルキル）アクリル酸アルキルを有し、前記（メタ）アクリル系重合体の全構成単位における前記α－（１－ヒドロキシアルキル）アクリル酸アルキルに由来する構成単位の合計含有割合が、５質量％以上である［１５］又は［１６］に記載の（メタ）アクリル系樹脂組成物の製造方法。
［１８］　前記重合工程、前記環化工程、及び前記環化工程の後の工程から選ばれる１つ以上の工程で添加剤が添加され、
　前記添加剤は、ヒンダードフェノール化合物及びヒンダードフェノール部位を有する有機リン化合物を含まない、［１５］～［１７］のいずれかに記載の（メタ）アクリル系樹脂組成物の製造方法。 As a result of intensive studies to solve the above problems, the present inventors found that the contamination was caused by the adhesion of stearyl phosphate used as a cyclization catalyst or a component derived therefrom (stearyl alcohol, etc.) to the surface of the roll. , And when an ester obtained from phosphoric acid, phosphorous acid, hypophosphorous acid, etc. and a lower or intermediate aliphatic alcohol (especially an aliphatic alcohol having 3 to 12 carbon atoms) is used as a cyclization catalyst, the cyclization step In , the catalyst is stable, the amount of catalyst used can be reduced, the generation of silver streaks is suppressed, and a (meth)acrylic resin composition with excellent stability can be obtained. When an ester obtained from phosphorous acid or the like and a lower or intermediate aliphatic alcohol is used as a cyclization catalyst, the catalyst is easily volatilized and removed in the devolatilization process, and furthermore, the lower or intermediate aliphatic alcohol generated by decomposition Since the alcohol is also removed in the devolatilization step, the inventors have found that the contamination of the rolls by the cyclization catalyst can be reduced, and completed the present invention.
That is, the present invention is specified by the following constituent requirements.
[1] A (meth)acrylic resin composition comprising a (meth)acrylic polymer having a ring structure that is at least one of a lactone ring structure and a glutaric anhydride structure in the main chain,
The content of phosphorus atoms in the (meth)acrylic resin composition is 1.0 ppm or more and 50 ppm or less,
A (meth)acrylic resin composition, wherein the content of a compound represented by the following formula (I) in the (meth)acrylic resin composition is 95 ppm or less.
Figure JPOXMLDOC01-appb-C000003
[In Formula (I), R 1 represents an aliphatic hydrocarbon group having 13 or more carbon atoms or an aromatic hydrocarbon group having 6 or more carbon atoms. ]
[2] The (meth)acrylic resin composition according to [1], wherein the content of the compound represented by the following formula (II) in the (meth)acrylic resin composition is 95 ppm or less.
Figure JPOXMLDOC01-appb-C000004
[In Formula (II), R 2 represents an aliphatic hydrocarbon group having 3 or more and 12 or less carbon atoms. ]
[3] The (meth)acrylic resin composition according to [1] or [2], wherein the content of the ring structural unit in the (meth)acrylic polymer having a ring structure is 5% by mass or more and 70% by mass or less. thing.
[4] The (meth)acrylic polymer according to any one of [1] to [3], wherein the content of the (meth)acrylic polymer having a ring structure in the (meth)acrylic resin composition is 50% by mass or more. ) acrylic resin composition.
[5] The (meth)acrylic resin composition according to any one of [1] to [4], which has a glass transition temperature of 120° C. or higher.
[6] The (meth)acrylic resin composition according to any one of [1] to [5], which does not contain a hindered phenol compound.
[7] The (meth)acrylic resin composition according to any one of [1] to [6], which does not contain an organophosphorus compound having a hindered phenol moiety.
[8] A molded article containing the (meth)acrylic resin composition according to any one of [1] to [7].
[9] The molded article according to [8], which is in the form of a sheet, film or lens.
[10] In the (meth)acrylic polymer, at least one of the following cyclization reactions (i) and (ii) is performed to form a ring structure in the main chain of the (meth)acrylic polymer. A method for producing a (meth)acrylic resin composition comprising a cyclization step of forming,
(i) a cyclization reaction to form a lactone ring structure between a hydroxy group and an ester group or a carboxyl group; (ii) a glutaric anhydride structure between a carboxyl group and an ester group or another carboxyl group; Cyclization reaction to form In the cyclization reaction, at least one selected from the group consisting of C 3-12 alkyl phosphate, C 3-12 alkyl phosphite, and C 3-12 hypophosphite As a catalyst, a method for producing a (meth)acrylic resin composition.
[11] The catalyst used in the cyclization reaction is selected from the group consisting of C 3-7 alkyl phosphate, C 3-7 alkyl phosphite and C 3-7 hypophosphite. The method for producing the (meth)acrylic resin composition according to [10], which is at least one.
[12] The catalyst according to [10] or [11], wherein the catalyst used in the cyclization reaction is at least one selected from the group consisting of butyl phosphate, butyl phosphite, and butyl hypophosphite. A method for producing a (meth)acrylic resin composition.
[13] The (meth)acrylic polymer according to any one of [10] to [12], wherein the amount of the catalyst used is 1000 ppm or less with respect to the total amount of the monomer components constituting the (meth)acrylic polymer. A method for producing an acrylic resin composition.
[14] The method for producing a (meth)acrylic resin composition according to any one of [10] to [13], wherein the decomposition temperature of the catalyst is 160°C or higher.
[15] The (meth)acrylic resin composition according to any one of [10] to [14], further comprising a polymerization step of polymerizing a (meth)acrylic monomer to form the (meth)acrylic polymer. manufacturing method.
[16] The (meth)acrylic according to [15], wherein the total content of structural units derived from the (meth)acrylic monomer in all structural units of the (meth)acrylic polymer is 50% by mass or more. A method for producing a resin composition.
[17] Having α-(1-hydroxyalkyl)alkyl acrylate as the (meth)acrylic monomer, and the α-(1-hydroxyalkyl)acrylic acid in all structural units of the (meth)acrylic polymer The method for producing a (meth)acrylic resin composition according to [15] or [16], wherein the total content of structural units derived from alkyl is 5% by mass or more.
[18] an additive is added in one or more steps selected from the polymerization step, the cyclization step, and a step after the cyclization step;
The method for producing a (meth)acrylic resin composition according to any one of [15] to [17], wherein the additive does not contain a hindered phenol compound or an organic phosphorus compound having a hindered phenol moiety.
　本発明によれば、ロール汚染を低減でき、さらにはシルバーストリークの発生が抑制されるとともに安定性に優れた（メタ）アクリル系樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a (meth)acrylic resin composition that can reduce roll contamination, suppress the generation of silver streaks, and has excellent stability.
　１．　（メタ）アクリル系樹脂組成物
　本発明の（メタ）アクリル系樹脂組成物は、主鎖にラクトン環構造及び無水グルタル酸構造の少なくとも一方である環構造を有する（メタ）アクリル系重合体を含み、組成物中のリン原子の含有量が、１．０ｐｐｍ以上５０ｐｐｍ以下であり、且つ組成物中の下記式（Ｉ）で表される化合物の含有量が、９５ｐｐｍ以下であることを特徴とする。本発明の（メタ）アクリル系樹脂組成物は、前記構成要件を有することから、ロール汚染を低減でき、さらにはシルバーストリークの発生が抑制されるとともに安定性に優れている。 1. (Meth)acrylic resin composition The (meth)acrylic resin composition of the present invention contains a (meth)acrylic polymer having a ring structure that is at least one of a lactone ring structure and a glutaric anhydride structure in the main chain. , the content of phosphorus atoms in the composition is 1.0 ppm or more and 50 ppm or less, and the content of the compound represented by the following formula (I) in the composition is 95 ppm or less. . Since the (meth)acrylic resin composition of the present invention has the above constituent elements, it is possible to reduce roll contamination, suppress the generation of silver streaks, and have excellent stability.
Figure JPOXMLDOC01-appb-C000005
［式（Ｉ）中、Ｒ1は炭素数１３以上の脂肪族炭化水素基、又は炭素数６以上の芳香族炭化水素基を表す。］
Figure JPOXMLDOC01-appb-C000005
[In Formula (I), R 1 represents an aliphatic hydrocarbon group having 13 or more carbon atoms or an aromatic hydrocarbon group having 6 or more carbon atoms. ]
　本発明において特に記載がない限り、「ｐｐｍ」との記載は質量換算で求められる値を意味する（例えば、１０，０００ｐｐｍは１質量％に該当する）。また、「Ｃ3-12」との記載は「炭素数３以上１２以下」を意味する。 Unless otherwise specified in the present invention, the description "ppm" means a value calculated in terms of mass (for example, 10,000 ppm corresponds to 1% by mass). Moreover, the description of " C3-12 " means "3 or more and 12 or less carbon atoms."
　１．１　（メタ）アクリル系重合体
　（メタ）アクリル系重合体は、（メタ）アクリル酸、（メタ）アクリル酸エステル、又はこれらの誘導体（以下、これらを総称して（メタ）アクリル系モノマーと称する場合がある）を単量体単位（つまり、構成単位）として有する重合体を意味する。なお、「（メタ）アクリル酸」はアクリル酸とメタクリル酸との両方を包含する用語とする。 1.1 (Meth)acrylic polymer The (meth)acrylic polymer is (meth)acrylic acid, (meth)acrylic acid ester, or derivatives thereof (hereinafter collectively referred to as (meth)acrylic monomer (sometimes referred to as ) as a monomer unit (that is, a structural unit). The term "(meth)acrylic acid" includes both acrylic acid and methacrylic acid.
　（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸２－エチルヘキシル等の（メタ）アクリル酸アルキル；（メタ）アクリル酸ベンジル等の（メタ）アクリル酸アラルキル（好ましくはメタクリル酸Ｃ2-20アラルキル）；（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ジシクロペンタニル等の（メタ）アクリル酸とヒドロキシ環状飽和炭化水素（好ましくは炭素数が５以上２０以下のヒドロキシ環状飽和炭化水素）とのエステル等が挙げられる。（メタ）アクリル酸エステルとしては、好ましくはメタクリル酸エステルであり、より好ましくはメタクリル酸アルキルであり、さらに好ましくはメタクリル酸Ｃ1-10アルキルであり、よりさらに好ましくはメタクリル酸Ｃ1-7アルキルであり、いっそう好ましくはメタクリル酸Ｃ1-4アルキルであり、特に好ましくはメタクリル酸Ｃ1-2アルキルである。 Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, t-(meth)acrylate, Alkyl (meth)acrylates such as butyl, n-hexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate (preferably C 2- methacrylate); 20 aralkyl); (meth)acrylic acid such as cyclohexyl (meth)acrylate and dicyclopentanyl (meth)acrylate and hydroxy cyclic saturated hydrocarbon (preferably hydroxy cyclic saturated hydrocarbon having 5 to 20 carbon atoms) and the like. The (meth)acrylic acid ester is preferably a methacrylic acid ester, more preferably an alkyl methacrylate, still more preferably a C 1-10 alkyl methacrylate, still more preferably a C 1-7 alkyl methacrylate and more preferably C 1-4 alkyl methacrylate, particularly preferably C 1-2 alkyl methacrylate.
　（メタ）アクリル酸エステル誘導体としては、ヒドロキシ基導入誘導体、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２，３，４，５，６－ペンタヒドロキシヘキシル、（メタ）アクリル酸２，３，４，５－テトラヒドロキシペンチル等の（メタ）アクリル酸ヒドロキシアルキル；α－（１－ヒドロキシアルキル）アクリル酸アルキル等が挙げられる。 (Meth)acrylic acid ester derivatives include hydroxy group-introduced derivatives such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3,4,5 (meth)acrylate, Hydroxyalkyl (meth)acrylates such as 6-pentahydroxyhexyl and 2,3,4,5-tetrahydroxypentyl (meth)acrylate; and α-(1-hydroxyalkyl)alkyl acrylates.
　（メタ）アクリル酸ヒドロキシアルキルとしては、（メタ）アクリル酸ヒドロキシＣ1-20アルキルが好ましく、（メタ）アクリル酸ヒドロキシＣ1-15アルキルがより好ましく、（メタ）アクリル酸ヒドロキシＣ1-10アルキルがさらに好ましく、（メタ）アクリル酸ヒドロキシＣ1-5アルキルがよりさらに好ましい。 The hydroxyalkyl (meth)acrylate is preferably hydroxyC 1-20 alkyl (meth)acrylate, more preferably hydroxyC 1-15 alkyl (meth)acrylate, and hydroxyC 1-10 alkyl (meth)acrylate. is more preferred, and hydroxy C 1-5 alkyl (meth)acrylate is even more preferred.
　α－（１－ヒドロキシアルキル）アクリル酸アルキルとしては、α－（１－ヒドロキシＣ1-20アルキル）アクリル酸Ｃ1-20アルキルが好ましく、α－（１－ヒドロキシＣ1-20アルキル）アクリル酸Ｃ1-20アルキルには、α－（ヒドロキシメチル）アクリル酸メチル、α－（ヒドロキシメチル）アクリル酸エチル、α－（ヒドロキシメチル）アクリル酸イソプロピル、α－（ヒドロキシメチル）アクリル酸ｎ－ブチル、α－（ヒドロキシメチル）アクリル酸ｔ－ブチル等のα－（ヒドロキシメチル）アクリル酸Ｃ1-20アルキル；α－（１－ヒドロキシエチル）アクリル酸メチル等のα－（１－ヒドロキシＣ2-20アルキル）アクリル酸Ｃ1-20アルキル等が含まれる。 The alkyl α-(1-hydroxyalkyl) acrylate is preferably C 1-20 alkyl α-(1 - hydroxyC 1-20 alkyl) acrylate, and α-(1-hydroxyC 1-20 alkyl) acrylate. C 1-20 alkyl includes methyl α-(hydroxymethyl)acrylate, ethyl α-(hydroxymethyl)acrylate, isopropyl α-(hydroxymethyl)acrylate, n-butyl α-(hydroxymethyl)acrylate, C 1-20 alkyl α-(hydroxymethyl)acrylate such as t-butyl α-(hydroxymethyl)acrylate; α-(1-hydroxyC 2-20 alkyl such as methyl α-(1-hydroxyethyl)acrylate alkyl) C 1-20 alkyl acrylates and the like are included.
　また（メタ）アクリル酸エステル誘導体としては、クロトン酸メチル等のβ－Ｃ1-10アルキルアクリル酸Ｃ1-10アルキル；（メタ）アクリル酸クロロメチル、（メタ）アクリル酸２－クロロエチル等のハロゲン導入誘導体；（メタ）アクリル酸ジシクロペンタニルオキシエチル等のエーテル結合導入誘導体等も含まれる。 (Meth)acrylic acid ester derivatives include β-C 1-10 alkyl acrylate such as methyl crotonate; halogens such as chloromethyl (meth)acrylate and 2-chloroethyl (meth)acrylate; Introduced derivatives: Also included are ether bond-introduced derivatives such as dicyclopentanyloxyethyl (meth)acrylate.
　（メタ）アクリル酸エステル誘導体としては、好ましくはヒドロキシ基導入誘導体であり、より好ましくはα－（１－ヒドロキシアルキル）アクリル酸アルキルであり、さらに好ましくはα－（１－ヒドロキシＣ1-20アルキル）アクリル酸Ｃ1-20アルキルであり、よりさらに好ましくはα－（ヒドロキシメチル）アクリル酸Ｃ1-20アルキルである。 The (meth)acrylic acid ester derivative is preferably a hydroxy group-introduced derivative, more preferably α-(1-hydroxyalkyl) alkyl acrylate, still more preferably α-(1-hydroxyC 1-20 alkyl ) C 1-20 alkyl acrylate, more preferably C 1-20 alkyl α-(hydroxymethyl)acrylate.
　（メタ）アクリル酸誘導体としては、前記メタクリル酸エステル誘導体のエステル結合を加水分解した化合物、例えば、クロトン酸、α－（ヒドロキシメチル）アクリル酸、２－（１－ヒドロキシエチル）アクリル酸等のα－ヒドロキシアルキルアクリル酸等が含まれる。 (Meth)acrylic acid derivatives include compounds obtained by hydrolyzing the ester bond of the methacrylic acid ester derivative, such as crotonic acid, α-(hydroxymethyl)acrylic acid, 2-(1-hydroxyethyl)acrylic acid, and the like. - hydroxyalkyl acrylic acid and the like.
　（メタ）アクリル系重合体が単量体単位として有する（メタ）アクリル系モノマーは、単独であってもよく、２種以上の組み合わせであってもよい。（メタ）アクリル系モノマーのうち（メタ）アクリル酸又は（メタ）アクリル酸エステルを必須単位として含むのが好ましく、（メタ）アクリル酸エステル（特にメタクリル酸エステル）を必須単位として含むのがより好ましい。前記必須単位の含有割合は、（メタ）アクリル系重合体中、例えば、３０質量％以上、好ましくは５０質量％以上、より好ましくは６０質量％以上、さらに好ましくは６５質量％以上、よりさらに好ましくは７０質量％以上、特に好ましくは７５質量％以上であり、例えば、１００質量％以下、好ましくは９５質量％以下、より好ましくは９０質量％以下、さらに好ましくは８５質量％以下である。なお（メタ）アクリル系重合体が、後述する環化反応等によって異なる単位になった（メタ）アクリル系モノマーに由来する単位を有する場合には、前記含有割合における（メタ）アクリル系モノマー単位の割合には、該異なる単位になった（メタ）アクリル系モノマーに由来する単位は含まないものとする。 The (meth)acrylic monomer that the (meth)acrylic polymer has as a monomer unit may be used alone or in combination of two or more. Among (meth)acrylic monomers, it preferably contains (meth)acrylic acid or (meth)acrylic acid ester as an essential unit, and more preferably contains (meth)acrylic acid ester (especially methacrylic acid ester) as an essential unit. . The content of the essential unit in the (meth)acrylic polymer is, for example, 30% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, and even more preferably is 70% by mass or more, particularly preferably 75% by mass or more, and is, for example, 100% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. Note that when the (meth)acrylic polymer has units derived from (meth)acrylic monomers that have become different units due to the cyclization reaction described later, etc., the proportion of (meth)acrylic monomer units in the above content ratio The ratio does not include the unit derived from the (meth)acrylic monomer that has become the different unit.
　（メタ）アクリル系重合体は、前記（メタ）アクリル系モノマーを他のモノマーと共重合することによって導入される構成単位を有していてもよい。このような他のモノマーとしては、重合性二重結合を有する化合物であれば特に限定されず、例えば、スチレン、ビニルトルエン、α－メチルスチレン、α－ヒドロキシメチルスチレン、α－ヒドロキシエチルスチレン等のスチレン系モノマー；Ｎ－ビニルピロリドン、Ｎ－ビニルカルバゾール等の含窒素複素環系ビニル化合物；アクリロニトリル、メタクリロニトリル等のビニルニトリル類；メタリルアルコール、アリルアルコール等のビニルアルコール類；エチレン、プロピレン、４－メチル－１－ペンテン等のオレフィン類；マレイン酸、フマル酸、クロトン酸、イタコン酸、シトラコン酸、マレイン酸モノメチルエステル、マレイン酸モノブチルエステル、イタコン酸モノメチルエステル、イタコン酸モノブチルエステル等のカルボキシル基含有エチレン性単官能モノマー；酢酸ビニル；２－ヒドロキシメチル－１－ブテン；メチルビニルケトン；等が挙げられる。他のモノマーとしては、スチレン系モノマー、含窒素複素環系ビニル化合物、カルボキシル基含有エチレン性単官能モノマーが好ましく、スチレン系モノマー、カルボキシル基含有エチレン性単官能モノマーがより好ましく、スチレン系モノマーがさらに好ましい。これら他のモノマー（構成単位）は１種のみを有していてもよいし２種以上を有していてもよい。他のモノマー（構成単位）は、（メタ）アクリル系重合体中、例えば、０質量％以上、好ましくは１質量％以上であり、例えば、３０質量％以下、好ましくは２０質量％以下、より好ましくは１０質量％以下、さらに好ましくは５質量％以下である。 The (meth)acrylic polymer may have a structural unit introduced by copolymerizing the (meth)acrylic monomer with another monomer. Such other monomers are not particularly limited as long as they are compounds having a polymerizable double bond. Examples include styrene, vinyltoluene, α-methylstyrene, α-hydroxymethylstyrene, α-hydroxyethylstyrene, and the like. Styrenic monomers; nitrogen-containing heterocyclic vinyl compounds such as N-vinylpyrrolidone and N-vinylcarbazole; vinyl nitriles such as acrylonitrile and methacrylonitrile; vinyl alcohols such as methallyl alcohol and allyl alcohol; ethylene, propylene, Olefins such as 4-methyl-1-pentene; Maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, monomethyl maleate, monobutyl maleate, monomethyl itaconate, monobutyl itaconate, etc. carboxyl group-containing ethylenic monofunctional monomer; vinyl acetate; 2-hydroxymethyl-1-butene; methyl vinyl ketone; As other monomers, styrene-based monomers, nitrogen-containing heterocyclic vinyl compounds, and carboxyl group-containing ethylenic monofunctional monomers are preferred, styrene-based monomers and carboxyl group-containing ethylenic monofunctional monomers are more preferred, and styrene-based monomers are further preferred. preferable. These other monomers (constituent units) may have only one type or may have two or more types. Other monomers (constituent units) in the (meth)acrylic polymer are, for example, 0% by mass or more, preferably 1% by mass or more, for example, 30% by mass or less, preferably 20% by mass or less, more preferably is 10% by mass or less, more preferably 5% by mass or less.
　（メタ）アクリル系重合体の全構成単位における、（メタ）アクリル系モノマーに由来する構成単位（すなわち、（メタ）アクリル酸単位、（メタ）アクリル酸エステル単位、及びこれらの誘導体に由来する構成単位）の合計含有割合は、成形体の透明性の観点から、５０質量％以上が好ましく、より好ましくは６０質量％以上、さらに好ましくは７０質量％以上、よりさらに好ましくは７５質量％以上である。上限は特になく、１００質量％であってもよい。また後述する環化反応によって異なる単位になった（メタ）アクリル系モノマーに由来する単位を有する（メタ）アクリル系重合体（つまり、環構造を有する（メタ）アクリル系重合体）については、環構造を有する（メタ）アクリル系重合体の全構成単位における、（メタ）アクリル系モノマーに由来する構成単位の合計含有割合は、３０質量％以上が好ましく、より好ましくは５０質量％以上、さらに好ましくは６０質量％以上、よりさらに好ましくは７０質量％以上、特に好ましくは７５質量％以上であり、９９質量％以下が好ましく、より好ましくは９５質量％以下であり、さらに好ましくは９０質量％以下であり、よりさらに好ましくは８５質量％以下である。 Structural units derived from (meth)acrylic monomers in all structural units of the (meth)acrylic polymer (i.e., (meth)acrylic acid units, (meth)acrylic acid ester units, and structures derived from derivatives thereof unit) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and even more preferably 75% by mass or more, from the viewpoint of transparency of the molded article. . There is no particular upper limit, and it may be 100% by mass. In addition, for a (meth)acrylic polymer having a unit derived from a (meth)acrylic monomer that has become a different unit due to the cyclization reaction described later (that is, a (meth)acrylic polymer having a ring structure), The total content of structural units derived from (meth)acrylic monomers in all structural units of the (meth)acrylic polymer having a structure is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably is 60% by mass or more, more preferably 70% by mass or more, particularly preferably 75% by mass or more, preferably 99% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less. Yes, more preferably 85% by mass or less.
　（メタ）アクリル系重合体の全構成単位における、（メタ）アクリル酸エステルのヒドロキシ基導入誘導体（好ましくはα－（１－ヒドロキシアルキル）アクリル酸アルキル）に由来する構成単位の合計含有割合は、１質量％以上が好ましく、より好ましくは５質量％以上であり、さらに好ましくは８質量％以上であり、よりさらに好ましくは１０質量％以上であり、７０質量％以下が好ましく、より好ましくは５０質量％以下であり、さらに好ましくは３０質量％以下である。また後述する環化反応によって異なる単位になった（メタ）アクリル系モノマーに由来する単位を有する（メタ）アクリル系重合体（つまり、環構造を有する（メタ）アクリル系重合体）については、環構造を有する（メタ）アクリル系重合体の全構成単位における、（メタ）アクリル酸エステルのヒドロキシ基導入誘導体に由来する構成単位の合計含有割合は、０質量％であってもよく、１０質量％以下が好ましく、より好ましくは８質量％以下であり、さらに好ましくは５質量％以下である。 The total content of structural units derived from a hydroxy group-introduced derivative of a (meth)acrylic acid ester (preferably α-(1-hydroxyalkyl) alkyl acrylate) in all structural units of the (meth)acrylic polymer is It is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, even more preferably 10% by mass or more, preferably 70% by mass or less, more preferably 50% by mass. % or less, more preferably 30 mass % or less. In addition, for a (meth)acrylic polymer having a unit derived from a (meth)acrylic monomer that has become a different unit due to the cyclization reaction described later (that is, a (meth)acrylic polymer having a ring structure), The total content of structural units derived from a hydroxy group-introduced derivative of a (meth)acrylic acid ester in all structural units of the (meth)acrylic polymer having a structure may be 0% by mass or 10% by mass. The following is preferable, more preferably 8% by mass or less, and even more preferably 5% by mass or less.
　主鎖にラクトン環構造及び無水グルタル酸構造の少なくとも一方である環構造を有する（メタ）アクリル系重合体は、例えば、ヒドロキシ基、エステル基、及び／又はカルボキシル基を有する（メタ）アクリル系重合体において、後述する環化反応を行うことにより形成できる。 A (meth)acrylic polymer having a ring structure that is at least one of a lactone ring structure and a glutaric anhydride structure in the main chain is, for example, a (meth)acrylic polymer having a hydroxy group, an ester group, and/or a carboxyl group. In coalescence, it can be formed by performing a cyclization reaction, which will be described later.
　ラクトン環構造としては、例えば、ラクトン環構造を形成し易いことから４員環以上８員環以下が好ましく、環構造の安定性に優れることから５員環又は６員環であることがより好ましく、６員環であることがさらに好ましい。６員環のラクトン環構造としては、例えば、下記式（１）に示される構造が挙げられる。 As the lactone ring structure, for example, a 4- to 8-membered ring is preferable because the lactone ring structure is easily formed, and a 5- or 6-membered ring is more preferable because the stability of the ring structure is excellent. , is more preferably a 6-membered ring. Examples of the six-membered lactone ring structure include structures represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　上記式（１）において、Ｒ1a、Ｒ2a及びＲ3aは、互いに独立して、水素原子又は炭素数が１以上２０以下の有機残基であり、当該有機残基は酸素原子を含んでいてもよい。
　式（１）における有機残基としては、例えば、置換基を有していてもよい炭素数１以上２０以下の炭化水素基等が挙げられる。当該炭化水素基としては、飽和又は不飽和の直鎖状、分岐状又は環状の脂肪族炭化水素基や芳香族炭化水素基が挙げられる。脂肪族炭化水素基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基等の炭素数１以上２０以下のアルキル基（好ましくは炭素数１以上１０以下のアルキル基であり、より好ましくは炭素数１以上６以下のアルキル基）；エテニル基、プロペニル基等の炭素数２以上２０以下のアルケニル基（好ましくは炭素数２以上１０以下のアルケニル基であり、より好ましくは炭素数２以上６以下のアルケニル基）；シクロペンチル基、シクロヘキシル基等の炭素数３以上２０以下のシクロアルキル基（好ましくは炭素数４以上１２以下のシクロアルキル基であり、より好ましくは炭素数５以上８以下のシクロアルキル基）；等が挙げられる。芳香族炭化水素基としては、例えば、フェニル基、トリル基、キシリル基、ナフチル基、ビフェニル基等の炭素数６以上２０以下のアリール基（好ましくは炭素数６以上１４以下のアリール基であり、より好ましくは炭素数６以上１０以下のアリール基）；ベンジル基、フェニルエチル基等の炭素数７以上２０以下のアラルキル基（好ましくは炭素数７以上１５以下のアラルキル基であり、より好ましくは炭素数７以上１１以下のアラルキル基）；等が挙げられる。これらの炭化水素基は酸素原子やハロゲン原子を含んでいてもよく、具体的には、炭化水素基の有する水素原子の１つ以上が、ヒドロキシ基、カルボキシル基、エーテル基、及びエステル基から選ばれる少なくとも１種の基により置換されていてもよい。 In the above formula (1), R 1a , R 2a and R 3a are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue contains an oxygen atom. good too.
Examples of the organic residue in formula (1) include a hydrocarbon group optionally having a substituent and having 1 to 20 carbon atoms. Examples of the hydrocarbon group include saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Examples of the aliphatic hydrocarbon group include alkyl groups having 1 to 20 carbon atoms (preferably alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, etc.). preferably an alkyl group having 1 to 6 carbon atoms); an alkenyl group having 2 to 20 carbon atoms such as an ethenyl group and a propenyl group (preferably an alkenyl group having 2 to 10 carbon atoms, more preferably 2 cycloalkyl group having 3 to 20 carbon atoms (preferably a cycloalkyl group having 4 to 12 carbon atoms, more preferably 5 to 8 carbon atoms, such as a cyclopentyl group and a cyclohexyl group); cycloalkyl group); and the like. Examples of the aromatic hydrocarbon group include aryl groups having 6 to 20 carbon atoms (preferably aryl groups having 6 to 14 carbon atoms, such as phenyl, tolyl, xylyl, naphthyl, and biphenyl groups, more preferably an aryl group having 6 to 10 carbon atoms); an aralkyl group having 7 to 20 carbon atoms such as a benzyl group and a phenylethyl group (preferably an aralkyl group having 7 to 15 carbon atoms; an aralkyl group having a number of 7 or more and 11 or less); These hydrocarbon groups may contain an oxygen atom or a halogen atom. Specifically, one or more hydrogen atoms of the hydrocarbon group are selected from hydroxy, carboxyl, ether and ester may be substituted by at least one group represented by
　式（１）に示されるラクトン環構造において、耐熱性に優れる（メタ）アクリル系重合体を得ることが容易な点から、Ｒ1a、Ｒ2aとしては、互いに独立して、水素原子又は炭素数１以上２０以下のアルキル基であることが好ましく、水素原子又はメチル基であることがより好ましく、Ｒ3aとしては、水素原子又はメチル基であることが好ましく、メチル基であることがより好ましい。 In the lactone ring structure represented by formula (1), since it is easy to obtain a (meth)acrylic polymer having excellent heat resistance, R 1a and R 2a each independently have a hydrogen atom or a carbon number It is preferably an alkyl group of 1 to 20, more preferably a hydrogen atom or a methyl group, and R 3a is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
　（メタ）アクリル系重合体は、ラクトン環構造を１種のみ有していてもよく、２種以上有していてよい。 The (meth)acrylic polymer may have only one type of lactone ring structure, or may have two or more types.
　（メタ）アクリル系重合体が主鎖にラクトン環構造を有する場合、当該重合体におけるラクトン環構造の含有割合は、例えば、１質量％以上、好ましくは５質量％以上、より好ましくは１０質量％以上であり、例えば、７０質量％以下、好ましくは５０質量％以下、より好ましくは３０質量％以下である。 When the (meth)acrylic polymer has a lactone ring structure in the main chain, the content of the lactone ring structure in the polymer is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass. For example, it is 70% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.
　なお（メタ）アクリル系重合体におけるラクトン環構造の含有割合は、ラクトン環化に関与する単量体（後述する（ｉ）の環化反応の場合におけるヒドロキシ基含有（メタ）アクリル系モノマーＡ及び（メタ）アクリル系モノマーＢ）の重合量と、ラクトン環化率とから下記式により、算出できる。
　　ラクトン環構造の含有割合（質量％）＝Ｚ1×Ｚ2×ＭＲ／Ｍｍ
　（式中、Ｚ1は、ラクトン環化前の重合体における、ラクトン環化に関与する原料単量体（後述する（ｉ）の環化反応の場合におけるヒドロキシ基含有（メタ）アクリル系モノマーＡ及び（メタ）アクリル系モノマーＢ）由来の構造単位の質量含有割合であり、ＭＲは生成するラクトン環構造単位の式量（ラクトン環形成元素と、ラクトン環に結合する主鎖以外の基の合計式量の意味）であり、Ｍｍはラクトン環化に関与する原料単量体（後述する（ｉ）の環化反応の場合におけるヒドロキシ基含有（メタ）アクリル系モノマーＡ及び（メタ）アクリル系モノマーＢ）の分子量（合計）であり、Ｚ2はラクトン環化率である） The content ratio of the lactone ring structure in the (meth)acrylic polymer is determined by the monomers involved in lactone cyclization (hydroxy group-containing (meth)acrylic monomer A and It can be calculated by the following formula from the polymerization amount of the (meth)acrylic monomer B) and the lactone cyclization rate.
Content ratio of lactone ring structure (% by mass) = Z 1 ×Z 2 ×M R /M m
(In the formula, Z 1 is a raw material monomer involved in lactone cyclization in the polymer before lactone cyclization (hydroxy group-containing (meth)acrylic monomer A in the case of cyclization reaction (i) described later and the mass content ratio of structural units derived from (meth)acrylic monomer B), and MR is the formula weight of the lactone ring structural unit to be produced (the lactone ring-forming element and the number of groups other than the main chain bonded to the lactone ring is the meaning of the total formula weight), and M m is a raw material monomer involved in lactone cyclization (hydroxy group-containing (meth)acrylic monomer A and (meth)acrylic monomer in the case of the cyclization reaction (i) described later. is the molecular weight (total) of the system monomer B), and Z2 is the lactone cyclization rate)
　また（メタ）アクリル系重合体におけるラクトン環構造の含有割合は、公知の方法、例えば、核磁気共鳴（1Ｈ－ＮＭＲ）法、及び／又は赤外分光分析（ＩＲ）法により評価できる。 Also, the content of the lactone ring structure in the (meth)acrylic polymer can be evaluated by known methods such as nuclear magnetic resonance ( 1 H-NMR) method and/or infrared spectroscopy (IR) method.
　無水グルタル酸構造としては、例えば、下記式（２）に示される構造が挙げられる。 Examples of glutaric anhydride structures include structures represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　上記式（２）において、Ｒ4a、Ｒ5aは、互いに独立して、水素原子又は炭素数１以上８以下のアルキル基である。
　式（２）における炭素数１以上８以下のアルキル基としては、直鎖状又は分岐状のアルキル基が好ましく挙げられ、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基等が挙げられる。 In formula (2) above, R 4a and R 5a are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
The alkyl group having 1 to 8 carbon atoms in formula (2) is preferably a linear or branched alkyl group, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, and the like.
　式（２）に示される無水グルタル酸構造において、耐熱性に優れる（メタ）アクリル系重合体を得ることが容易な点から、Ｒ4a、Ｒ5aとしては、互いに独立して、水素原子又は炭素数１以上４以下のアルキル基であることが好ましく、水素原子又はメチル基であることがより好ましい。 In the glutaric anhydride structure represented by the formula (2), since it is easy to obtain a (meth)acrylic polymer having excellent heat resistance, R 4a and R 5a each independently represent a hydrogen atom or a carbon It is preferably an alkyl group having a number of 1 or more and 4 or less, more preferably a hydrogen atom or a methyl group.
　（メタ）アクリル系重合体は、無水グルタル酸構造を１種のみ有していてもよく、２種以上有していてよい。 The (meth)acrylic polymer may have only one type of glutaric anhydride structure, or may have two or more types.
　（メタ）アクリル系重合体が主鎖に無水グルタル酸構造を有する場合、当該重合体における無水グルタル酸構造の含有割合は、例えば、１質量％以上、好ましくは５質量％以上、より好ましくは１０質量％以上であり、例えば、７０質量％以下、好ましくは５０質量％以下、より好ましくは３０質量％以下である。 When the (meth)acrylic polymer has a glutaric anhydride structure in the main chain, the content of the glutaric anhydride structure in the polymer is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more. % by mass or more, for example, 70% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.
　なお（メタ）アクリル系重合体における無水グルタル酸構造の含有割合は、例えば、特開２００６－１３１６８９号公報に記載の手法により求めることができる。 The content of the glutaric anhydride structure in the (meth)acrylic polymer can be determined, for example, by the method described in JP-A-2006-131689.
　（メタ）アクリル系重合体における、環構造単位の含有割合は、５質量％以上が好ましく、８質量％以上がより好ましく、１０質量％以上がさらに好ましく、７０質量％以下が好ましく、５０質量％以下がより好ましく、４５質量％以下がさらに好ましく、３０質量％以下がよりさらに好ましい。環構造単位の含有割合が前記範囲内であることにより、耐熱性に優れ、また機械的強度に優れた（メタ）アクリル系樹脂組成物を得ることができる。なお前記環構造単位の含有割合における環構造単位は、（メタ）アクリル系重合体の主鎖に環構造を有する単位を意味する。 The content of the ring structural unit in the (meth)acrylic polymer is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, preferably 70% by mass or less, and 50% by mass. The following is more preferable, 45% by mass or less is even more preferable, and 30% by mass or less is even more preferable. A (meth)acrylic resin composition having excellent heat resistance and mechanical strength can be obtained by setting the content of the ring structural unit within the above range. The cyclic structural unit in the content ratio of the cyclic structural unit means a unit having a cyclic structure in the main chain of the (meth)acrylic polymer.
　（メタ）アクリル系重合体における環化率は、成形時の発泡抑制の観点から、９５．０質量％以上が好ましく、９５．５質量％以上がより好ましく、９６．０質量以上％がさらに好ましく、９６．５質量％以上がよりさらに好ましい。上限は特になく、１００質量％であってもよい。 The cyclization rate in the (meth)acrylic polymer is preferably 95.0% by mass or more, more preferably 95.5% by mass or more, and even more preferably 96.0% by mass or more, from the viewpoint of suppressing foaming during molding. , 96.5% by mass or more is even more preferable. There is no particular upper limit, and it may be 100% by mass.
　環化率は、例えば、重合で得られた重合体組成からすべてのヒドロキシ基がアルコール又は水として脱アルコール又は脱水した際に起こる質量減少量を基準にし、ダイナミックＴＧ測定において質量減少が始まる前の１５０℃から重合体の分解が始まる前の３００℃までの脱アルコール反応又は脱水反応による質量減少から求めることができる。すなわち、環構造を有した重合体のダイナミックＴＧ測定において１５０℃から３００℃までの間の質量減少率の測定を行い、得られた実測質量減少率を（Ｘ）とする。他方、当該重合体の組成から、その重合体組成に含まれる全ての水酸基が環形成に関与するため脱アルコール又は脱水すると仮定した時の理論質量減少率（すなわち、その組成上において１００％脱アルコール反応又は脱水反応が起きたと仮定して算出した質量減少率）を（Ｙ）とする。なお、理論質量減少率（Ｙ）は、より具体的には、重合体中の脱アルコール反応又は脱水反応に関与する構造（ヒドロキシ基）を有する原料単量体のモル比、すなわち当該重合体組成における前記原料単量体の含有率から算出することができる。これらの値（Ｘ、Ｙ）を式：１－（実測質量減少率（Ｘ）／理論質量減少率（Ｙ））に代入してその値を求め、％で表記すると、環化率（脱アルコール又は脱水反応率）が得られる。 The cyclization rate is, for example, based on the amount of mass reduction that occurs when all hydroxy groups are dealcoholized or dehydrated as alcohol or water from the polymer composition obtained by polymerization, and the amount before the mass reduction starts in dynamic TG measurement. It can be determined from the mass reduction due to the dealcoholization reaction or dehydration reaction from 150° C. to 300° C. before decomposition of the polymer begins. That is, the mass reduction rate is measured from 150° C. to 300° C. in the dynamic TG measurement of a polymer having a ring structure, and the measured mass reduction rate obtained is defined as (X). On the other hand, from the composition of the polymer, the theoretical mass reduction rate when assuming dealcoholization or dehydration because all hydroxyl groups contained in the polymer composition participate in ring formation (i.e., 100% dealcoholization on the composition (Y) is the mass reduction rate calculated on the assumption that a reaction or dehydration reaction has occurred. The theoretical mass reduction rate (Y) is, more specifically, the molar ratio of the raw material monomer having a structure (hydroxy group) involved in the dealcoholization reaction or dehydration reaction in the polymer, that is, the polymer composition It can be calculated from the content of the raw material monomer in. Substituting these values (X, Y) into the formula: 1-(measured mass reduction rate (X)/theoretical mass reduction rate (Y)) to obtain the value and expressing it in %, the cyclization rate (dealcoholization Or dehydration reaction rate) is obtained.
　（メタ）アクリル系重合体の全構成単位における、（メタ）アクリル系モノマーに由来する構成単位（好ましくは（メタ）アクリル酸エステル由来の単位）と環構造単位との合計含有割合は、９０質量％以上が好ましく、９３質量％以上がより好ましく、９５質量％以上がさらに好ましい。これにより、（メタ）アクリル系重合体の透明性や耐熱性を高めることが容易になる。 The total content of structural units derived from (meth)acrylic monomers (preferably units derived from (meth)acrylic acid esters) and ring structural units in all structural units of the (meth)acrylic polymer is 90 mass. % or more is preferred, 93 mass % or more is more preferred, and 95 mass % or more is even more preferred. This facilitates enhancing the transparency and heat resistance of the (meth)acrylic polymer.
　（メタ）アクリル系重合体は、ラクトン環構造及び無水グルタル酸構造の少なくとも一方を環構造として有していればよいが、（メタ）アクリル系樹脂組成物の耐熱性向上や光学特性向上の観点から、ラクトン環構造を有していることがより好ましい。 The (meth)acrylic polymer may have at least one of a lactone ring structure and a glutaric anhydride structure as a ring structure. Therefore, it is more preferable to have a lactone ring structure.
　（メタ）アクリル系重合体の重量平均分子量（Ｍｗ）は、例えば、８．０万以上、好ましくは１０．０万以上、より好ましくは１０．５万以上、さらに好ましくは１１．０万以上であり、例えば、３０．０万以下、好ましくは２５．０万以下、より好ましくは２０．０万以下である。（メタ）アクリル系重合体の重量平均分子量が前記範囲内にあることにより、樹脂としての必要な強度を維持しながら、成形時の流動性も良好な（メタ）アクリル系樹脂組成物を得ることができる。 The weight average molecular weight (Mw) of the (meth)acrylic polymer is, for example, 80,000 or more, preferably 100,000 or more, more preferably 105,000 or more, and still more preferably 110,000 or more. Yes, for example, 300,000 or less, preferably 250,000 or less, more preferably 200,000 or less. To obtain a (meth)acrylic resin composition having good fluidity during molding while maintaining the necessary strength as a resin by having the weight average molecular weight of the (meth)acrylic polymer within the above range. can be done.
　（メタ）アクリル系重合体の分子量分布（Ｍｗ／Ｍｎ；Ｍｗは（メタ）アクリル系重合体の重量平均分子量を表し、Ｍｎは（メタ）アクリル系重合体の数平均分子量を表す）は、例えば、３．５以下、好ましくは３．０以下、より好ましくは２．５以下であり、例えば、１．１以上、好ましくは１．２以上、より好ましくは２．０以上である。 The molecular weight distribution (Mw/Mn; Mw represents the weight average molecular weight of the (meth)acrylic polymer, and Mn represents the number average molecular weight of the (meth)acrylic polymer) of the (meth)acrylic polymer, for example , 3.5 or less, preferably 3.0 or less, more preferably 2.5 or less, for example, 1.1 or more, preferably 1.2 or more, more preferably 2.0 or more.
　（メタ）アクリル系樹脂組成物における、環構造を有する（メタ）アクリル系重合体の含有割合は、例えば、５０質量％以上、好ましくは７０質量％以上、より好ましくは９０質量％以上、さらに好ましくは９５質量％以上である。また（メタ）アクリル系樹脂組成物における、環構造を有する（メタ）アクリル系重合体の含有割合の上限としては、１００質量％未満である。 The content of the (meth)acrylic polymer having a ring structure in the (meth)acrylic resin composition is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably is 95% by mass or more. The upper limit of the content of the (meth)acrylic polymer having a ring structure in the (meth)acrylic resin composition is less than 100% by mass.
　１．２　リン原子
　本発明の（メタ）アクリル系樹脂組成物は、リン原子を含有する。当該リン原子は、（メタ）アクリル系重合体の環化反応に使用する触媒に由来することが好ましい。 1.2 Phosphorus Atom The (meth)acrylic resin composition of the present invention contains a phosphorus atom. The phosphorus atom is preferably derived from the catalyst used for the cyclization reaction of the (meth)acrylic polymer.
　（メタ）アクリル系樹脂組成物における、リン原子の含有量は、１．０ｐｐｍ以上５０ｐｐｍ以下であり、１．５ｐｐｍ以上４５ｐｐｍ以下が好ましく、２．０ｐｐｍ以上４０ｐｐｍ以下がより好ましく、２０ｐｐｍ以上３４ｐｐｍ以下がさらに好ましい。リン原子の含有量が前記範囲内であることにより、環化率を高め、（メタ）アクリル系重合体が有する環構造単位の含有割合を適度な範囲にできるため、耐熱性に優れ、また機械的強度に優れた（メタ）アクリル系樹脂組成物を得ることができる。またリン原子の含有量が５０ｐｐｍ以下であることにより、シルバーストリークの発生が抑制されるとともに安定性に優れた（メタ）アクリル系樹脂組成物を得ることができる。具体的には、リン原子の含有量が５０ｐｐｍ以下であれば、腐食性を有するリン原子が十分少ないので、安定性に優れる。なお、リン原子の含有量は有効数字２桁で特定するものとする。 The content of phosphorus atoms in the (meth)acrylic resin composition is 1.0 ppm or more and 50 ppm or less, preferably 1.5 ppm or more and 45 ppm or less, more preferably 2.0 ppm or more and 40 ppm or less, and 20 ppm or more and 34 ppm or less. More preferred. When the content of phosphorus atoms is within the above range, the cyclization rate can be increased and the content of the ring structural units of the (meth)acrylic polymer can be set within an appropriate range. A (meth)acrylic resin composition having excellent mechanical strength can be obtained. Further, when the content of phosphorus atoms is 50 ppm or less, it is possible to obtain a (meth)acrylic resin composition that suppresses the generation of silver streaks and has excellent stability. Specifically, when the content of phosphorus atoms is 50 ppm or less, the number of corrosive phosphorus atoms is sufficiently small, and the stability is excellent. In addition, the content of phosphorus atoms shall be specified with two significant digits.
　１．３　式（Ｉ）で表される化合物
　本発明の（メタ）アクリル系樹脂組成物は、下記式（Ｉ）で表される化合物を含んでいてもよいが、なるべく含まないことが好ましい。具体的には、（メタ）アクリル系樹脂組成物における、式（Ｉ）で表される化合物の含有量は、９５ｐｐｍ以下であり、９０ｐｐｍ以下が好ましく、８０ｐｐｍ以下がより好ましく、６０ｐｐｍ以下がさらに好ましく、０ｐｐｍ（すなわち、実施例に記載の方法にて検出されないこと）であることが最も好ましい。式（Ｉ）で表される化合物の含有量が前記範囲内であることにより、成形の際に（メタ）アクリル系樹脂組成物とロールとの密着性が向上し、ロール汚染の発生を抑制できる。なお、式（Ｉ）で表される化合物の特定及びその含有量は、後述する実施例に記載の方法にて求めることができる。また、ｐｐｍで表した場合の小数第一位を四捨五入して特定するものとする。 1.3 Compound Represented by Formula (I) The (meth)acrylic resin composition of the present invention may contain a compound represented by the following formula (I), but preferably does not contain it as much as possible. Specifically, the content of the compound represented by formula (I) in the (meth)acrylic resin composition is 95 ppm or less, preferably 90 ppm or less, more preferably 80 ppm or less, and even more preferably 60 ppm or less. , 0 ppm (that is, not detected by the method described in the Examples). When the content of the compound represented by formula (I) is within the above range, the adhesion between the (meth)acrylic resin composition and the roll is improved during molding, and the occurrence of roll contamination can be suppressed. . The identification and content of the compound represented by the formula (I) can be obtained by the method described in Examples below. In addition, it shall be specified by rounding off to the first decimal place when expressed in ppm.
Figure JPOXMLDOC01-appb-C000008
［式（Ｉ）中、Ｒ1は炭素数１３以上の脂肪族炭化水素基、又は炭素数６以上の芳香族炭化水素基を表す。］
Figure JPOXMLDOC01-appb-C000008
[In Formula (I), R 1 represents an aliphatic hydrocarbon group having 13 or more carbon atoms or an aromatic hydrocarbon group having 6 or more carbon atoms. ]
　式（Ｉ）におけるＲ1で表される脂肪族炭化水素基としては、飽和又は不飽和であってもよく、鎖状又は環状であってもよい。
　Ｒ1で表される炭素数１３以上の脂肪族炭化水素基としては、例えば、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基等の炭素数１３以上のアルキル基；トリデセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、オクタデセニル基、オクタデカジエニル基等の炭素数１３以上のアルケニル基；シクロトリデシル基、シクロテトラデシル基、シクロペンタデシル基、シクロヘキサデシル基、シクロヘプタデシル基、シクロオクタデシル基等の炭素数１３以上のシクロアルキル基；等が挙げられる。
　Ｒ1で表される炭素数６以上の芳香族炭化水素基としては、例えば、フェニル基、トリル基、キシリル基、ナフチル基、ビフェニル基等の炭素数６以上のアリール基；ベンジル基、フェニルエチル基等の炭素数７以上のアラルキル基；等が挙げられる。 The aliphatic hydrocarbon group represented by R 1 in formula (I) may be saturated or unsaturated, and may be chain or cyclic.
Examples of aliphatic hydrocarbon groups having 13 or more carbon atoms represented by R 1 include tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups having 13 or more carbon atoms. Alkyl groups; tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, octadecenyl group, alkenyl groups having 13 or more carbon atoms such as octadecadienyl group; cyclotridecyl group, cyclotetradecyl group, cyclopentadecyl group, cyclohexyl a cycloalkyl group having 13 or more carbon atoms such as a sadecyl group, a cycloheptadecyl group, a cyclooctadecyl group; and the like.
Examples of aromatic hydrocarbon groups having 6 or more carbon atoms represented by R 1 include aryl groups having 6 or more carbon atoms such as phenyl, tolyl, xylyl, naphthyl, and biphenyl; benzyl, phenylethyl; an aralkyl group having 7 or more carbon atoms such as a group;
　１．４　式（ＩＩ）で表される化合物
　本発明の（メタ）アクリル系樹脂組成物は、下記式（ＩＩ）で表される化合物を含んでいてもよいが、なるべく含まないことが好ましい。具体的には、（メタ）アクリル系樹脂組成物における、式（ＩＩ）で表される化合物の含有量は、９５ｐｐｍ以下であり、９０ｐｐｍ以下が好ましく、８０ｐｐｍ以下がより好ましく、６０ｐｐｍ以下がさらに好ましく、０ｐｐｍ（すなわち、実施例に記載の方法にて検出されないこと）であることが最も好ましい。式（ＩＩ）で表される化合物の含有量が前記範囲内であることにより、ロール汚染を一層低減でき、さらにはシルバーストリークの発生が一層抑制されるとともに安定性に優れた（メタ）アクリル系樹脂組成物を得ることができる。なお、式（ＩＩ）で表される化合物の特定及びその含有量は、式（Ｉ）で表される化合物と同じ方法で求めることができる。また、ｐｐｍで表した場合の小数第一位を四捨五入して特定するものとする。 1.4 Compound Represented by Formula (II) The (meth)acrylic resin composition of the present invention may contain a compound represented by the following formula (II), but preferably does not contain it as much as possible. Specifically, the content of the compound represented by formula (II) in the (meth)acrylic resin composition is 95 ppm or less, preferably 90 ppm or less, more preferably 80 ppm or less, and even more preferably 60 ppm or less. , 0 ppm (that is, not detected by the method described in the Examples). When the content of the compound represented by the formula (II) is within the above range, it is possible to further reduce roll contamination, further suppress the generation of silver streaks, and have excellent stability. A resin composition can be obtained. The identification and content of the compound represented by formula (II) can be determined by the same method as for the compound represented by formula (I). In addition, it shall be specified by rounding off to the first decimal place when expressed in ppm.
Figure JPOXMLDOC01-appb-C000009
［式（ＩＩ）中、Ｒ2は炭素数３以上１２以下の脂肪族炭化水素基を表す。］
Figure JPOXMLDOC01-appb-C000009
[In Formula (II), R 2 represents an aliphatic hydrocarbon group having 3 or more and 12 or less carbon atoms. ]
　式（ＩＩ）におけるＲ2で表される脂肪族炭化水素基としては、飽和又は不飽和であってもよく、鎖状又は環状であってもよい。
　Ｒ2で表される炭素数３以上１２以下の脂肪族炭化水素基としては、例えば、ｎ－プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の炭素数３以上１２以下のアルキル基；プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基等の炭素数３以上１２以下のアルケニル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等の炭素数３以上１２以下のシクロアルキル基；等が挙げられる。
　Ｒ2としては、炭素数３以上１０以下の脂肪族炭化水素基が好ましく、炭素数３以上８以下の脂肪族炭化水素基がより好ましく、炭素数３以上７以下の脂肪族炭化水素基がさらに好ましい。 The aliphatic hydrocarbon group represented by R 2 in formula (II) may be saturated or unsaturated, and may be linear or cyclic.
Examples of the aliphatic hydrocarbon group having 3 to 12 carbon atoms represented by R 2 include n-propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, alkyl groups having 3 to 12 carbon atoms such as hexyl group, heptyl group and octyl group; alkenyl groups having 3 to 12 carbon atoms such as propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group and octenyl group; Cycloalkyl groups having 3 to 12 carbon atoms such as propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups; and the like.
R 2 is preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, more preferably an aliphatic hydrocarbon group having 3 to 8 carbon atoms, and further an aliphatic hydrocarbon group having 3 to 7 carbon atoms. preferable.
　１．５　他のアルコール
　本発明の（メタ）アクリル系樹脂組成物は、式（Ｉ）で表される化合物及び式（ＩＩ）で表される化合物以外のアルコール（他のアルコールと称する）を含んでいてもよい。特に他のアルコールがメタノール、エタノール等の低分子量アルコールである場合、成形時の加熱により揮発して除去されるためロール汚染の原因とならない。しかし、他のアルコールの含有量は少ないほど好ましく、例えば、１０００ｐｐｍ以下、好ましくは５００ｐｐｍ以下、より好ましくは３００ｐｐｍ以下であり、０ｐｐｍであってもよい。 1.5 Other alcohols The (meth)acrylic resin composition of the present invention contains alcohols (referred to as other alcohols) other than the compounds represented by formula (I) and formula (II). You can stay. In particular, if the other alcohol is a low-molecular-weight alcohol such as methanol or ethanol, it will volatilize and be removed by heating during molding, so that it will not cause contamination of the rolls. However, it is preferable that the content of other alcohols is as small as possible.
　１．６　その他の成分
　本発明の（メタ）アクリル系樹脂組成物は、上述した環構造を有する（メタ）アクリル系重合体やリン原子以外に、必要に応じて他の成分を含んでいてもよい。 1.6 Other Components The (meth)acrylic resin composition of the present invention may optionally contain other components in addition to the (meth)acrylic polymer having a ring structure and the phosphorus atom described above. good.
　本発明の（メタ）アクリル系樹脂組成物は、上記他の成分として、例えば、環構造を有さない（メタ）アクリル系重合体や、（メタ）アクリル系重合体以外の重合体を含有していてもよい。（メタ）アクリル系重合体以外の重合体としては、例えば、ポリエチレン、ポリプロピレン、エチレン－プロピレン重合体、ポリ（４－メチル－１－ペンテン）等のオレフィン系重合体；塩化ビニル、塩素化ビニル樹脂等の含ハロゲン系重合体；ポリスチレン、スチレン－メタクリル酸メチル共重合体、スチレン－アクリロニトリル共重合体、アクリロニトリル－ブタジエン－スチレン共重合体等のスチレン系重合体；ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル；ナイロン６、ナイロン６６、ナイロン６１０等のポリアミド；ポリアセタール；ポリカーボネート；ポリフェニレンオキシド；ポリフェニレンスルフィド；ポリエーテルエーテルケトン；ポリサルホン；ポリエーテルサルホン；ポリオキシペンジレン；ポリアミドイミド；シクロオレフィンポリマー；セルロース誘導体；ポリブタジエン系ゴム、（メタ）アクリル系ゴムを配合したＡＢＳ樹脂やＡＳＡ樹脂等のゴム質重合体等が挙げられる。（メタ）アクリル系樹脂組成物において、環構造を有する（メタ）アクリル系重合体以外の重合体の含有量は、環構造を有する（メタ）アクリル系重合体１００質量部に対して、１００質量部以下が好ましく、４０質量部以下がより好ましく、１０質量部以下がさらに好ましく、５質量部以下がよりさらに好ましく、０質量部であってもよい。 The (meth)acrylic resin composition of the present invention contains, as the other component, for example, a (meth)acrylic polymer having no ring structure or a polymer other than the (meth)acrylic polymer. may be Examples of polymers other than (meth)acrylic polymers include olefin polymers such as polyethylene, polypropylene, ethylene-propylene polymer, and poly(4-methyl-1-pentene); vinyl chloride and chlorinated vinyl resins. halogen-containing polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer; polyesters such as phthalates; polyamides such as nylon 6, nylon 66, nylon 610; polyacetals; polycarbonates; polyphenylene oxides; polyphenylene sulfides; cellulose derivatives; rubbery polymers such as ABS resins and ASA resins blended with polybutadiene rubbers and (meth)acrylic rubbers; In the (meth)acrylic resin composition, the content of the polymer other than the (meth)acrylic polymer having a ring structure is 100 parts by mass with respect to 100 parts by mass of the (meth)acrylic polymer having a ring structure. The amount is preferably 40 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and may be 0 parts by mass.
　また本発明の（メタ）アクリル系樹脂組成物は、本発明の効果を損なわない範囲であれば、種々の添加剤を含有していてもよい。添加剤としては、例えば、紫外線吸収剤；フェノール系酸化防止剤（例えば、ヒドロキノン、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、トコフェロール、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン等）、リン系酸化防止剤（例えば、トリフェニルホスファイト、トリス（２，４－ジ－ｔ－ブチルフェニル）ホスファイト等）、イオウ系酸化防止剤（例えば、２－メルカプトベンズイミダゾール、ジラウリル３，３’－チオジプロピオネート等）等の酸化防止剤；耐光安定剤、耐候安定剤、熱安定剤等の安定剤；ガラス繊維、炭素繊維等の補強材；近赤外線吸収剤；トリス（ジブロモプロピル）ホスフェート、トリアリルホスフェート、酸化アンチモン等の難燃剤；位相差上昇剤、位相差低減剤、位相差安定剤等の位相差調整剤；アニオン系、カチオン系、ノニオン系の界面活性剤を含む帯電防止剤；相溶化剤；安定化剤；無機顔料、有機顔料、染料等の着色剤；有機フィラーや無機フィラー；樹脂改質剤；有機充填剤や無機充填剤；等が挙げられる。樹脂組成物の固形分１００質量％中の各添加剤の含有割合は、好ましくは０質量％以上５質量％以下、より好ましくは０質量％以上２質量％以下の範囲内である。 In addition, the (meth)acrylic resin composition of the present invention may contain various additives as long as they do not impair the effects of the present invention. Additives include, for example, ultraviolet absorbers; phenolic antioxidants (eg, hydroquinone, 2,6-di-t-butyl-p-cresol, tocopherol, 1,3,5-trimethyl-2,4,6 -tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, etc.), phosphorus-based antioxidants (e.g., triphenylphosphite, tris(2,4-di-t-butylphenyl)phosphite etc.), antioxidants such as sulfur-based antioxidants (e.g., 2-mercaptobenzimidazole, dilauryl 3,3'-thiodipropionate, etc.); stabilizers such as light stabilizers, weather stabilizers, heat stabilizers, etc. ; glass fiber, reinforcing material such as carbon fiber; near-infrared absorber; flame retardants such as tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide; Retardation adjusters; antistatic agents containing anionic, cationic, and nonionic surfactants; compatibilizers; stabilizers; inorganic pigments, organic pigments, coloring agents such as dyes; organic fillers and inorganic fillers; modifiers; organic fillers and inorganic fillers; and the like. The content of each additive in 100% by mass of the solid content of the resin composition is preferably 0% by mass or more and 5% by mass or less, more preferably 0% by mass or more and 2% by mass or less.
　前記紫外線吸収剤としては、ベンゾフェノン系化合物、サリシレート系化合物、ベンゾエート系化合物、トリアゾール系化合物、及びトリアジン系化合物等が挙げられ、公知の紫外線吸収剤を用いることができる。ベンゾフェノン系化合物としては、２，４－ジヒドロキシベンゾフェノン、４－ｎ－オクチルオキシ－２－ヒドロキシベンゾフェノン、２，２’－ジヒドロキシ－４，４’－ジメトキシベンゾフェノン等が挙げられる。サリシレート系化合物としては、ｐ－ｔ－ブチルフェニルサリシレート等が挙げられる。ベンゾエート系化合物としては、２，４－ジ－ｔ－ブチルフェニル－３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシベンゾエート等が挙げられる。トリアゾール系化合物としては、２，２’－メチレンビス［４－（１，１，３，３－テトラメチルブチル）－６－（２Ｈ－ベンゾトリアゾール－２－イル）フェノール］、２－（３，５－ジ－ｔｅｒｔ－ブチル－２－ヒドロキシフェニル）－５－クロロベンゾトリアゾール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－ｐ－クレゾール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）フェノール、２－ベンゾトリアゾール－２－イル－４，６－ジ－ｔｅｒｔ－ブチルフェノール、２－［５－クロロ（２Ｈ）－ベンゾトリアゾール－２－イル］－４－メチル－６－ｔ－ブチルフェノール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ジ－ｔ－ブチルフェノール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４－（１，１，３，３－テトラメチルブチル）フェノール等が挙げられる。トリアジン系化合物としては、２－［４，６－ビス（ビフェニル－４－イル）－１，３，６－トリアジ－２－イル］－５－［（２－エチルヘキシル）オキシ］フェノール、２－モノ（ヒドロキシフェニル）－１，３，５－トリアジン化合物、２，４－ビス（ヒドロキシフェニル）－１，３，５－トリアジン化合物、２，４，６－トリス（ヒドロキシフェニル）－１，３，５－トリアジン化合物等が挙げられる。市販の紫外線吸収剤としては、例えば、トリアジン系紫外線吸収剤であるチヌビン（登録商標）１５７７、チヌビン（登録商標）４６０、チヌビン（登録商標）４７７（ＢＡＳＦジャパン社製）、アデカスタブ（登録商標）ＬＡ－Ｆ７０（ＡＤＥＫＡ社製）、トリアゾール系紫外線吸収剤であるアデカスタブ（登録商標）ＬＡ－３１（ＡＤＥＫＡ社製）等が挙げられる。紫外線吸収剤は、１種のみを用いてもよく、２種類以上を併用してもよい。 Examples of the ultraviolet absorber include benzophenone-based compounds, salicylate-based compounds, benzoate-based compounds, triazole-based compounds, triazine-based compounds, and the like, and known ultraviolet absorbers can be used. Benzophenone compounds include 2,4-dihydroxybenzophenone, 4-n-octyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and the like. Salicylate-based compounds include pt-butylphenyl salicylate and the like. Benzoate compounds include 2,4-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate and the like. Triazole compounds include 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(3,5 -di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4 ,6-bis(1-methyl-1-phenylethyl)phenol, 2-benzotriazol-2-yl-4,6-di-tert-butylphenol, 2-[5-chloro(2H)-benzotriazole-2- yl]-4-methyl-6-t-butylphenol, 2-(2H-benzotriazol-2-yl)-4,6-di-t-butylphenol, 2-(2H-benzotriazol-2-yl)-4 -(1,1,3,3-tetramethylbutyl)phenol and the like. Triazine compounds include 2-[4,6-bis(biphenyl-4-yl)-1,3,6-triazi-2-yl]-5-[(2-ethylhexyl)oxy]phenol, 2-mono (Hydroxyphenyl)-1,3,5-triazine compound, 2,4-bis(hydroxyphenyl)-1,3,5-triazine compound, 2,4,6-tris(hydroxyphenyl)-1,3,5 - triazine compounds and the like. Commercially available UV absorbers include, for example, triazine-based UV absorbers Tinuvin (registered trademark) 1577, Tinuvin (registered trademark) 460, Tinuvin (registered trademark) 477 (manufactured by BASF Japan), Adekastab (registered trademark) LA. -F70 (manufactured by ADEKA), Adekastab (registered trademark) LA-31 (manufactured by ADEKA), which is a triazole-based UV absorber, and the like. Only one type of ultraviolet absorber may be used, or two or more types may be used in combination.
　一方で、本発明の（メタ）アクリル系樹脂組成物は、ロール汚染をより効果的に抑制するために、ヒンダードフェノール化合物及び／又はヒンダードフェノール化合物の発生源となる化合物は含まない方が好ましい。ヒンダードフェノール化合物はロール汚染の原因となるからである。ヒンダードフェノール化合物としは、例えば、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン等のヒンダードフェノール系酸化防止剤等が挙げられる。ヒンダードフェノール化合物の発生源となる化合物としては、例えば、ヒンダードフェノール部位を有する有機リン化合物が挙げられ、具体的には、トリス（２，４－ジ－ｔ－ブチルフェニル）ホスファイト等のヒンダードフェノール部位を有するリン系酸化防止剤等が挙げられる。なお、ヒンダードフェノール化合物とは立体的に嵩高い置換基、例えば、t－ブチル基等の第３級アルキル基を少なくとも１個以上有するフェノール化合物であり、少なくとも１個の第３級アルキル基を有するフェノール化合物が好ましい。 On the other hand, the (meth)acrylic resin composition of the present invention preferably does not contain a hindered phenol compound and/or a compound that is a source of hindered phenol compounds, in order to more effectively suppress roll contamination. preferable. This is because hindered phenol compounds cause roll contamination. Hindered phenol compounds include, for example, 2,6-di-t-butyl-p-cresol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4 -hydroxybenzyl) benzene and other hindered phenol-based antioxidants. Examples of the compound that is the source of the hindered phenol compound include organic phosphorus compounds having a hindered phenol moiety, specifically tris(2,4-di-t-butylphenyl) phosphite and the like. Phosphorus-based antioxidants having hindered phenol moieties and the like can be mentioned. Incidentally, the hindered phenol compound is a phenolic compound having at least one or more sterically bulky substituents, for example, a tertiary alkyl group such as a t-butyl group, and at least one tertiary alkyl group. Phenolic compounds with
　１．７　特性
　本発明の（メタ）アクリル系樹脂組成物は、リン原子の含有量が、１．０ｐｐｍ以上５０ｐｐｍ以下であり、前述の式（Ｉ）で表される化合物の含有量が９５ｐｐｍ以下であり、また好ましくは前述の式（ＩＩ）で表される化合物の含有量が９５ｐｐｍ以下であることにより、ロール汚染を低減でき、さらにはシルバーストリークの発生が抑制されるとともに安定性に優れる。 1.7 Properties The (meth)acrylic resin composition of the present invention has a phosphorus atom content of 1.0 ppm or more and 50 ppm or less, and a content of the compound represented by the above formula (I) of 95 ppm or less. and preferably the content of the compound represented by the above formula (II) is 95 ppm or less, so that roll contamination can be reduced, silver streak generation is suppressed, and stability is excellent.
　（メタ）アクリル系樹脂組成物の重量平均分子量（Ｍｗ）は、例えば、５．０万以上、好ましくは８．０万以上、より好ましくは１０．０万以上、さらに好ましくは１１．５万以上、よりさらに好ましくは１２．０万以上であり、例えば、３０．０万以下、好ましくは２５．０万以下、より好ましくは２０．０万以下である。（メタ）アクリル系樹脂組成物の重量平均分子量が前記範囲内にあることにより、樹脂としての必要な強度を維持しながら、成形時の流動性も良好な（メタ）アクリル系樹脂組成物を得ることができる。 The weight average molecular weight (Mw) of the (meth)acrylic resin composition is, for example, 50,000 or more, preferably 80,000 or more, more preferably 100,000 or more, and still more preferably 115,000 or more. , more preferably 120,000 or more, for example, 300,000 or less, preferably 250,000 or less, and more preferably 200,000 or less. When the weight average molecular weight of the (meth)acrylic resin composition is within the above range, it is possible to obtain a (meth)acrylic resin composition having good fluidity during molding while maintaining the necessary strength as a resin. be able to.
　（メタ）アクリル系樹脂組成物の数平均分子量（Ｍｎ）は、例えば、３．０万以上、好ましくは３．５万以上、より好ましくは４．０万以上であり、例えば、２５．０万以下、好ましくは２０．０万以下、より好ましくは１５．０万以下である。（メタ）アクリル系樹脂組成物の数平均分子量が前記範囲内にあることにより、樹脂としての必要な強度を維持しながら、成形時の流動性も良好な（メタ）アクリル系樹脂組成物を得ることができる。 The number average molecular weight (Mn) of the (meth)acrylic resin composition is, for example, 30,000 or more, preferably 35,000 or more, more preferably 40,000 or more, for example, 250,000 or less, It is preferably 200,000 or less, more preferably 150,000 or less. When the number average molecular weight of the (meth)acrylic resin composition is within the above range, it is possible to obtain a (meth)acrylic resin composition having good fluidity during molding while maintaining the necessary strength as a resin. can.
　（メタ）アクリル系樹脂組成物の分子量分布（Ｍｗ／Ｍｎ；Ｍｗは（メタ）アクリル系樹脂組成物の重量平均分子量を表し、Ｍｎは（メタ）アクリル系樹脂組成物の数平均分子量を表す）は、例えば、３．５以下、好ましくは３．０以下、より好ましくは２．５以下であり、下限は特になく、例えば、１．１以上であってもよい。 The molecular weight distribution (Mw/Mn; Mw represents the weight average molecular weight of the (meth)acrylic resin composition, and Mn represents the number average molecular weight of the (meth)acrylic resin composition) of the (meth)acrylic resin composition, For example, it is 3.5 or less, preferably 3.0 or less, more preferably 2.5 or less, and there is no particular lower limit. For example, it may be 1.1 or more.
　（メタ）アクリル系樹脂組成物は、１１０℃以上にガラス転移温度を有することが好ましい。１１０℃以上にガラス転移温度を有することにより、樹脂組成物の耐熱性が高まる。（メタ）アクリル系樹脂組成物は、１１０℃以上にガラス転移温度を複数有していてもよい。（メタ）アクリル系樹脂組成物が有するガラス転移温度は、より好ましくは１２０℃以上であり、さらに好ましくは１２３℃以上である。成形時の加工性を高める観点からは、（メタ）アクリル系樹脂組成物が有するガラス転移温度は、３００℃未満が好ましく、２００℃以下がより好ましく、１８０℃以下がさらに好ましい。 The (meth)acrylic resin composition preferably has a glass transition temperature of 110°C or higher. Having a glass transition temperature of 110° C. or higher increases the heat resistance of the resin composition. The (meth)acrylic resin composition may have multiple glass transition temperatures of 110° C. or higher. The glass transition temperature of the (meth)acrylic resin composition is more preferably 120° C. or higher, still more preferably 123° C. or higher. From the viewpoint of enhancing workability during molding, the glass transition temperature of the (meth)acrylic resin composition is preferably less than 300°C, more preferably 200°C or less, and even more preferably 180°C or less.
　（メタ）アクリル系樹脂組成物は、式（Ｉ）で表される化合物の含有量が９５ｐｐｍ以下であることにより、密着性が良好である。 The (meth)acrylic resin composition has good adhesion because the content of the compound represented by formula (I) is 95 ppm or less.
　（メタ）アクリル系樹脂組成物は、密着性が良好であるため、成形時のロール汚染が抑制される。成形時にロールに汚染が発生すると、成形体の外観（平滑性）が損なわれる恐れや、ロール表面の汚染を除去するためにラインを停止することにより生産効率が低下する恐れがある。 Since the (meth)acrylic resin composition has good adhesion, contamination of rolls during molding is suppressed. If the rolls become contaminated during molding, there is a risk that the appearance (smoothness) of the molded product will be impaired, and production efficiency will be reduced by stopping the line to remove the contamination on the roll surface.
　２．　（メタ）アクリル系樹脂組成物の製造方法
　本発明の（メタ）アクリル系樹脂組成物の製造方法は、（メタ）アクリル系重合体において環化反応を行い、前記（メタ）アクリル系重合体の主鎖にラクトン環構造及び無水グルタル酸構造の少なくとも一方の環構造を形成する環化工程を含み、前記環化反応の触媒として特定の環化触媒を用いることを特徴とする。
　また本発明の（メタ）アクリル系樹脂組成物の製造方法は、前記（メタ）アクリル系重合体を（メタ）アクリル系モノマーを重合して形成する重合工程を含むことが好ましい。 2. Method for producing a (meth)acrylic resin composition In the method for producing a (meth)acrylic resin composition of the present invention, a (meth)acrylic polymer is subjected to a cyclization reaction, and the (meth)acrylic polymer is The method is characterized by including a cyclization step of forming at least one of a lactone ring structure and a glutaric anhydride structure on the main chain, and using a specific cyclization catalyst as a catalyst for the cyclization reaction.
The method for producing the (meth)acrylic resin composition of the present invention preferably includes a polymerization step of polymerizing the (meth)acrylic monomer to form the (meth)acrylic polymer.
　２．１　（メタ）アクリル系モノマー
　（メタ）アクリル系モノマーは重合成分であり、（メタ）アクリル系モノマーとしては、上記で説明した（メタ）アクリル系モノマーと同様のモノマーが挙げられ、その好ましい態様も同様である。 2.1 (Meth)acrylic monomer The (meth)acrylic monomer is a polymerizable component, and examples of the (meth)acrylic monomer include the same monomers as the (meth)acrylic monomers described above, which are preferred. Aspects are also the same.
　具体的には、重合に使用する（メタ）アクリル系モノマーとしては、単独であってもよく、２種以上の組み合わせであってもよい。重合に使用する（メタ）アクリル系モノマーとしては、（メタ）アクリル酸又は（メタ）アクリル酸エステルを少なくとも含むのが好ましく、（メタ）アクリル酸エステルを少なくとも含むのがより好ましい。また重合に使用する（メタ）アクリル系モノマーとしては、（メタ）アクリル酸及び／又は（メタ）アクリル酸エステルに加えてさらに（メタ）アクリル酸エステル誘導体を含むのが好ましい。特に重合に使用する（メタ）アクリル系モノマーとしては、（メタ）アクリル酸エステル、及び（メタ）アクリル酸エステルのヒドロキシ基導入誘導体を含むのが好ましい。重合に使用する単量体成分全量に対する（メタ）アクリル系モノマー全量の割合は、成形体の透明性の観点から、５０質量％以上が好ましく、より好ましくは６０質量％以上、さらに好ましくは７０質量％以上、よりさらに好ましくは７５質量％以上であり、上限は特になく、１００質量％であってもよい。重合に使用する（メタ）アクリル系モノマー中の（メタ）アクリル酸及び／又は（メタ）アクリル酸エステルの含有割合は、例えば、３０質量％以上、好ましくは５０質量％以上、より好ましくは６０質量％以上、さらに好ましくは６５質量％以上、よりさらに好ましくは７０質量％以上、特に好ましくは７５質量％以上であり、例えば、１００質量％以下、好ましくは９５質量％以下、より好ましくは９０質量％以下、さらに好ましくは８５質量％以下である。重合に使用する単量体成分全量に対する（メタ）アクリル酸エステル誘導体（好ましくはα－（１－ヒドロキシアルキル）アクリル酸アルキル）の含有割合は、例えば、１質量％以上、好ましくは５質量％以上、より好ましくは８質量％以上、さらに好ましくは１０質量％以上であり、例えば、７０質量％以下、好ましくは５０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下である。 Specifically, the (meth)acrylic monomer used for polymerization may be used alone or in combination of two or more. The (meth)acrylic monomer used for polymerization preferably contains at least (meth)acrylic acid or (meth)acrylic acid ester, and more preferably contains at least (meth)acrylic acid ester. In addition to (meth)acrylic acid and/or (meth)acrylic acid ester, the (meth)acrylic monomer used for polymerization preferably further contains a (meth)acrylic acid ester derivative. In particular, (meth)acrylic monomers used for polymerization preferably include (meth)acrylic acid esters and hydroxy group-introduced derivatives of (meth)acrylic acid esters. The ratio of the total amount of the (meth)acrylic monomer to the total amount of the monomer components used for polymerization is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass, from the viewpoint of the transparency of the molded article. % or more, more preferably 75% by mass or more, and there is no particular upper limit, and it may be 100% by mass. The content of (meth)acrylic acid and/or (meth)acrylic acid ester in the (meth)acrylic monomer used for polymerization is, for example, 30% by mass or more, preferably 50% by mass or more, more preferably 60% by mass. % or more, more preferably 65 mass % or more, still more preferably 70 mass % or more, particularly preferably 75 mass % or more, for example, 100 mass % or less, preferably 95 mass % or less, more preferably 90 mass % 85% by mass or less, more preferably 85% by mass or less. The content of the (meth)acrylic acid ester derivative (preferably α-(1-hydroxyalkyl) alkyl acrylate) relative to the total amount of monomer components used for polymerization is, for example, 1% by mass or more, preferably 5% by mass or more. , More preferably 8% by mass or more, still more preferably 10% by mass or more, for example, 70% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less .
　重合成分である単量体成分としては、前記（メタ）アクリル系モノマー以外の他のモノマーを含んでいてもよく、他のモノマーとしては、上記で説明した他のモノマーと同様のモノマーが挙げられ、その好ましい態様も同様である。 The monomer component, which is a polymerization component, may contain other monomers other than the (meth)acrylic monomers, and examples of the other monomers include the same monomers as the other monomers described above. , and preferred embodiments thereof are also the same.
　重合に使用する他のモノマーは、１種のみであってもよく、２種以上であってもよい。単量体成分全量に対する他のモノマー全量の割合は、例えば、０質量％以上、好ましくは１質量％以上であり、例えば、３０質量％以下であり、好ましくは２０質量％以下、より好ましくは１０質量％以下である。 The other monomers used for polymerization may be of only one type, or may be of two or more types. The ratio of the total amount of other monomers to the total amount of monomer components is, for example, 0% by mass or more, preferably 1% by mass or more, for example, 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass. % by mass or less.
　２．２　重合開始剤
　（メタ）アクリル系モノマーを用いた重合反応時には、必要に応じて重合開始剤を使用してもよい。 2.2 Polymerization Initiator In the polymerization reaction using the (meth)acrylic monomer, a polymerization initiator may be used as necessary.
　重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２－アミジノプロパン）・二塩酸塩、ジメチル－２，２’－アゾビス（２－メチルプロピオネート）、４，４’－アゾビス（４－シアノペンタン酸）等のアゾ化合物；過硫酸カリウム等の過硫酸塩類；クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、ｔ－ブチルパーオキシイソプロピルカーボネート、ｔ－アミルパーオキシ－２－エチルヘキサノエート、ｔ－アミルパーオキシオクトエート、ｔ－アミルパーオキシイソノナノエート、ｔ－アミルパーオキシイソプロピルカーボネート、ｔ－アミルパーオキシ２－エチルヘキシルカーボネート等の有機過酸化物等を用いることができる。これらは１種のみを用いてもよく、２種以上を併用してもよい。これらの中でも、水素引き抜き力が強い有機過酸化物を用いることが好ましい。 Examples of polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, dimethyl-2,2'-azobis(2-methylpropane). azo compounds such as 4,4′-azobis (4-cyanopentanoic acid); persulfates such as potassium persulfate; cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, t-amylperoxyoctoate, t-amylperoxyisononanoate, t-amylper Organic peroxides such as oxyisopropyl carbonate and t-amylperoxy 2-ethylhexyl carbonate can be used. These may use only 1 type and may use 2 or more types together. Among these, it is preferable to use an organic peroxide having a strong hydrogen abstraction power.
　重合開始剤の使用量は、重合速度を高め、未反応の単量体成分の残存量を低減させる観点から、単量体成分の全量に対して、例えば、５００ｐｐｍ以上、好ましくは１０００ｐｐｍ以上、より好ましくは１５００ｐｐｍ以上である。また、重合開始剤の使用量は、単量体成分の全量に対して、例えば、２質量％以下、好ましくは１質量％以下、より好ましくは０．５質量％以下である。 From the viewpoint of increasing the polymerization rate and reducing the residual amount of unreacted monomer components, the amount of the polymerization initiator used is, for example, 500 ppm or more, preferably 1000 ppm or more, or more, relative to the total amount of the monomer components. Preferably it is 1500 ppm or more. The amount of the polymerization initiator used is, for example, 2% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, relative to the total amount of the monomer components.
　重合開始剤の分解を促進するために、例えば、亜硫酸水素ナトリウム等の還元剤；硫酸第一鉄等の遷移金属塩；等の重合開始剤の分解剤を反応系内に適量で添加してもよい。 In order to promote the decomposition of the polymerization initiator, for example, a reducing agent such as sodium hydrogen sulfite; a transition metal salt such as ferrous sulfate; good.
　２．３　連鎖移動剤
　（メタ）アクリル系重合体の重量平均分子量を調整するために、反応系内に連鎖移動剤を添加してもよい。反応系内に連鎖移動剤を添加することにより、（メタ）アクリル系重合体を低分子量化させることができる。連鎖移動剤としては、有機チオール化合物；四塩化炭素、四臭化炭素、塩化メチレン、ブロモホルム、ブロモトリクロロエタン等のハロゲン化合物；α－メチルスチレンダイマー、α－テルピネン、γ－テルピネン、ジペンテン、ターピノーレン等の不飽和炭化水素化合物等が挙げられる。これら連鎖移動剤は１種のみを用いてもよく、２種以上を併用してもよい。これらの中でも、転化率の低下を抑制できる点から、有機チオール化合物が好ましい。 2.3 Chain Transfer Agent A chain transfer agent may be added to the reaction system in order to adjust the weight average molecular weight of the (meth)acrylic polymer. By adding a chain transfer agent to the reaction system, the (meth)acrylic polymer can be made to have a low molecular weight. Examples of chain transfer agents include organic thiol compounds; halogen compounds such as carbon tetrachloride, carbon tetrabromide, methylene chloride, bromoform, and bromotrichloroethane; Examples include unsaturated hydrocarbon compounds. These chain transfer agents may be used alone or in combination of two or more. Among these, an organic thiol compound is preferable because it can suppress a decrease in conversion rate.
　前記有機チオール化合物としては、単官能チオール化合物、多官能チオール化合物が挙げられる。
　前記単官能チオール化合物としては、例えば、チオフェノール、２－メルカプトベンゾチアゾール、２－メルカプトベンゾイミダゾール、２－メルカプトベンゾオキサゾール、３－メルカプト－１，２，４－トリアゾール、チオグリコール酸オクチル等の芳香族環を有する単官能チオール化合物；芳香族環を有さない脂肪族系の単官能チオール化合物が挙げられる。また前記脂肪族系の単官能チオール化合物としては、例えば、２－メルカプトプロピオン酸オクチル、３－メルカプトプロピオン酸オクチル、メルカプトプロピオン酸２－エチルヘキシルエステル、オクタン酸２－メルカプトエチルエステル等の脂肪族炭化水素基の炭素原子間にヘテロ原子を含有する単官能チオール化合物；ブタンチオール、オクタンチオール、１－ドデカンチオール（ｎ－ドデシルメルカプタンともいう）、オクタデカンチオール、シクロヘキシルメルカプタン等の脂肪族炭化水素基の炭素原子間にヘテロ原子を含有しないアルキルチオール化合物が挙げられる。前記ヘテロ原子としては酸素原子、窒素原子等が挙げられる。
　前記多官能チオール化合物としては、例えば、１，４－ジメチルメルカプトベンゼン、１，３，５－トリアジン－２，４，６－トリチオール等の芳香族環を有する多官能チオール化合物；１，８－ジメルカプト－３，６－ジオキサオクタン、エチレングリコールビスチオグリコレート、トリメチロールプロパントリスチオグリコレート、トリメチロールプロパントリスチオプロピオネート、トリメチロールプロパントリスチオブタネート、ペンタエリスリトールテトラキスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、ペンタエリスリトールテトラキス（４－メルカプトブタネート）、ペンタエリストールテトラキス（６－メルカプトヘキサネート）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）等の芳香族環を有さない脂肪族系の多官能チオール化合物が挙げられる。 Examples of the organic thiol compound include monofunctional thiol compounds and polyfunctional thiol compounds.
Examples of the monofunctional thiol compound include aromatics such as thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, and octyl thioglycolate. a monofunctional thiol compound having an aromatic ring; and an aliphatic monofunctional thiol compound having no aromatic ring. Examples of the aliphatic monofunctional thiol compound include aliphatic hydrocarbons such as octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, and 2-mercaptoethyl octanoate. Monofunctional thiol compounds containing heteroatoms between the carbon atoms of the group; carbon atoms of aliphatic hydrocarbon groups such as butanethiol, octanethiol, 1-dodecanethiol (also referred to as n-dodecylmercaptan), octadecanethiol, and cyclohexylmercaptan Included are alkylthiol compounds that do not contain heteroatoms in between. Examples of the heteroatom include an oxygen atom and a nitrogen atom.
Examples of the polyfunctional thiol compound include polyfunctional thiol compounds having an aromatic ring such as 1,4-dimethylmercaptobenzene and 1,3,5-triazine-2,4,6-trithiol; 1,8-dimercapto -3,6-dioxaoctane, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhiobutanate, pentaerythritol tetrakisthioglycolate, pentaerythritol Having an aromatic ring such as tetrakisthiopropionate, pentaerythritol tetrakis (4-mercaptobutanate), pentaerythritol tetrakis (6-mercaptohexanate), dipentaerythritol hexakis (3-mercaptopropionate) and aliphatic polyfunctional thiol compounds that do not have
　有機チオール化合物としては、単官能チオール化合物が好ましく、脂肪族系の単官能チオール化合物がより好ましく、アルキルチオール化合物がさらに好ましい。 As the organic thiol compound, monofunctional thiol compounds are preferred, aliphatic monofunctional thiol compounds are more preferred, and alkylthiol compounds are even more preferred.
　連鎖移動剤の使用量は、単量体成分の全量に対して、例えば、２００ｐｐｍ以上、好ましくは４００ｐｐｍ以上、より好ましくは５００ｐｐｍ以上であり、例えば、５質量％以下、好ましくは１質量％以下、より好ましくは０．５質量％以下である。 The amount of the chain transfer agent used is, for example, 200 ppm or more, preferably 400 ppm or more, more preferably 500 ppm or more, for example, 5% by mass or less, preferably 1% by mass or less, relative to the total amount of the monomer components. More preferably, it is 0.5% by mass or less.
　連鎖移動剤及び重合開始剤の使用量比は（連鎖移動剤の使用量／重合開始剤の使用量；質量比）、好ましくは０．１０以上、より好ましくは０．１５以上、さらに好ましくは０．２０以上であり、また好ましくは２．０以下、より好ましくは１．５以下、さらに好ましくは１．０以下である。連鎖移動剤及び重合開始剤の使用量比が前記範囲内にあることにより、重合速度を適切に保つことができ、また分子量分布を狭くすることができる。 The ratio of the amount of the chain transfer agent and the polymerization initiator used (amount of chain transfer agent used/amount of polymerization initiator used; mass ratio) is preferably 0.10 or more, more preferably 0.15 or more, and still more preferably 0. 0.20 or more, preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.0 or less. When the amount ratio of the chain transfer agent and the polymerization initiator is within the above range, the polymerization rate can be appropriately maintained and the molecular weight distribution can be narrowed.
　２．４　重合反応（重合工程）
　（メタ）アクリル系モノマーの重合形式としては、バッチ重合であっても、連続重合であってもよいが、連鎖移動剤を使用する場合には、未反応連鎖移動剤の残存量を低減できるためバッチ重合が好ましい。
　また、（メタ）アクリル系モノマーの重合は、塊状重合、溶液重合、乳化重合、懸濁重合のいずれでもよいが、安全性が高く、異物混入の恐れが低い点で、溶液重合が好ましい。 2.4 Polymerization reaction (polymerization process)
The polymerization form of the (meth)acrylic monomer may be batch polymerization or continuous polymerization. When a chain transfer agent is used, the residual amount of unreacted chain transfer agent can be reduced. Batch polymerization is preferred.
Polymerization of the (meth)acrylic monomer may be bulk polymerization, solution polymerization, emulsion polymerization, or suspension polymerization, but solution polymerization is preferred because of its high safety and low risk of foreign matter contamination.
　溶液重合で使用可能な溶媒としては、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒；テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、アニソール等のエーテル系溶媒；酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、３－メトキシブチルアセテート等のエステル系溶媒；メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ等のセロソルブ系溶媒；メタノール、エタノール、イソプロパノール、ｎ－ブタノール等のアルコール系溶媒；アセトニトリル、プロピオニトリル、ブチロニトリル、ベンゾニトリル等のニトリル系溶媒；クロロホルム、ジクロロメタン等のハロゲン系溶媒；ジメチルスルホキシド等が挙げられる。重合溶媒としては、芳香族炭化水素系溶媒及びケトン系溶媒が好ましく、より好ましく芳香族炭化水素系溶媒、特に好ましくはトルエンである。これらの重合溶媒は、１種のみを用いてもよく、２種以上を併用してもよい。 Solvents usable in solution polymerization include aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Ether solvents such as anisole; Ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; Cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve; methanol, ethanol, isopropanol, n alcohol solvents such as butanol; nitrile solvents such as acetonitrile, propionitrile, butyronitrile and benzonitrile; halogen solvents such as chloroform and dichloromethane; As the polymerization solvent, aromatic hydrocarbon-based solvents and ketone-based solvents are preferred, aromatic hydrocarbon-based solvents are more preferred, and toluene is particularly preferred. These polymerization solvents may be used alone or in combination of two or more.
　重合反応液中のモノマー（単量体成分）の合計濃度は、例えば、５質量％以上、好ましくは１０質量％以上、より好ましくは３０質量％以上であり、例えば、９０質量％以下、好ましくは８０質量％以下、より好ましくは７０質量％以下である。重合反応における溶媒の使用量としては、重合反応液中のモノマーの合計濃度が前記範囲内であれば特に限定されない。 The total concentration of the monomers (monomer components) in the polymerization reaction solution is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less. The amount of solvent used in the polymerization reaction is not particularly limited as long as the total concentration of the monomers in the polymerization reaction solution is within the above range.
　モノマー、及び必要に応じて用いる溶媒の添加方法は特に限定されない。その添加方法としては、それぞれ、全量を初期仕込みとしてもよく、一定量を初期仕込みとして残りを重合反応中に反応系内へ一括又は継続して添加してもよい。前記継続は連続であってもよく、分割添加等のような断続であってもよいが、連続又は間隔が１０分以下の断続であることが好ましく、連続であることがより好ましい。
　また、必要に応じて用いる重合開始剤及び連鎖移動剤の添加方法も特に限定されない。その添加方法としては、それぞれ、全量を初期仕込みとしてもよく、一定量を初期仕込みとして残りを重合反応中に反応系内へ一括又は継続して添加してもよく、全量を添加によって反応系に導入してもよい。前記継続は連続であってもよく、分割添加等のような断続であってもよいが、連続又は間隔が１０分以下の断続であることが好ましく、連続であることがより好ましい。なお、重合開始剤は、得られる（メタ）アクリル系重合体の分子量分布を狭くできるため、全量を重合反応中に反応系内へ継続して添加する、又は一定量を初期仕込みとして残りを重合反応中に反応系内へ継続して添加するのが好ましい。 There are no particular restrictions on the method of adding the monomer and the solvent used as necessary. As for the method of addition, the total amount of each may be initially charged, or a fixed amount may be initially charged and the remainder may be added all at once or continuously to the reaction system during the polymerization reaction. The continuation may be continuous or intermittent such as divided addition, preferably continuous or intermittent at intervals of 10 minutes or less, more preferably continuous.
Moreover, the method of adding the polymerization initiator and the chain transfer agent, which are used as necessary, is not particularly limited. As the method of addition, the total amount of each may be initially charged, or a fixed amount may be initially charged and the remainder may be added all at once or continuously to the reaction system during the polymerization reaction, or the total amount may be added to the reaction system by addition. may be introduced. The continuation may be continuous or intermittent such as divided addition, preferably continuous or intermittent at intervals of 10 minutes or less, more preferably continuous. In addition, since the polymerization initiator can narrow the molecular weight distribution of the obtained (meth)acrylic polymer, the total amount is continuously added to the reaction system during the polymerization reaction, or a certain amount is initially charged and the rest is polymerized. It is preferable to continuously add to the reaction system during the reaction.
　（メタ）アクリル系モノマーを重合させる際の雰囲気は、特に限定されないが、重合反応の効率を高める観点から、窒素ガス等の不活性ガスであることが好ましい。 Although the atmosphere in which the (meth)acrylic monomer is polymerized is not particularly limited, it is preferably an inert gas such as nitrogen gas from the viewpoint of increasing the efficiency of the polymerization reaction.
　（メタ）アクリル系モノマーを重合させる際の重合温度は、例えば、４０℃以上、好ましくは６０℃以上、より好ましくは８０℃以上であり、重合開始剤を用いる場合には、使用する重合開始剤の１０時間半減期温度以上とするのが好ましい。なお１０時間半減期温度とは、重合開始剤の半減期が１０時間となる温度のことを意味する。また重合温度は、例えば、１８０℃以下、好ましくは１５０℃以下、より好ましくは１２０℃以下であり、溶媒を用いる場合には、使用する溶媒のリフラックス温度以下とするのが好ましい。 The polymerization temperature for polymerizing the (meth)acrylic monomer is, for example, 40° C. or higher, preferably 60° C. or higher, more preferably 80° C. or higher. When a polymerization initiator is used, the polymerization initiator to be used 10-hour half-life temperature or higher. The 10-hour half-life temperature means the temperature at which the half-life of the polymerization initiator is 10 hours. The polymerization temperature is, for example, 180° C. or lower, preferably 150° C. or lower, more preferably 120° C. or lower, and when a solvent is used, it is preferably not higher than the reflux temperature of the solvent used.
　（メタ）アクリル系モノマーを重合させる際の重合時間は、特に限定されず、重合反応の進行状況に応じて適宜設定すればよいが、通常、２～８時間程度である。 The polymerization time for polymerizing the (meth)acrylic monomer is not particularly limited, and may be appropriately set according to the progress of the polymerization reaction, but is usually about 2 to 8 hours.
　全てのモノマー、及び必要に応じて重合開始剤、連鎖移動剤、溶媒を添加した後、必要に応じて熟成を行ってもよい。熟成によりモノマーの転化率がさらに向上する。熟成工程では、適当な温度、例えば、重合温度±３０℃程度で（好ましくは重合温度で、又は重合温度以上で）攪拌を継続することが好ましい。熟成の時間は、例えば、０時間以上１０時間以下、好ましくは１時間以上５時間以下である。 After adding all the monomers and, if necessary, the polymerization initiator, chain transfer agent, and solvent, aging may be performed as necessary. Aging further improves monomer conversion. In the aging step, it is preferable to continue stirring at an appropriate temperature, for example, about ±30° C. of the polymerization temperature (preferably at the polymerization temperature or above the polymerization temperature). The aging time is, for example, 0 hours or more and 10 hours or less, preferably 1 hour or more and 5 hours or less.
　反応終了時のモノマーの転化率は、例えば、８０％以上、好ましくは８５％以上、より好ましくは８８％以上である。 The conversion rate of the monomer at the end of the reaction is, for example, 80% or higher, preferably 85% or higher, and more preferably 88% or higher.
　重合反応により得られる（メタ）アクリル系重合体の全構成単位における、（メタ）アクリル系モノマーに由来する構成単位の合計含有割合は、成形体の透明性の観点から、５０質量％以上が好ましく、より好ましくは６０質量％以上、さらに好ましくは７０質量％以上、よりさらに好ましくは７５質量％以上である。上限は特になく、１００質量％であってもよい。また、重合反応により得られる（メタ）アクリル系重合体の全構成単位における（メタ）アクリル酸エステル誘導体（好ましくはα－（１－ヒドロキシアルキル）アクリル酸アルキル）に由来する構成単位の合計含有割合は、好ましくは５質量％以上、より好ましくは８質量％以上、さらに好ましくは１０質量％以上であり、例えば、７０質量％以下、好ましくは５０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下である。 The total content of structural units derived from (meth)acrylic monomers in all structural units of the (meth)acrylic polymer obtained by the polymerization reaction is preferably 50% by mass or more from the viewpoint of the transparency of the molded product. , more preferably 60% by mass or more, still more preferably 70% by mass or more, and even more preferably 75% by mass or more. There is no particular upper limit, and it may be 100% by mass. In addition, the total content of structural units derived from (meth)acrylic acid ester derivatives (preferably α-(1-hydroxyalkyl)alkyl acrylate) in all structural units of the (meth)acrylic polymer obtained by the polymerization reaction is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, for example, 70% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less, and further Preferably, it is 20% by mass or less.
　２．５　環化触媒
　本発明では、環化触媒としてリン酸Ｃ3-12アルキルエステル、亜リン酸Ｃ3-12アルキルエステル、及び次亜リン酸Ｃ3-12アルキルエステルからなる群から選ばれる少なくとも１種を用いることにより、環化反応を効率的に行い、且つ得られる（メタ）アクリル系樹脂組成物の密着性の低下を抑制できる。 2.5 Cyclization Catalyst In the present invention, the cyclization catalyst is selected from the group consisting of C 3-12 alkyl phosphate, C 3-12 alkyl phosphite, and C 3-12 hypophosphite. By using at least one of them, it is possible to efficiently perform the cyclization reaction and to suppress deterioration of adhesion of the obtained (meth)acrylic resin composition.
　リン酸Ｃ3-12アルキルエステルとしては、例えば、リン酸モノプロピル、リン酸ジプロピル、リン酸トリプロピル、リン酸モノイソプロピル、リン酸ジイソプロピル、リン酸トリイソプロピル、リン酸モノブチル、リン酸ジブチル、リン酸トリブチル、リン酸モノｔｅｒｔ－ブチル、リン酸ジｔｅｒｔ－ブチル、リン酸トリｔｅｒｔ－ブチル、リン酸モノペンチル、リン酸ジペンチル、リン酸トリペンチル、リン酸モノヘキシル、リン酸ジヘキシル、リン酸トリヘキシル、リン酸モノヘプチル、リン酸ジヘプチル、リン酸トリヘプチル、リン酸モノオクチル、リン酸ジオクチル、リン酸トリオクチル等が挙げられる。リン酸Ｃ3-12アルキルエステルとしては、リン酸Ｃ3-10アルキルエステルが好ましく、リン酸Ｃ3-8アルキルエステルがより好ましく、リン酸Ｃ3-7アルキルエステルがさらに好ましい。リン酸Ｃ3-8アルキルエステルは、リン酸Ｃ3-8直鎖アルキルエステルが好ましく、リン酸Ｃ3-8モノ直鎖アルキルエステル、リン酸Ｃ3-8ジ直鎖アルキルエステルがより好ましい。リン酸Ｃ3-7アルキルエステルは、リン酸Ｃ3-7直鎖アルキルエステルが好ましく、リン酸Ｃ3-7モノ直鎖アルキルエステル、リン酸Ｃ3-7ジ直鎖アルキルエステルがより好ましい。リン酸Ｃ3-12アルキルエステルは、リン酸モノブチル、リン酸ジブチルが特に好ましい。 Examples of C 3-12 alkyl phosphate include monopropyl phosphate, dipropyl phosphate, tripropyl phosphate, monoisopropyl phosphate, diisopropyl phosphate, triisopropyl phosphate, monobutyl phosphate, dibutyl phosphate, phosphorus tributyl acid, mono-tert-butyl phosphate, di-tert-butyl phosphate, tri-tert-butyl phosphate, monopentyl phosphate, dipentyl phosphate, tripentyl phosphate, monohexyl phosphate, dihexyl phosphate, trihexyl phosphate, phosphorus monoheptyl phosphate, diheptyl phosphate, triheptyl phosphate, monooctyl phosphate, dioctyl phosphate, trioctyl phosphate and the like. The C 3-12 alkyl phosphate is preferably a C 3-10 alkyl phosphate, more preferably a C 3-8 alkyl phosphate, and even more preferably a C 3-7 alkyl phosphate. The C 3-8 alkyl phosphate is preferably a C 3-8 straight-chain alkyl phosphate, more preferably a C 3-8 mono-straight-chain alkyl phosphate and a C 3-8 di-straight-chain alkyl phosphate. The C 3-7 alkyl phosphate is preferably a C 3-7 straight-chain alkyl phosphate, more preferably a C 3-7 mono-straight-chain alkyl phosphate and a C 3-7 di-straight-chain alkyl phosphate. Among the C 3-12 alkyl phosphates, monobutyl phosphate and dibutyl phosphate are particularly preferred.
　亜リン酸Ｃ3-12アルキルエステルとしては、例えば、亜リン酸モノプロピル、亜リン酸ジプロピル、亜リン酸トリプロピル、亜リン酸モノイソプロピル、亜リン酸ジイソプロピル、亜リン酸トリイソプロピル、亜リン酸モノブチル、亜リン酸ジブチル、亜リン酸トリブチル、亜リン酸モノｔｅｒｔ－ブチル、亜リン酸ジｔｅｒｔ－ブチル、亜リン酸トリｔｅｒｔ－ブチル、亜リン酸モノペンチル、亜リン酸ジペンチル、亜リン酸トリペンチル、亜リン酸モノヘキシル、亜リン酸ジヘキシル、亜リン酸トリヘキシル、亜リン酸モノヘプチル、亜リン酸ジヘプチル、亜リン酸トリヘプチル、亜リン酸モノオクチル、亜リン酸ジオクチル、亜リン酸トリオクチル等が挙げられる。亜リン酸Ｃ3-12アルキルエステルとしては、亜リン酸Ｃ3-10アルキルエステルが好ましく、亜リン酸Ｃ3-8アルキルエステルがより好ましく、亜リン酸Ｃ3-7アルキルエステルがさらに好ましい。亜リン酸Ｃ3-8アルキルエステルは、亜リン酸Ｃ3-8直鎖アルキルエステルがさらに好ましく、亜リン酸Ｃ3-8モノ直鎖アルキルエステル、亜リン酸Ｃ3-8ジ直鎖アルキルエステルがよりさらに好ましい。亜リン酸Ｃ3-7アルキルエステルは、亜リン酸Ｃ3-7直鎖アルキルエステルが好ましく、リ亜ン酸Ｃ3-7モノ直鎖アルキルエステル、亜リン酸Ｃ3-7ジ直鎖アルキルエステルがより好ましい。亜リン酸Ｃ3-12アルキルエステルは、亜リン酸モノブチル、亜リン酸ジブチルが特に好ましい。 Examples of C 3-12 alkyl phosphite include monopropyl phosphite, dipropyl phosphite, tripropyl phosphite, monoisopropyl phosphite, diisopropyl phosphite, triisopropyl phosphite, phosphite monobutyl acid, dibutyl phosphite, tributyl phosphite, mono-tert-butyl phosphite, di-tert-butyl phosphite, tri-tert-butyl phosphite, monopentyl phosphite, dipentyl phosphite, phosphorous tripentyl phosphite, monohexyl phosphite, dihexyl phosphite, trihexyl phosphite, monoheptyl phosphite, diheptyl phosphite, triheptyl phosphite, monooctyl phosphite, dioctyl phosphite, trioctyl phosphite, etc. mentioned. The C 3-12 alkyl phosphite is preferably a C 3-10 alkyl phosphite, more preferably a C 3-8 alkyl phosphite, and even more preferably a C 3-7 alkyl phosphite. The C 3-8 alkyl phosphite is more preferably C 3-8 straight-chain alkyl phosphite, C 3-8 mono-straight-chain alkyl phosphite, C 3-8 di-straight-chain alkyl phosphite Esters are even more preferred. The C 3-7 alkyl phosphite is preferably C 3-7 straight-chain alkyl phosphite, C 3-7 mono-straight-chain alkyl phosphite, C 3-7 di-straight-chain alkyl phosphite Esters are more preferred. Among the C 3-12 alkyl phosphites, monobutyl phosphite and dibutyl phosphite are particularly preferred.
　次亜リン酸Ｃ3-12アルキルエステルとしては、例えば、次亜リン酸モノプロピル、次亜リン酸ジプロピル、次亜リン酸トリプロピル、次亜リン酸モノイソプロピル、次亜リン酸ジイソプロピル、次亜リン酸トリイソプロピル、次亜リン酸モノブチル、次亜リン酸ジブチル、次亜リン酸トリブチル、次亜リン酸モノｔｅｒｔ－ブチル、次亜リン酸ジｔｅｒｔ－ブチル、次亜リン酸トリｔｅｒｔ－ブチル、次亜リン酸モノペンチル、次亜リン酸ジペンチル、次亜リン酸トリペンチル、次亜リン酸モノヘキシル、次亜リン酸ジヘキシル、次亜リン酸トリヘキシル、次亜リン酸モノヘプチル、次亜リン酸ジヘプチル、次亜リン酸トリヘプチル、次亜リン酸モノオクチル、次亜リン酸ジオクチル、次亜リン酸トリオクチル等が挙げられる。次亜リン酸Ｃ3-12アルキルエステルとしては、次亜リン酸Ｃ3-10アルキルエステルが好ましく、次亜リン酸Ｃ3-8アルキルエステルがより好ましく、次亜リン酸Ｃ3-7アルキルエステルがさらに好ましい。次亜リン酸Ｃ3-8アルキルエステルは、次亜リン酸Ｃ3-8直鎖アルキルエステルがさらに好ましく、次亜リン酸Ｃ3-8モノ直鎖アルキルエステル、次亜リン酸Ｃ3-8ジ直鎖アルキルエステルがよりさらに好ましい。次亜リン酸Ｃ3-7アルキルエステルは、次亜リン酸Ｃ3-7直鎖アルキルエステルがさらに好ましく、次亜リン酸Ｃ3-7モノ直鎖アルキルエステル、次亜リン酸Ｃ3-7ジ直鎖アルキルエステルがよりさらに好ましい。次亜リン酸Ｃ3-12アルキルエステルは、次亜リン酸モノブチル、次亜リン酸ジブチルが特に好ましい。 Hypophosphite C 3-12 alkyl esters include, for example, monopropyl hypophosphite, dipropyl hypophosphite, tripropyl hypophosphite, monoisopropyl hypophosphite, diisopropyl hypophosphite, hypophosphite triisopropyl phosphate, monobutyl hypophosphite, dibutyl hypophosphite, tributyl hypophosphite, mono-tert-butyl hypophosphite, di-tert-butyl hypophosphite, tri-tert-butyl hypophosphite, monopentyl hypophosphite, dipentyl hypophosphite, tripentyl hypophosphite, monohexyl hypophosphite, dihexyl hypophosphite, trihexyl hypophosphite, monoheptyl hypophosphite, diheptyl hypophosphite, triheptyl phosphite, monooctyl hypophosphite, dioctyl hypophosphite, trioctyl hypophosphite and the like. The C 3-12 alkyl hypophosphite is preferably a C 3-10 alkyl hypophosphite, more preferably a C 3-8 alkyl hypophosphite, and a C 3-7 alkyl hypophosphite. is more preferred. The C 3-8 alkyl hypophosphite is more preferably C 3-8 linear alkyl hypophosphite, C 3-8 mono linear alkyl hypophosphite, C 3-8 hypophosphite Dilinear alkyl esters are even more preferred. The C 3-7 alkyl hypophosphite is more preferably C 3-7 linear alkyl hypophosphite, C 3-7 mono linear alkyl hypophosphite, C 3-7 hypophosphite Dilinear alkyl esters are even more preferred. As the C 3-12 alkyl hypophosphite, monobutyl hypophosphite and dibutyl hypophosphite are particularly preferred.
　環化触媒は、１種のみを用いてもよく、２種類以上を併用してもよい。２種類以上を併用する場合は、その１つをリン酸ステアリルとしてもよい。というのも、本発明の思想の１つは、環化触媒の全体量におけるリン酸ステアリルの割合を従来よりも少なくする点にある。 Only one kind of the cyclization catalyst may be used, or two or more kinds thereof may be used in combination. When two or more types are used together, one of them may be stearyl phosphate. This is because one of the ideas of the present invention is to make the proportion of stearyl phosphate in the total amount of the cyclization catalyst smaller than before.
　環化触媒としては、触媒活性が高い点でリン酸Ｃ3-12アルキルエステルが好ましい。 As the cyclization catalyst, a phosphoric acid C 3-12 alkyl ester is preferable because of its high catalytic activity.
　環化触媒の分解温度としては、１６０℃以上が好ましく、より好ましくは１８０℃以上、さらに好ましくは２００℃以上であり、上限は特になく、例えば３００℃以下であってもよい。例えば、リン酸ブチルの分解温度は２２０℃であり、リン酸オクチルの分解温度は２４７℃である。 The decomposition temperature of the cyclization catalyst is preferably 160°C or higher, more preferably 180°C or higher, and still more preferably 200°C or higher. For example, the decomposition temperature of butyl phosphate is 220°C and the decomposition temperature of octyl phosphate is 247°C.
　２．６　環化反応（環化工程）
　前記重合反応終了後の（メタ）アクリル系重合体を、前記環化触媒存在下で加熱することにより、脱水縮合又は脱アルコール縮合を生じさせ、主鎖にラクトン環構造及び無水グルタル酸構造の少なくとも一方である環構造を有する（メタ）アクリル系重合体を形成する。 2.6 Cyclization reaction (cyclization step)
By heating the (meth)acrylic polymer after completion of the polymerization reaction in the presence of the cyclization catalyst, dehydration condensation or dealcoholization condensation is caused, and at least a lactone ring structure and a glutaric anhydride structure are formed on the main chain. On the one hand, a (meth)acrylic polymer having a ring structure is formed.
　具体的には、重合工程で形成された（メタ）アクリル系重合体において、下記（ｉ）及び（ｉｉ）の環化反応のうち少なくとも片方の環化反応を行う。
　（ｉ）ヒドロキシ基と、エステル基又はカルボキシル基との間で、ラクトン環構造を形成する環化反応
　（ｉｉ）カルボキシル基と、エステル基又は他のカルボキシル基との間で、無水グルタル酸構造を形成する環化反応 Specifically, in the (meth)acrylic polymer formed in the polymerization step, at least one of the following cyclization reactions (i) and (ii) is performed.
(i) a cyclization reaction to form a lactone ring structure between a hydroxy group and an ester group or a carboxyl group; (ii) a glutaric anhydride structure between a carboxyl group and an ester group or another carboxyl group; cyclization reaction to form
　上記（ｉ）の環化反応の場合、例えば、まず上記重合反応においてα－（１－ヒドロキシアルキル）アクリル酸アルキル等のヒドロキシ基含有（メタ）アクリル系モノマーＡを単独重合して、又は前記ヒドロキシ基含有（メタ）アクリル系モノマーＡと、（メタ）アクリル酸、（メタ）アクリル酸エステル等の（メタ）アクリル系モノマーＢとを共重合して、（メタ）アクリル系重合体の分子鎖にヒドロキシ基と、エステル基又はカルボキシル基とを導入する。そして環化反応において、ヒドロキシ基と、エステル基又はカルボキシル基との間で脱アルコール又は脱水環化縮合を生じさせることによりラクトン環構造を形成できる。
　（ｉ）の環化反応におけるヒドロキシ基含有（メタ）アクリル系モノマーＡとしては、前述の（メタ）アクリル酸エステルのヒドロキシ基導入誘導体が挙げられ、その好ましい態様も同様である。また（メタ）アクリル系モノマーＢとしては、前述の（メタ）アクリル酸、（メタ）アクリル酸エステルが挙げられ、その好ましい態様も同様である。 In the case of the cyclization reaction (i), for example, first, in the polymerization reaction, a hydroxy group-containing (meth)acrylic monomer A such as alkyl α-(1-hydroxyalkyl)acrylate is homopolymerized, or the hydroxy A group-containing (meth)acrylic monomer A and a (meth)acrylic monomer B such as (meth)acrylic acid or (meth)acrylic acid ester are copolymerized to form a (meth)acrylic polymer molecular chain. A hydroxy group and an ester group or a carboxyl group are introduced. In the cyclization reaction, a lactone ring structure can be formed by dealcoholization or dehydration cyclocondensation between a hydroxy group and an ester group or a carboxyl group.
Examples of the hydroxy group-containing (meth)acrylic monomer A in the cyclization reaction (i) include hydroxy group-introduced derivatives of the aforementioned (meth)acrylic acid esters, and preferred embodiments thereof are the same. The (meth)acrylic monomer B includes the above-described (meth)acrylic acid and (meth)acrylic acid ester, and preferred embodiments thereof are also the same.
　上記（ｉｉ）の環化反応の場合、例えば、まず上記重合反応において（メタ）アクリル酸を単独重合して（メタ）アクリル系重合体の分子鎖にカルボキシル基を導入、又は（メタ）アクリル酸、（メタ）アクリル酸エステル等の（メタ）アクリル系モノマーＢを重合（好ましくは共重合）して、（メタ）アクリル系重合体の分子鎖にカルボキシル基とエステル基とを導入する。そして環化反応において、２個のカルボキシル基間で脱水環化縮合を生じさせるか、カルボキシル基とエステル基との間で脱アルコールを生じさせることにより無水グルタル酸構造を形成できる。
　（ｉｉ）の環化反応における（メタ）アクリル系モノマーＢとしては、前述の（メタ）アクリル酸、（メタ）アクリル酸エステルが挙げられ、その好ましい態様も同様である。 In the case of the cyclization reaction (ii), for example, first, in the polymerization reaction, (meth)acrylic acid is homopolymerized to introduce a carboxyl group into the molecular chain of the (meth)acrylic polymer, or (meth)acrylic acid A (meth)acrylic monomer B such as a (meth)acrylic acid ester is polymerized (preferably copolymerized) to introduce a carboxyl group and an ester group into the molecular chain of the (meth)acrylic polymer. In the cyclization reaction, a glutaric anhydride structure can be formed by dehydration cyclocondensation between two carboxyl groups or by dealcoholization between a carboxyl group and an ester group.
Examples of the (meth)acrylic monomer B in the cyclization reaction (ii) include the above-mentioned (meth)acrylic acid and (meth)acrylic acid esters, and preferred embodiments thereof are also the same.
　なお（メタ）アクリル系重合体が二重結合部分や、エステル基、カルボキシル基又は酸無水物基を有する場合には、環化反応前に、二重結合部分へのヒドロキシ基の付加反応、エステル基の加水分解、カルボキシル基又は酸無水物基のエステル化反応等により、（メタ）アクリル系重合体に後から環化反応において反応するヒドロキシ基、エステル基、又はカルボキシル基を導入してもよい。 When the (meth)acrylic polymer has a double bond portion, an ester group, a carboxyl group, or an acid anhydride group, addition reaction of a hydroxy group to the double bond portion, ester A hydroxy group, an ester group, or a carboxyl group that reacts in a cyclization reaction may be subsequently introduced into the (meth)acrylic polymer by hydrolysis of the group, esterification reaction of the carboxyl group or acid anhydride group, or the like. .
　なお前記環化反応においては、（メタ）アクリル系重合体が有するヒドロキシ基、エステル基、及び／又はカルボキシル基の少なくとも一部が反応すればよく、（メタ）アクリル系重合体において前述の環構造単位の含有割合、及び環化率の範囲内となるように反応すればよい。 In the cyclization reaction, at least part of the hydroxy groups, ester groups, and/or carboxyl groups of the (meth)acrylic polymer may react, and the ring structure of the (meth)acrylic polymer The reaction may be carried out so as to be within the ranges of the content ratio of the units and the cyclization rate.
　環化反応は、溶媒の存在下で行ってもよく、環化反応で使用可能な溶媒としては、前述の重合反応で使用可能な溶媒と同じ種類挙げられ、好ましい態様も同様である。
　前記重合反応を溶液重合で行った場合、溶液重合で使用した溶媒を一旦除去した後に新たに溶媒を添加してもよく、溶液重合で使用した溶媒を引き続き環化反応での溶媒として使用してもよいが、生産効率の点から溶液重合で使用した溶媒を引き続き環化反応での溶媒として使用することが好ましい。 The cyclization reaction may be carried out in the presence of a solvent, and the solvents that can be used in the cyclization reaction include the same types of solvents that can be used in the polymerization reaction described above, and preferred embodiments are also the same.
When the polymerization reaction is carried out by solution polymerization, a new solvent may be added after removing the solvent used in the solution polymerization, or the solvent used in the solution polymerization may be used as a solvent in the cyclization reaction. However, from the viewpoint of production efficiency, it is preferable to continue to use the solvent used in the solution polymerization as the solvent in the cyclization reaction.
　環化反応液中の（メタ）アクリル系重合体の濃度は、例えば、５質量％以上、好ましくは１０質量％以上、より好ましくは３０質量％以上であり、例えば、９０質量％以下、好ましくは８０質量％以下、より好ましくは７０質量％以下である。環化反応における溶媒の使用量としては、環化反応液中の（メタ）アクリル系重合体の濃度が前記範囲内であれば特に限定されない。 The concentration of the (meth)acrylic polymer in the cyclization reaction solution is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less. The amount of solvent used in the cyclization reaction is not particularly limited as long as the concentration of the (meth)acrylic polymer in the cyclization reaction solution is within the above range.
　環化触媒の使用量は、例えば、（メタ）アクリル系重合体を構成する単量体成分の全量に対して、１００ｐｐｍ以上１０００ｐｐｍ以下が好ましく、より好ましくは１１０ｐｐｍ以上、さらに好ましくは１２０ｐｐｍ以上、よりさらに好ましくは１５０ｐｐｍ以上であり、またより好ましくは９００ｐｐｍ以下、さらに好ましくは８００ｐｐｍ以下、よりさらに好ましくは７００ｐｐｍ以下である。環化触媒の使用量が前記範囲内であることにより、環化率を高め、（メタ）アクリル系重合体に環構造単位を所望の割合形成しながら、シルバーストリークの発生が抑制されるとともに安定性に優れた（メタ）アクリル系樹脂組成物を得ることができる。 The amount of the cyclization catalyst used is, for example, preferably 100 ppm or more and 1000 ppm or less, more preferably 110 ppm or more, still more preferably 120 ppm or more, and more It is more preferably 150 ppm or more, more preferably 900 ppm or less, still more preferably 800 ppm or less, and even more preferably 700 ppm or less. When the amount of the cyclization catalyst used is within the above range, the cyclization rate is increased, and the generation of silver streaks is suppressed and stabilized while forming the desired ratio of ring structural units in the (meth)acrylic polymer. A (meth)acrylic resin composition having excellent properties can be obtained.
　環化反応時の環化触媒の添加方法としては、全量を初期仕込みとしてもよく、一定量を初期仕込みとして残りを環化反応中に反応系内へ一括又は継続して添加してもよく、全量を添加によって反応系に導入してもよい。前記継続は連続であってもよく、分割添加等のような断続であってもよいが、連続又は間隔が１０分以下の断続であることが好ましく、連続であることがより好ましい。 As a method for adding the cyclization catalyst during the cyclization reaction, the entire amount may be initially charged, or a fixed amount may be initially charged and the remainder may be added all at once or continuously to the reaction system during the cyclization reaction. The entire amount may be introduced into the reaction system by addition. The continuation may be continuous or intermittent such as divided addition, preferably continuous or intermittent at intervals of 10 minutes or less, more preferably continuous.
　環化反応の反応温度は、例えば、５０℃～３００℃であり、好ましくは７０℃～１５０℃である。環化反応の反応時間は、例えば、５分～６時間程度であり、好ましくは３０分～３時間である。
　本発明の環化触媒によれば、環化反応を効率的に行えるため、反応時間が３時間未満であっても、環化率が高く、（メタ）アクリル系重合体において前述の環構造単位の含有割合の範囲内となる環化を達成できる。 The reaction temperature for the cyclization reaction is, for example, 50°C to 300°C, preferably 70°C to 150°C. The reaction time for the cyclization reaction is, for example, about 5 minutes to 6 hours, preferably 30 minutes to 3 hours.
According to the cyclization catalyst of the present invention, since the cyclization reaction can be performed efficiently, even if the reaction time is less than 3 hours, the cyclization rate is high, and the above-mentioned ring structural unit in the (meth)acrylic polymer can achieve cyclization within the range of the content ratio of
　環化反応は、重合反応を行う反応釜で行い、さらにオートクレーブや多管式熱交換器等で環化反応を進行させることが好ましい。 It is preferable that the cyclization reaction is carried out in a reaction vessel in which the polymerization reaction is carried out, and further progressed in an autoclave, multitubular heat exchanger, or the like.
　環化工程後は、脱揮工程を含む後処理を行うことが好ましい。
　脱揮工程とは、溶媒、残存モノマー等の揮発分と、前記環化反応により副生したアルコールを除去する処理工程をいう。また環化触媒としてリン酸Ｃ3-12アルキルエステル、亜リン酸Ｃ3-12アルキルエステル、及び次亜リン酸Ｃ3-12アルキルエステルからなる群から選ばれる少なくとも１種を用いれば、脱揮工程において揮散して除去されやすい。さらに脱揮工程を加熱条件下で行うことにより、前記環化触媒が分解してアルコールが発生するが、当該アルコールも除去されることが好ましい。 After the cyclization step, post-treatment including a devolatilization step is preferably performed.
The devolatilization step is a treatment step for removing volatile matter such as solvent and residual monomers, and alcohol by-produced by the cyclization reaction. If at least one selected from the group consisting of C 3-12 alkyl phosphate, C 3-12 alkyl phosphite, and C 3-12 hypophosphite is used as a cyclization catalyst, devolatilization Easy to volatilize and be removed in the process. Furthermore, by performing the devolatilization step under heating conditions, the cyclization catalyst is decomposed to generate alcohol, and it is preferable that the alcohol is also removed.
　脱揮が不十分であると、（メタ）アクリル系樹脂組成物中の残存揮発分が多く、成形時に発泡が生じて成形不良となる。
　また環化触媒として炭素数が１３以上のリン酸アルキルエステル、亜リン酸アルキルエステル、又は次亜リン酸アルキルエステルを用いた場合には、これらの化合物が分解して発生する高級アルコール（炭素数１３以上のアルコール）は揮発し難いため、（メタ）アクリル系樹脂組成物中に残存し、（メタ）アクリル系樹脂組成物の密着性を低下させる。 If the devolatilization is insufficient, the (meth)acrylic resin composition has a large amount of residual volatile matter, and foaming occurs during molding, resulting in poor molding.
When alkyl phosphates, alkyl phosphites, or alkyl hypophosphites having 13 or more carbon atoms are used as the cyclization catalyst, higher alcohols (carbon atoms alcohol of 13 or more) is difficult to volatilize, so it remains in the (meth)acrylic resin composition and reduces the adhesion of the (meth)acrylic resin composition.
　脱揮に使用する装置は特に限定されないが、例えば、オートクレーブ、釜型反応器、熱交換器と脱揮槽とからなる装置、ベント付押出機等が使用でき、乾燥機を使用してもよい。 The device used for devolatilization is not particularly limited, but for example, an autoclave, a kettle-type reactor, a device consisting of a heat exchanger and a devolatilization tank, a vented extruder, etc. can be used, and a dryer may be used. .
　脱揮にベント付押出機を用いる場合、押出機は、シリンダと、シリンダ内に設けられたスクリューとを有し、加熱手段を備えていることが好ましい。シリンダには、ベントが１つ又は複数設けられていることが好ましく、ベントは、押出機内の移送方向に対して、少なくとも原料投入部の下流側に設けられることがより好ましく、原料投入部の上流側にも設けられてもよい。押出機内に供給された重合体を、スクリューで混練しながら押出機の上流側から下流側へ移送される過程で脱揮が進む。押出機の下流側にはダイスが設けられていることが好ましく、ダイスから重合体を吐出することにより、所定の形状に成形することができる。例えば、棒状に成形された重合体を細かく切断すれば、ペレットを製造することができる。また押出機のダイス部には、ポリマーフィルターが設けられることが好ましい。 When using a vented extruder for devolatilization, the extruder preferably has a cylinder, a screw provided in the cylinder, and heating means. It is preferable that the cylinder is provided with one or more vents, and the vent is more preferably provided at least downstream of the raw material charging section with respect to the transfer direction in the extruder, and upstream of the raw material charging section. It may also be provided on the side. Volatilization progresses in the process in which the polymer fed into the extruder is conveyed from the upstream side to the downstream side of the extruder while being kneaded by a screw. A die is preferably provided on the downstream side of the extruder, and the polymer can be molded into a predetermined shape by discharging the polymer from the die. For example, pellets can be produced by finely cutting a rod-shaped polymer. Moreover, it is preferable that the die part of the extruder is provided with a polymer filter.
　脱揮処理温度は、１５０℃～３５０℃の範囲が好ましく、２００℃～３００℃の範囲がより好ましい。脱揮処理温度が１５０℃より低いと、脱揮が不充分となり残存揮発分が多くなるという問題があり、３５０℃より高いと、着色や分解が起こるという問題があるために好ましくない。脱揮処理時の減圧度は、１３．３ｈＰａ以上（例えば、１３．３ｈＰａ～８００ｈＰａ程度）が好ましい。 The devolatilization treatment temperature is preferably in the range of 150°C to 350°C, more preferably in the range of 200°C to 300°C. When the devolatilization treatment temperature is lower than 150°C, the devolatilization becomes insufficient and the remaining volatile matter increases. The degree of pressure reduction during the devolatilization treatment is preferably 13.3 hPa or more (for example, about 13.3 hPa to 800 hPa).
　前記重合工程、前記環化工程、及び前記環化工程の後の工程から選ばれる１つ以上の工程において、前記添加剤を添加してもよい。ただし、添加剤としては、前記ヒンダードフェノール化合物及び／又は前記ヒンダードフェノール化合物の発生源となる化合物は含まないことが好ましい。 The additive may be added in one or more steps selected from the polymerization step, the cyclization step, and the steps after the cyclization step. However, it is preferable that the additive does not contain the hindered phenol compound and/or the compound that is the source of the hindered phenol compound.
　３．　成形体
　（メタ）アクリル樹脂組成物は、種々の形態に成形して、各種製品乃至部品として使用できる。成形体の形状は用途に応じて適宜設定すればよく、例えば、板状、粒状、粉状、塊状、粒子凝集体状、球状、楕円球状、レンズ状、立方体状、柱状、棒状、錐形状、筒状、針状、繊維状、中空糸状、多孔質状等が挙げられる。これら（メタ）アクリル樹脂組成物の成形体は、例えば、射出成形、押出成形、ブロー成形等の（メタ）アクリル樹脂粒子の熱溶融を経る工程、またはその一次成形体をさらに二次成形（真空成形、圧縮成形等）することによって製造可能である。前記（メタ）アクリル樹脂粒子の形状としては、例えば、粒子径が１μｍ～１０００μｍの粉体、長径が１ｍｍ～１０ｍｍ程度の円柱状又は球状等のペレット、またはそれらの混合物であることが好ましい。 3. Molded Article The (meth)acrylic resin composition can be molded into various shapes and used as various products or parts. The shape of the molded article may be appropriately set according to the application, and examples thereof include plate-like, granular, powdery, lumpy, particle aggregate, spherical, ellipsoidal, lens-like, cubic, columnar, rod-like, cone-like, Cylindrical, acicular, fibrous, hollow fiber, porous and the like can be mentioned. Molded bodies of these (meth)acrylic resin compositions can be formed by, for example, injection molding, extrusion molding, blow molding, or other processes in which (meth)acrylic resin particles are thermally melted, or the primary molded body is further subjected to secondary molding (vacuum molding). molding, compression molding, etc.). The shape of the (meth)acrylic resin particles is preferably, for example, powder with a particle diameter of 1 μm to 1000 μm, cylindrical or spherical pellets with a major diameter of about 1 mm to 10 mm, or a mixture thereof.
　前記（メタ）アクリル系樹脂粒子は、さらにフィルム状に成形して光学フィルムとしてもよい。光学フィルムは、例えば、偏光子保護フィルム、位相差フィルム、視野角補償フィルム、光拡散フィルム、反射フィルム、反射防止フィルム、防眩フィルム、輝度向上フィルム、タッチパネル用導電フィルムである。 The (meth)acrylic resin particles may be further formed into a film to form an optical film. Examples of optical films include polarizer protective films, retardation films, viewing angle compensation films, light diffusion films, reflective films, antireflection films, antiglare films, brightness enhancement films, and conductive films for touch panels.
　これらの光学フィルムは、一般的には、（メタ）アクリル樹脂組成物からなる（メタ）アクリル樹脂層と、（メタ）アクリル樹脂層の表面に設けられたプライマー層とを有し、プライマー層は粒子を含む。 These optical films generally have a (meth)acrylic resin layer made of a (meth)acrylic resin composition and a primer layer provided on the surface of the (meth)acrylic resin layer. Contains particles.
　プライマー層は、例えば、ウレタン樹脂、セルロース樹脂、ポリオール樹脂、ポリカルボン酸樹脂、及びポリエステル樹脂から選ばれる少なくとも１つの樹脂からなる層である。 The primer layer is, for example, a layer made of at least one resin selected from urethane resin, cellulose resin, polyol resin, polycarboxylic acid resin, and polyester resin.
　粒子は有機粒子でも無機粒子でもよい。有機粒子は、例えば、（メタ）アクリル系モノマーを構成単位に有する（メタ）アクリル系重合体、スチレン系モノマーを構成単位に有するスチレン系重合体等の有機重合体を含む粒子である。有機重合体の構成単位（（メタ）アクリル系モノマーやスチレン系モノマー等）はケミカルリサイクル等のリサイクルを経て用意されたものでもよい。無機粒子は、例えば、シリカ粒子、アルミナ粒子、チタニア粒子、ジルコニア粒子、ガラス質の粒子等である。これらの粒子もリサイクルを経て用意されたものでもよい。 The particles may be organic particles or inorganic particles. The organic particles are, for example, particles containing an organic polymer such as a (meth)acrylic polymer having a (meth)acrylic monomer as a structural unit or a styrene polymer having a styrene monomer as a structural unit. The constituent units ((meth)acrylic monomer, styrene monomer, etc.) of the organic polymer may be those prepared through recycling such as chemical recycling. Examples of inorganic particles include silica particles, alumina particles, titania particles, zirconia particles, vitreous particles, and the like. These particles may also be prepared through recycling.
　（メタ）アクリル樹脂組成物の成形温度は、特に限定されないが、１５０℃～３５０℃の範囲が好ましく、２００℃～３００℃の範囲がより好ましい。 The molding temperature of the (meth)acrylic resin composition is not particularly limited, but is preferably in the range of 150°C to 350°C, more preferably in the range of 200°C to 300°C.
　本発明の（メタ）アクリル系樹脂組成物は、ロール汚染を低減でき、さらには、シルバーストリークの発生が抑制されるとともに安定性に優れているため、当該（メタ）アクリル系樹脂組成物を用いた成形品は、外観に優れ、また高効率に生産すること可能性である。 The (meth)acrylic resin composition of the present invention can reduce roll contamination, further suppresses the generation of silver streaks and has excellent stability, so the (meth)acrylic resin composition is used. Molded products with excellent appearance can be produced with high efficiency.
　本願は、２０２２年１月１４日に出願された日本国特許出願第２０２２－００４６７９号に基づく優先権の利益を主張するものである。２０２２年１月１４日に出願された日本国特許出願第２０２２－００４６７９号の明細書の全内容が、本願に参考のため援用される。 This application claims the benefit of priority based on Japanese Patent Application No. 2022-004679 filed on January 14, 2022. The entire contents of the specification of Japanese Patent Application No. 2022-004679 filed on January 14, 2022 are incorporated herein by reference.
　以下、実験例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実験例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。なお以下の実験例では、特に断りがない限り、「部」は「質量部」を意味し、「ｐｐｍ」は「質量ｐｐｍ」を、「％」は「質量％」を意味する。 Hereinafter, the present invention will be described in more detail with reference to experimental examples, but the present invention is not limited by the following experimental examples, and can be modified appropriately within the scope of the above and later descriptions. It is of course possible to implement them, and all of them are included in the technical scope of the present invention. In the following experimental examples, unless otherwise specified, "parts" means "mass parts", "ppm" means "mass ppm", and "%" means "mass %".
　始めに、以下の実験例で採用した測定方法について説明する。
（１）重量平均分子量、数平均分子量、分子量分布
　重合溶液中および重合後の（メタ）アクリル系樹脂の重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）および分子量分布（Ｍｗ／Ｍｎ）は、ゲル浸透クロマトグラフィー（ＧＰＣ）を用いて、ポリスチレン換算により求めた。測定に用いた装置及び測定条件は以下の通りである。
　測定システム：東ソー製ＧＰＣシステムＨＬＣ－８２２０
　測定側カラム構成：
　・ガードカラム（東ソー製、ＴＳＫ　ｇｕａｒｄｃｏｌｕｍｎ　ＳｕｐｅｒＨＺ－Ｌ）
　・分離カラム（東ソー製、ＴＳＫ　Ｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｍ）、２本直列接続
　リファレンス側カラム構成：
　・リファレンスカラム（東ソー製、ＴＳＫ　ｇｅｌ　ＳｕｐｅｒＨ－ＲＣ）
　展開溶媒：クロロホルム（和光純薬工業製、特級）
　展開溶媒の流量：０．６ｍＬ／分
　標準試料：ＴＳＫ標準ポリスチレン（東ソー製、ＰＳ－オリゴマーキット） First, the measurement methods employed in the following experimental examples will be described.
(1) Weight average molecular weight, number average molecular weight, molecular weight distribution The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the (meth)acrylic resin in the polymerization solution and after polymerization are It calculated|required by polystyrene conversion using a gel permeation chromatography (GPC). The apparatus and measurement conditions used for the measurement are as follows.
Measurement system: Tosoh GPC system HLC-8220
Measurement side column configuration:
・Guard column (manufactured by Tosoh, TSK guardcolumn SuperHZ-L)
・ Separation column (manufactured by Tosoh, TSK Gel Super HZM-M), two columns connected in series Reference side column configuration:
・ Reference column (manufactured by Tosoh, TSK gel SuperH-RC)
Developing solvent: Chloroform (manufactured by Wako Pure Chemical Industries, special grade)
Flow rate of developing solvent: 0.6 mL / min Standard sample: TSK standard polystyrene (manufactured by Tosoh, PS-oligomer kit)
（２）転化率
　重合反応時の転化率（重合率）（質量％）は、得られた重合溶液中の未反応単量体濃度（質量％）をガスクロマトグラフィー（島津製作所社製、装置名：ＧＣ１７Ａ）を用いて測定し、式（Ａ）より算出した。
　転化率（重合率）＝１００×（１－Ｍ１／Ｍ０）　　…（Ａ）
　式中、Ｍ１は重合溶液中の未反応単量体濃度（質量％）を示し、Ｍ０は仕込み原料溶液中の単量体濃度（質量％）を示す。 (2) Conversion rate The conversion rate (polymerization rate) (mass%) during the polymerization reaction was obtained by measuring the unreacted monomer concentration (mass%) in the resulting polymerization solution by gas chromatography (manufactured by Shimadzu Corporation, device name : GC17A) and calculated from the formula (A).
Conversion rate (polymerization rate) = 100 x (1-M1/M0) (A)
In the formula, M1 indicates the unreacted monomer concentration (% by mass) in the polymerization solution, and M0 indicates the monomer concentration (% by mass) in the raw material solution.
（３）ガラス転移温度
　（メタ）アクリル系樹脂組成物のガラス転移温度（Ｔｇ）は、ＪＩＳ　Ｋ７１２１の規定に準拠して、始点法により求めた。具体的には、示差走査熱量計（株式会社リガク製、Ｔｈｅｒｍｏ　ｐｌｕｓ　ＥＶＯ　ＤＳＣ－８２３０）を用い、窒素ガスフロー（１００ｍｌ／分）下、約１０ｍｇの試料を常温から２００℃まで昇温（昇温速度２０℃／分）して得られたＤＳＣ曲線から評価した。リファレンスには、α－アルミナを用いた。 (3) Glass transition temperature The glass transition temperature (Tg) of the (meth)acrylic resin composition was determined by the starting point method in accordance with JIS K7121. Specifically, using a differential scanning calorimeter (Thermo plus EVO DSC-8230 manufactured by Rigaku Co., Ltd.), a sample of about 10 mg was heated from room temperature to 200 ° C. under nitrogen gas flow (100 ml / min) (heating The evaluation was made from the DSC curve obtained at a speed of 20°C/min). α-alumina was used as a reference.
（４）ラクトン環化率
　（メタ）アクリル系樹脂組成物２部をクロロホルム２０部に溶解し、得られた溶液をメタノール２００部に滴下して沈殿物を含む溶液を得た。沈殿物を含む溶液をろ過し、沈殿物を抽出し、８０℃の真空乾燥機で４時間乾燥することによってサンプルを得た。得られたサンプルを以下の方法（ダイナミックＴＧ法）にて分析し、式（Ｂ）よりラクトン環化率（％）を算出した。
　測定装置：差動型示差熱天秤（株式会社リガク製、ＴｈｅｒｍｏＰｌｕｓ２　ＴＧ－８１２０、ダイナミックＴＧ）
　測定条件：試料量１０ｍｇ
　昇温速度：１０℃／分
　雰囲気：窒素フロー４００ｍＬ／分
　方法：階段状等温制御法（６０℃から４００℃までの範囲内における質量減少速度値０．００５％／秒以下に制御）にて昇温
　ラクトン環化率＝１－（Ｘ／Ｙ）　　…（Ｂ）
　式（Ｂ）中、Ｘは質量減少の始まる前の１５０℃から重合体の分解が始まる３００℃までの脱アルコール反応における質量減少率（質量％）を示し、Ｙは当該重合体組成から全ての水酸基が脱アルコール（ラクトン環化）すると仮定した場合の理論質量減少率（すなわち、当該重合体組成において起こりうる脱アルコール反応が１００％起きたと仮定して算出した重量減少率；質量％）を示す。例えば、実施例、及び比較例で得られる重合体の場合、ラクトン環化反応によって発生するメタノールの分子量は３２であり、２－（ヒドロキシメチル）アクリル酸メチルの分子量は１１６、ラクトン環化前重合体の組成比は１２質量％であるから、理論質量減少率Ｙは、（３２／１１６）×１２＝３．３１質量％となる。 (4) Lactone Cyclization Rate Two parts of the (meth)acrylic resin composition were dissolved in 20 parts of chloroform, and the resulting solution was added dropwise to 200 parts of methanol to obtain a solution containing precipitates. A sample was obtained by filtering the solution containing the precipitate, extracting the precipitate, and drying it in a vacuum dryer at 80° C. for 4 hours. The obtained sample was analyzed by the following method (dynamic TG method), and the lactone cyclization rate (%) was calculated from the formula (B).
Measuring device: Differential differential thermal balance (Rigaku Corporation, ThermoPlus2 TG-8120, Dynamic TG)
Measurement conditions: sample amount 10 mg
Heating rate: 10 ° C./min Atmosphere: Nitrogen flow 400 mL/min Method: Elevated by a stepped isothermal control method (controlled to a mass reduction rate value of 0.005% / sec or less within the range from 60 ° C. to 400 ° C.) Warm lactone cyclization rate = 1-(X/Y) (B)
In formula (B), X represents the mass reduction rate (% by mass) in the dealcoholization reaction from 150 ° C. before mass reduction starts to 300 ° C. where decomposition of the polymer starts, and Y represents all Shows the theoretical weight loss rate when it is assumed that the hydroxyl group is dealcoholized (lactone cyclization) (that is, the weight loss rate calculated assuming that the dealcoholization reaction that can occur in the polymer composition has occurred 100%; mass%) . For example, in the case of the polymers obtained in Examples and Comparative Examples, the molecular weight of methanol generated by the lactone cyclization reaction is 32, the molecular weight of methyl 2-(hydroxymethyl)acrylate is 116, and the molecular weight of methyl 2-(hydroxymethyl)acrylate is 116. Since the combined composition ratio is 12% by mass, the theoretical mass reduction rate Y is (32/116)×12=3.31% by mass.
（５）リン原子含有量
　（メタ）アクリル系樹脂組成物０．２部を２－ブタノン９９．８部に溶解したサンプル溶液に対して、ＩＣＰ発光分光分析装置（サーモフィッシャーサイエンティフィック製、ｉＣＡＰ６５００　Ｄｕｏ）を用いて（メタ）アクリル系樹脂組成物中のリン原子含有量（ｐｐｍ）を測定した。 (5) Phosphorus atom content (Meth) For a sample solution obtained by dissolving 0.2 parts of an acrylic resin composition in 99.8 parts of 2-butanone, an ICP emission spectrometer (manufactured by Thermo Fisher Scientific, iCAP6500 Duo) was used to measure the phosphorus atom content (ppm) in the (meth)acrylic resin composition.
（６）アルコール成分測定
　サンプル準備：（メタ）アクリル系樹脂組成物２部をクロロホルム２０部に溶解し、得られた溶液をメタノール２００部に滴下して沈殿物を含む溶液を得た。沈殿物を含む溶液をろ過し、メタノール可溶成分を抽出し、乾燥することによって得たサンプルを、アセトンに溶解してサンプル溶液を得た。
　測定：得られたサンプル溶液をＧＣ－ＭＳを用いて測定し、メタノール以外の検出されるアルコール成分を特定した。さらに、サンプル溶液をガスクロマトグラフィー（島津製作所社製、装置名：ＧＣ１７Ａ）を用いて測定し、（メタ）アクリル系樹脂組成物中のメタノール以外のアルコール成分含有量（ｐｐｍ）を定量した。 (6) Alcohol component measurement Sample preparation: 2 parts of the (meth)acrylic resin composition was dissolved in 20 parts of chloroform, and the obtained solution was dropped into 200 parts of methanol to obtain a solution containing precipitates. A sample solution obtained by filtering the solution containing the precipitate, extracting methanol-soluble components, and drying the sample was dissolved in acetone to obtain a sample solution.
Measurement: The obtained sample solution was measured using GC-MS to identify detected alcohol components other than methanol. Furthermore, the sample solution was measured using gas chromatography (manufactured by Shimadzu Corporation, device name: GC17A) to quantify the alcohol component content (ppm) other than methanol in the (meth)acrylic resin composition.
（７）密着性評価
　（メタ）アクリル系樹脂組成物をアルミ薄板（日本テストパネル製、膜厚０．１ｍｍ）で挟み、さらにアルミ薄板の上からＳＵＳ板で挟み、手動式加熱プレス機（株式会社井元製作所製、ＩＭＣ－１８０Ｃ型）を用いて、２５０℃で５分間溶融プレス成形した。その後ＳＵＳ板で挟んだままプレス機から取り出して１分間冷却した後、アルミ薄板を剥がす際に、アルミ薄板に樹脂組成物が全面的に付着した場合には密着性を「良」、樹脂組成物が一部付着した場合には密着性を「普」、樹脂組成物が付着することなく剥がせた場合には密着性を「不良」と判定した。 (7) Adhesion evaluation A (meth)acrylic resin composition is sandwiched between aluminum thin plates (manufactured by Nippon Test Panel, film thickness 0.1 mm), and further sandwiched between aluminum thin plates with SUS plates. It was melt press molded at 250° C. for 5 minutes using IMC-180C type manufactured by Imoto Seisakusho. After that, it was removed from the press while sandwiched between the SUS plates, cooled for 1 minute, and when the aluminum thin plate was peeled off, if the resin composition adhered to the entire surface of the aluminum thin plate, the adhesion was "good", and the resin composition was evaluated as "good". The adhesion was judged to be "Normal" when the resin composition partially adhered, and the adhesion was judged to be "Poor" when the resin composition could be peeled off without adhering.
（８）ロール汚染評価
　（メタ）アクリル系樹脂組成物について、オープン製膜を行うことによりロール汚染の評価をした。
　具体的には、以下の手順で製膜した。
　直径６５ｍｍ、Ｌ／Ｄ＝３２のバリアフライト型スクリューを有するベント付単軸押出機を用いて溶融製膜を行った。押出機のシリンダとギアポンプの温度を２７５℃、ポリマーフィルターおよびＴダイの温度を２７０℃に設定した。（メタ）アクリル系樹脂組成物からなるペレットは、ホッパーに加温した除湿空気を送風することにより６５℃に加温した。また、ホッパー下部に窒素導入管を設けて、押出機内に窒素ガスを導入した。ベント口から２５Ｔｏｒｒにて吸引を行いながら、ペレットを単軸スクリューにて溶融させ、ギアポンプを用いて、ろ過精度５μｍのリーフディスク型のポリマーフィルターに通した。次いで、幅６００ｍｍのＴダイより溶融樹脂を押出し、１１５℃に温調された硬質クロムメッキの冷却ロール上にキャスティングすることで、膜厚１４５μｍの原反フィルムを取得した。
　上記溶融製膜後、キャスティングした冷却ロール表面を目視にて観察し、白濁が確認されない場合には「良」、フィルムの幅方向において端部にのみ白濁が確認された場合には「普」、フィルムの幅方向において中央部にも白濁が確認された場合には「不良」と判定した。 (8) Evaluation of roll contamination The (meth)acrylic resin composition was evaluated for roll contamination by performing open film formation.
Specifically, the film was formed by the following procedure.
A vented single-screw extruder having a barrier flight type screw with a diameter of 65 mm and L/D=32 was used for melt film formation. The extruder cylinder and gear pump temperatures were set at 275°C, and the polymer filter and T-die temperatures at 270°C. The pellets made of the (meth)acrylic resin composition were heated to 65° C. by blowing heated dehumidified air into the hopper. A nitrogen inlet pipe was provided at the bottom of the hopper to introduce nitrogen gas into the extruder. The pellets were melted with a single screw while being sucked from the vent port at 25 Torr, and passed through a leaf disk type polymer filter with a filtration accuracy of 5 μm using a gear pump. Then, the molten resin was extruded from a T-die with a width of 600 mm and cast on a hard chromium-plated cooling roll temperature-controlled at 115° C. to obtain a raw film with a thickness of 145 μm.
After the above-mentioned melt film formation, the surface of the cast cooling roll was visually observed. If white turbidity was also observed in the central portion in the width direction of the film, it was determined as "defective".
（９）発泡性評価
　１００℃の真空乾燥機にて４時間乾燥した（メタ）アクリル系樹脂組成物を、ＪＩＳ－Ｋ７２１０に規定のシリンダー内に充填し、成形加工を想定した温度である２８０℃で２０分間保持した後、ストランド状に押し出して、得られたストランドの上部標線と下部標線との間にシルバーストリークが存在するか否かを、目視により確認した。シルバーストリークの発生が確認された場合を「×」、確認されなかった場合を「○」とした。 (9) Foamability evaluation The (meth)acrylic resin composition dried for 4 hours in a vacuum dryer at 100 ° C. is filled in a cylinder specified in JIS-K7210, and the temperature is 280 ° C., which is the temperature assumed for molding. After holding for 20 minutes at , it was extruded into a strand, and the presence or absence of silver streaks between the upper and lower marked lines of the resulting strand was visually confirmed. When the generation of silver streaks was confirmed, it was evaluated as "×", and when it was not confirmed, it was evaluated as "○".
　実施例１
　攪拌装置、温度センサー、冷却コンデンサ、及び窒素導入管を備えた反応釜に、メタクリル酸メチル（ＭＭＡ）８３．５部、２－（ヒドロキシメチル）アクリル酸メチル（ＭＨＭＡ；α－（ヒドロキシメチル）アクリル酸メチルともいう）１２部、及びトルエン８８．７部を仕込み、これに窒素を通じつつ、１０５℃まで昇温させた。昇温に伴う還流が始まったところで、重合開始剤としてｔ－アミルパーオキシイソノナノエート２０重量％トルエン溶液（アルケマ吉富株式会社製、ルペロックス（登録商標）５７０Ｔ２０）０．５３５部を添加した。続けて、スチレン（Ｓｔ）４．５部、及びｎ－ドデシルメルカプタン（ｎＤＭ）０．１５部からなる溶液を２時間かけて滴下した。また、ｔ－アミルパーオキシイソノナノエート２０重量％トルエン溶液１．０６５部を４時間かけて滴下した。これらＳｔ、ｎＤＭ、ｔ－アミルパーオキシイソナノエートを滴下している間、混合液を約１０５～１１０℃で還流し、溶液重合を進行させた。滴下終了後、同温度でさらに２時間の熟成を行った。重合が終了した時点（重合開始から６時間経過した時点）における分子量（Ｍｗ）及び転化率を、重合溶液の一部を抜き取って評価したところ、それぞれ１５．７万、９１．３質量％であった。 Example 1
83.5 parts of methyl methacrylate (MMA), methyl 2-(hydroxymethyl) acrylate (MHMA; α-(hydroxymethyl) acrylic 12 parts of methyl acid) and 88.7 parts of toluene were charged, and the temperature was raised to 105° C. while nitrogen was passed through. When refluxing with temperature rise started, 0.535 parts of a 20% by weight toluene solution of t-amylperoxyisononanoate (manufactured by Arkema Yoshitomi Co., Ltd., Luperox (registered trademark) 570T20) was added as a polymerization initiator. Subsequently, a solution consisting of 4.5 parts of styrene (St) and 0.15 parts of n-dodecylmercaptan (nDM) was added dropwise over 2 hours. Further, 1.065 parts of a 20% by weight toluene solution of t-amylperoxyisononanoate was added dropwise over 4 hours. While the St, nDM and t-amylperoxyisonanoate were being added dropwise, the mixture was refluxed at about 105-110° C. to allow solution polymerization to proceed. After completion of dropping, aging was further performed at the same temperature for 2 hours. When the molecular weight (Mw) and the conversion rate at the end of the polymerization (6 hours after the start of the polymerization) were evaluated by extracting a part of the polymerization solution, they were 157,000 and 91.3% by mass, respectively. rice field.
　次に、得られた重合溶液に、環化縮合反応の触媒（環化触媒）として、リン酸ブチル（ＳＣ有機化学株式会社製、Ｐｈｏｓｌｅｘ　Ａ－４）０．０３１２部を加え、約９０～１１０℃の還流下において２時間、ラクトン環構造を形成するための環化縮合反応を進行させた。さらに、得られた重合溶液を、２３５℃に加熱した多管式熱交換器に通して環化縮合反応を完結させた。 Next, 0.0312 parts of butyl phosphate (Phoslex A-4, manufactured by SC Organic Chemical Co., Ltd.) is added to the obtained polymerization solution as a catalyst for the cyclization condensation reaction (cyclization catalyst), and the The cyclization condensation reaction to form the lactone ring structure was allowed to proceed for 2 hours under reflux at °C. Furthermore, the resulting polymerization solution was passed through a shell and tube heat exchanger heated to 235° C. to complete the cyclization condensation reaction.
　その後、ベントタイプスクリュー二軸押出機（Ｌ／Ｄ＝５２．５）を用いて、得られた重合溶液を樹脂量換算で１００部／時の処理速度で導入し脱揮処理を行った。上記押出機は、１個のリアベント、４個のフォアベント（以下、上流側から第１、第２、第３、第４ベントと称する）、及び第３ベントと第４ベントとの間にサイドフィーダーを備えており、回転数８０ｒｐｍ、減圧度２５～８００ｈＰａ、バレル温度２５５℃（２５５℃の熱媒で加熱）とした。また、上記押出機は、先端部にリーフディスク型のポリマーフィルター（濾過精度１０μｍ）が配置されており、ポリマーフィルターの先端部に設けられた押出ダイには、細孔が樹脂吐出面の円周に沿って多数、貫通形成され、ウォータリングカット方式のカッターが取り付けられている。また、カット、水冷固化後に遠心乾燥機による脱水設備が設けられ、気体による搬送により、貯蔵サイロへ搬送する構成となっている。
　重合溶液を導入する際には、イオン交換水を１．５部／時の投入速度で第２、第３ベントの上流から、イオン交換水を３部／時の投入速度で第４ベントの上流から投入した。
　脱揮終了後、リーフディスク型のポリマーフィルター（濾過精度：１０μｍ）を通過させた後、押出ダイが有するダイス（細孔）から溶融状態の（メタ）アクリル系樹脂組成物を押し出し、カット、水冷固化後に遠心乾燥機による脱水、搬送後、貯蔵サイロで冷却することにより（メタ）アクリル系樹脂組成物（Ａ－１）を得た。得られた（メタ）アクリル系樹脂組成物（Ａ－１）の配合組成を表１に、各物性を表２に示す。 Thereafter, using a vent-type screw twin-screw extruder (L/D=52.5), the obtained polymerization solution was introduced at a processing rate of 100 parts/hour in terms of resin amount, and devolatilization treatment was performed. The extruder has one rear vent, four fore vents (hereinafter referred to as first, second, third, and fourth vents from the upstream side), and side vents between the third and fourth vents. Equipped with a feeder, the number of revolutions was 80 rpm, the degree of pressure reduction was 25 to 800 hPa, and the barrel temperature was 255° C. (heated with a heat medium of 255° C.). In addition, the extruder has a leaf disk-shaped polymer filter (filtration accuracy of 10 μm) at the tip, and the extrusion die provided at the tip of the polymer filter has pores formed around the circumference of the resin ejection surface. A large number of water ring cut type cutters are installed along the ridge. After cutting and water-cooling solidification, a dehydration facility using a centrifugal dryer is provided, and the material is transported to a storage silo by gas transportation.
When introducing the polymerization solution, ion-exchanged water is introduced at a rate of 1.5 parts/hour from the upstream of the second and third vents, and ion-exchanged water is introduced at a rate of 3 parts/hour from the upstream of the fourth vent. put in from
After the completion of devolatilization, after passing through a leaf disk type polymer filter (filtration accuracy: 10 μm), the molten (meth)acrylic resin composition is extruded from the die (pore) of the extrusion die, cut, and water cooled. After solidification, it was dehydrated using a centrifugal dryer, transported, and then cooled in a storage silo to obtain a (meth)acrylic resin composition (A-1). Table 1 shows the composition of the obtained (meth)acrylic resin composition (A-1), and Table 2 shows its physical properties.
　実施例２
　環化縮合反応の触媒（環化触媒）として、リン酸ブチル（ＳＣ有機化学株式会社製、Ｐｈｏｓｌｅｘ　Ａ－４）０．０４６８部を加えた以外は実施例１と同様にして、（メタ）アクリル系樹脂組成物（Ａ－２）を得た。得られた（メタ）アクリル系樹脂組成物（Ａ－２）の配合組成を表１に、各物性を表２に示す。 Example 2
As a catalyst (cyclization catalyst) for the cyclization condensation reaction, (meth)acrylic A system resin composition (A-2) was obtained. Table 1 shows the compounding composition of the obtained (meth)acrylic resin composition (A-2), and Table 2 shows each physical property.
　実施例３
　環化縮合反応の触媒（環化触媒）として、リン酸ブチル（ＳＣ有機化学株式会社製、Ｐｈｏｓｌｅｘ　Ａ－４）０．０６２４部を加えた以外は実施例１と同様にして、（メタ）アクリル系樹脂組成物（Ａ－３）を得た。得られた（メタ）アクリル系樹脂組成物（Ａ－３）の配合組成を表１に、各物性を表２に示す。 Example 3
(Meth)acrylic (meth)acrylic A system resin composition (A-3) was obtained. Table 1 shows the composition of the obtained (meth)acrylic resin composition (A-3), and Table 2 shows its physical properties.
　実施例４
　実施例２と同様にして環化縮合反応を完結後、ベントタイプスクリュー二軸押出機（Ｌ／Ｄ＝５２．５）を用いて脱揮処理を行った。その際、紫外線吸収剤（株式会社ＡＤＥＫＡ製、アデカスタブ（登録商標）ＬＡ－Ｆ７０）３５質量％のトルエン溶液を１．９２部／時の投入速度で第３ベントの上流から投入した以外は、実施例２と同様に実施し、（メタ）アクリル系樹脂組成物（Ａ－４）を得た。得られた（メタ）アクリル系樹脂組成物（Ａ－４）の配合組成を表１に、各物性を表２に示す。 Example 4
After completing the cyclization condensation reaction in the same manner as in Example 2, devolatilization treatment was performed using a vent-type screw twin-screw extruder (L/D=52.5). At that time, a toluene solution of 35% by mass of an ultraviolet absorber (ADEKA Co., Ltd., ADEKA STAB (registered trademark) LA-F70) was introduced from the upstream of the third vent at an injection rate of 1.92 parts / hour. It was carried out in the same manner as in Example 2 to obtain a (meth)acrylic resin composition (A-4). Table 1 shows the formulation of the obtained (meth)acrylic resin composition (A-4), and Table 2 shows its physical properties.
　実施例５
　環化縮合反応の触媒（環化触媒）として、リン酸オクチル（ＳＣ有機化学株式会社製、Ｐｈｏｓｌｅｘ　Ａ－８Ｎ）０．０４７５部を加えた以外は実施例１と同様にして、（メタ）アクリル系樹脂組成物（Ａ－５）を得た。得られた（メタ）アクリル系樹脂（Ａ－５）組成物の配合組成を表１に、各物性を表２に示す。 Example 5
(Meth)acrylic (meth)acrylic A system resin composition (A-5) was obtained. Table 1 shows the formulation of the obtained (meth)acrylic resin (A-5) composition, and Table 2 shows each physical property.
　比較例１
　攪拌装置、温度センサー、冷却コンデンサ、及び窒素導入管を備えた反応釜に、ＭＭＡ８３．５部、ＭＨＭＡ１２部、ｎＤＭ０．０７部、及びトルエン８８．７部を仕込み、これに窒素を通じつつ、１０５℃まで昇温させた。昇温に伴う還流が始まったところで、重合開始剤としてｔ－アミルパーオキシイソノナノエート２０重量％トルエン溶液（アルケマ吉富株式会社製、ルペロックス（登録商標）５７０Ｔ２０）０．４５１部を添加した。続けて、Ｓｔ４．５部、及びｔ－アミルパーオキシイソノナノエート２０重量％トルエン溶液０．８９９部からなる溶液を２時間かけて滴下した。これらＳｔ、及びｔ－アミルパーオキシイソナノエートを滴下している間、混合液を約１０５～１１０℃で還流し、溶液重合を進行させた。滴下終了後、同温度でさらに４時間の熟成を行った。重合が終了した時点（重合開始から６時間経過した時点）における分子量(Ｍｗ)及び転化率を、重合溶液の一部を抜き取って評価したところ、それぞれ１５．３万、９４．５質量％であった。 Comparative example 1
83.5 parts of MMA, 12 parts of MHMA, 0.07 parts of nDM, and 88.7 parts of toluene were charged into a reactor equipped with a stirrer, temperature sensor, cooling condenser, and nitrogen inlet tube, and heated to 105°C while passing nitrogen through the reactor. The temperature was raised to When the reflux started with the temperature rise, 0.451 part of a 20% by weight toluene solution of t-amylperoxyisononanoate (manufactured by Arkema Yoshitomi Co., Ltd., Luperox (registered trademark) 570T20) was added as a polymerization initiator. Subsequently, a solution consisting of 4.5 parts of St and 0.899 parts of a 20% by weight toluene solution of t-amylperoxyisononanoate was added dropwise over 2 hours. While the St and t-amylperoxyisonanoate were being added dropwise, the mixed solution was refluxed at about 105 to 110° C. to proceed solution polymerization. After completion of dropping, aging was further performed at the same temperature for 4 hours. When the molecular weight (Mw) and the conversion rate at the end of the polymerization (6 hours after the start of the polymerization) were evaluated by extracting a part of the polymerization solution, they were 153,000 and 94.5% by mass, respectively. rice field.
　次に、得られた重合溶液に、環化縮合反応の触媒（環化触媒）として、リン酸ステアリル（ＳＣ有機化学株式会社製、Ｐｈｏｓｌｅｘ　Ａ－１８）０．０７５部を加え、約９０～１１０℃の還流下において２時間、ラクトン環構造を形成するための環化縮合反応を進行させた。さらに、得られた重合溶液を、２３５℃に加熱した多管式熱交換器に通して環化縮合反応を完結させた。 Next, 0.075 parts of stearyl phosphate (Phoslex A-18, manufactured by SC Organic Chemical Co., Ltd.) is added to the obtained polymerization solution as a catalyst for the cyclization condensation reaction (cyclization catalyst), and the The cyclization condensation reaction to form the lactone ring structure was allowed to proceed for 2 hours under reflux at °C. Furthermore, the resulting polymerization solution was passed through a shell and tube heat exchanger heated to 235° C. to complete the cyclization condensation reaction.
　その後、実施例１で使用したベントタイプスクリュー二軸押出機（Ｌ／Ｄ＝５２．５）を用いて、得られた重合溶液を樹脂量換算で１００部／時の処理速度で導入し脱揮処理を行った。重合溶液を導入する際には、イオン交換水を１．５部／時の投入速度で第２、第４ベントの上流から、オクチル酸亜鉛トルエン溶液（日本化学産業株式会社製、ニッカオクチックス亜鉛１．８％）：フェノール系酸化防止剤（株式会社ＡＤＥＫＡ製、アデカスタブ（登録商標）ＡＯ－６０）：硫黄系酸化防止剤（株式会社ＡＤＥＫＡ製、アデカスタブ（登録商標）ＡＯ－４１２Ｓ）＝３３．７４：１：１からなるトルエン溶液を０．１６５部／時の投入速度で第３ベントの上流から投入した。
　脱揮終了後、リーフディスク型のポリマーフィルター（濾過精度：５μｍ）を通過させた後、押出ダイが有するダイス（細孔）から溶融状態の（メタ）アクリル系樹脂組成物を押し出し、カット、水冷固化後に遠心乾燥機による脱水、搬送後、貯蔵サイロで冷却することにより（メタ）アクリル系樹脂組成物（Ａ－６）を得た。得られた（メタ）アクリル系樹脂（Ａ－６）組成物の配合組成を表１に、各物性を表２に示す。 After that, using the vent-type screw twin-screw extruder (L/D = 52.5) used in Example 1, the obtained polymerization solution was introduced at a processing rate of 100 parts / hour in terms of resin amount and devolatilized. processed. When introducing the polymerization solution, ion-exchanged water was introduced from the upstream of the second and fourth vents at a rate of 1.5 parts/hour, and a toluene solution of zinc octylate (Nippon Kagaku Sangyo Co., Ltd., Nikka Octix Zinc 1.8%): Phenolic antioxidant (ADEKA Corporation, ADEKA STAB (registered trademark) AO-60): Sulfur-based antioxidant (ADEKA Corporation, ADEKA STAB (registered trademark) AO-412S) = 33. A toluene solution consisting of 74:1:1 was charged upstream of the third vent at a rate of 0.165 parts/hour.
After the completion of devolatilization, after passing through a leaf disk type polymer filter (filtration accuracy: 5 μm), the molten (meth)acrylic resin composition is extruded from the die (pore) of the extrusion die, cut, and water cooled. After solidification, it was dehydrated using a centrifugal dryer, transported, and then cooled in a storage silo to obtain a (meth)acrylic resin composition (A-6). Table 1 shows the composition of the obtained (meth)acrylic resin (A-6) composition, and Table 2 shows each physical property.
　比較例２
　環化縮合反応の触媒（環化触媒）として、リン酸メチル（ＳＣ有機化学株式会社製、Ｐｈｏｓｌｅｘ　Ａ－１）０．１部を加えた以外は実施例１と同様にして、（メタ）アクリル系樹脂組成物（Ａ－７）を得た。得られた（メタ）アクリル系樹脂（Ａ－７）組成物の配合組成を表１に、各物性を表２に示す。 Comparative example 2
(Meth)acrylic (meth)acrylic A system resin composition (A-7) was obtained. Table 1 shows the formulation of the obtained (meth)acrylic resin (A-7) composition, and Table 2 shows each physical property.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　表２から明らかなように、実施例１～５で得られた（メタ）アクリル系樹脂組成物（Ａ－１）～（Ａ－５）は何れも密着性についての評価が良好であり、比較例１で得られた（メタ）アクリル系樹脂組成物（Ａ－６）は密着性についての評価が悪かった。特に、リン酸ブチルを使用して得られた（メタ）アクリル系樹脂組成物（Ａ－１）～（Ａ－４）は、密着性について優れた結果を示した。 As is clear from Table 2, the (meth)acrylic resin compositions (A-1) to (A-5) obtained in Examples 1 to 5 all had good adhesion evaluation, and the comparison The (meth)acrylic resin composition (A-6) obtained in Example 1 was poorly evaluated for adhesion. In particular, the (meth)acrylic resin compositions (A-1) to (A-4) obtained using butyl phosphate exhibited excellent adhesion.
　また、表２から明らかなように、実施例１～５で得られた（メタ）アクリル系樹脂組成物（Ａ－１）～（Ａ－５）は何れもロール汚染についての評価が良好であり、比較例１で得られた（メタ）アクリル系樹脂組成物（Ａ－６）はロール汚染についての評価が悪かった。特に、リン酸ブチルを使用して得られた（メタ）アクリル系樹脂組成物（Ａ－１）～（Ａ－４）は、ロール汚染について優れた結果を示した。 In addition, as is clear from Table 2, the (meth)acrylic resin compositions (A-1) to (A-5) obtained in Examples 1 to 5 all had good evaluations for roll contamination. , the (meth)acrylic resin composition (A-6) obtained in Comparative Example 1 was poorly evaluated for roll contamination. In particular, the (meth)acrylic resin compositions (A-1) to (A-4) obtained using butyl phosphate showed excellent results regarding roll contamination.
　また、表２から明らかなように、実施例１～５で得られた（メタ）アクリル系樹脂組成物（Ａ－１）～（Ａ－５）は何れも発泡性についての評価が良好であり、比較例２で得られた（メタ）アクリル系樹脂組成物（Ａ－７）は発泡性についての評価が悪かった。
  In addition, as is clear from Table 2, the (meth)acrylic resin compositions (A-1) to (A-5) obtained in Examples 1 to 5 all had good evaluations of foamability. , the (meth)acrylic resin composition (A-7) obtained in Comparative Example 2 was poorly evaluated for foamability.

Claims (18)

  1. 　主鎖にラクトン環構造及び無水グルタル酸構造の少なくとも一方である環構造を有する（メタ）アクリル系重合体を含む（メタ）アクリル系樹脂組成物であって、
    　（メタ）アクリル系樹脂組成物中のリン原子の含有量が、１．０ｐｐｍ以上５０ｐｐｍ以下であり、
    　（メタ）アクリル系樹脂組成物中の下記式（Ｉ）で表される化合物の含有量が、９５ｐｐｍ以下であることを特徴とする（メタ）アクリル系樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
    ［式（Ｉ）中、Ｒ1は炭素数１３以上の脂肪族炭化水素基、又は炭素数６以上の芳香族炭化水素基を表す。］     A (meth)acrylic resin composition comprising a (meth)acrylic polymer having a ring structure that is at least one of a lactone ring structure and a glutaric anhydride structure in the main chain,
    The content of phosphorus atoms in the (meth)acrylic resin composition is 1.0 ppm or more and 50 ppm or less,
    A (meth)acrylic resin composition, wherein the content of a compound represented by the following formula (I) in the (meth)acrylic resin composition is 95 ppm or less.
    Figure JPOXMLDOC01-appb-C000001
    [In Formula (I), R 1 represents an aliphatic hydrocarbon group having 13 or more carbon atoms or an aromatic hydrocarbon group having 6 or more carbon atoms. ]
  2. 　（メタ）アクリル系樹脂組成物中の下記式（ＩＩ）で表される化合物の含有量が、９５ｐｐｍ以下である請求項１に記載の（メタ）アクリル系樹脂組成物。
    Figure JPOXMLDOC01-appb-C000002
    ［式（ＩＩ）中、Ｒ2は炭素数３以上１２以下の脂肪族炭化水素基を表す。］     The (meth)acrylic resin composition according to claim 1, wherein the content of the compound represented by the following formula (II) in the (meth)acrylic resin composition is 95 ppm or less.
    Figure JPOXMLDOC01-appb-C000002
    [In Formula (II), R 2 represents an aliphatic hydrocarbon group having 3 or more and 12 or less carbon atoms. ]
  3. 　環構造を有する（メタ）アクリル系重合体における環構造単位の含有割合が、５質量％以上７０質量％以下である請求項１に記載の（メタ）アクリル系樹脂組成物。 The (meth)acrylic resin composition according to claim 1, wherein the content of the ring structural unit in the (meth)acrylic polymer having a ring structure is 5% by mass or more and 70% by mass or less.
  4. 　（メタ）アクリル系樹脂組成物中の環構造を有する（メタ）アクリル系重合体の含有量が、５０質量％以上である請求項１に記載の（メタ）アクリル系樹脂組成物。 The (meth)acrylic resin composition according to claim 1, wherein the content of the (meth)acrylic polymer having a ring structure in the (meth)acrylic resin composition is 50% by mass or more.
  5. 　ガラス転移温度が１２０℃以上である請求項１に記載の（メタ）アクリル系樹脂組成物。 The (meth)acrylic resin composition according to claim 1, which has a glass transition temperature of 120°C or higher.
  6. 　ヒンダードフェノール化合物を含まない請求項１に記載の（メタ）アクリル系樹脂組成物。 The (meth)acrylic resin composition according to claim 1, which does not contain a hindered phenol compound.
  7. 　ヒンダードフェノール部位を有する有機リン化合物を含まない請求項１に記載の（メタ）アクリル系樹脂組成物。 The (meth)acrylic resin composition according to claim 1, which does not contain an organophosphorus compound having a hindered phenol moiety.
  8. 　請求項１～７のいずれかに記載の（メタ）アクリル系樹脂組成物を含む成形体。 A molded article containing the (meth)acrylic resin composition according to any one of claims 1 to 7.
  9. 　シート、フィルム又はレンズ状である請求項８に記載の成形体。 The molded article according to claim 8, which is in the form of a sheet, film or lens.
  10. 　（メタ）アクリル系重合体において、下記（ｉ）及び（ｉｉ）の環化反応のうち少なくとも片方の環化反応を行い、前記（メタ）アクリル系重合体の主鎖に環構造を形成する環化工程を含む（メタ）アクリル系樹脂組成物の製造方法であって、
    　（ｉ）ヒドロキシ基と、エステル基又はカルボキシル基との間で、ラクトン環構造を形成する環化反応
    　（ｉｉ）カルボキシル基と、エステル基又は他のカルボキシル基との間で、無水グルタル酸構造を形成する環化反応
    　前記環化反応において、リン酸Ｃ3-12アルキルエステル、亜リン酸Ｃ3-12アルキルエステル、及び次亜リン酸Ｃ3-12アルキルエステルからなる群から選ばれる少なくとも１種を触媒として用いることを特徴とする（メタ）アクリル系樹脂組成物の製造方法。     In the (meth)acrylic polymer, at least one of the cyclization reactions (i) and (ii) below is performed to form a ring structure on the main chain of the (meth)acrylic polymer. A method for producing a (meth)acrylic resin composition including a curing step,
    (i) a cyclization reaction to form a lactone ring structure between a hydroxy group and an ester group or a carboxyl group; (ii) a glutaric anhydride structure between a carboxyl group and an ester group or another carboxyl group; Cyclization reaction to form In the cyclization reaction, at least one selected from the group consisting of C 3-12 alkyl phosphate, C 3-12 alkyl phosphite, and C 3-12 hypophosphite As a catalyst, a method for producing a (meth)acrylic resin composition.
  11. 　前記環化反応で用いられる前記触媒が、リン酸Ｃ3-７アルキルエステル、亜リン酸Ｃ3-７アルキルエステル、及び次亜リン酸Ｃ3-７アルキルエステルからなる群から選ばれる少なくとも１種である請求項１０に記載の（メタ）アクリル系樹脂組成物の製造方法。 The catalyst used in the cyclization reaction is at least one selected from the group consisting of C 3-7 alkyl phosphate, C 3-7 alkyl phosphite, and C 3-7 hypophosphite. The method for producing a (meth)acrylic resin composition according to claim 10.
  12. 　前記環化反応で用いられる前記触媒が、リン酸ブチル、亜リン酸ブチル、及び次亜リン酸ブチルからなる群から選ばれる少なくとも１種である請求項１０に記載の（メタ）アクリル系樹脂組成物の製造方法。 11. The (meth)acrylic resin composition according to claim 10, wherein the catalyst used in the cyclization reaction is at least one selected from the group consisting of butyl phosphate, butyl phosphite, and butyl hypophosphite. A method of making things.
  13. 　前記触媒の使用量が、前記（メタ）アクリル系重合体を構成する単量体成分の全量に対して１０００ｐｐｍ以下である請求項１０に記載の（メタ）アクリル系樹脂組成物の製造方法。 The method for producing a (meth)acrylic resin composition according to claim 10, wherein the amount of the catalyst used is 1000 ppm or less with respect to the total amount of monomer components constituting the (meth)acrylic polymer.
  14. 　前記触媒の分解温度が１６０℃以上である請求項１０に記載の（メタ）アクリル系樹脂組成物の製造方法。 The method for producing a (meth)acrylic resin composition according to claim 10, wherein the decomposition temperature of the catalyst is 160°C or higher.
  15. 　（メタ）アクリル系モノマーを重合して前記（メタ）アクリル系重合体を形成する重合工程をさらに含む請求項１０～１４のいずれかに記載の（メタ）アクリル系樹脂組成物の製造方法。 The method for producing a (meth)acrylic resin composition according to any one of claims 10 to 14, further comprising a polymerization step of polymerizing a (meth)acrylic monomer to form the (meth)acrylic polymer.
  16. 　前記（メタ）アクリル系重合体の全構成単位における前記（メタ）アクリル系モノマーに由来する構成単位の合計含有割合が、５０質量％以上である請求項１５に記載の（メタ）アクリル系樹脂組成物の製造方法。 The (meth)acrylic resin composition according to claim 15, wherein the total content of structural units derived from the (meth)acrylic monomer in all structural units of the (meth)acrylic polymer is 50% by mass or more. A method of making things.
  17. 　前記（メタ）アクリル系モノマーとしてα－（１－ヒドロキシアルキル）アクリル酸アルキルを有し、前記（メタ）アクリル系重合体の全構成単位における前記α－（１－ヒドロキシアルキル）アクリル酸アルキルに由来する構成単位の合計含有割合が、５質量％以上である請求項１５に記載の（メタ）アクリル系樹脂組成物の製造方法。 Having α-(1-hydroxyalkyl)alkyl acrylate as the (meth)acrylic monomer, and derived from the α-(1-hydroxyalkyl)alkyl acrylate in all structural units of the (meth)acrylic polymer The method for producing a (meth)acrylic resin composition according to claim 15, wherein the total content of the constituent units is 5% by mass or more.
  18. 　前記重合工程、前記環化工程、及び前記環化工程の後の工程から選ばれる１つ以上の工程で添加剤が添加され、
    　前記添加剤は、ヒンダードフェノール化合物及びヒンダードフェノール部位を有する有機リン化合物を含まない、請求項１５に記載の（メタ）アクリル系樹脂組成物の製造方法。     an additive is added in one or more steps selected from the polymerization step, the cyclization step, and a step after the cyclization step;
    16. The method for producing a (meth)acrylic resin composition according to claim 15, wherein the additive does not contain a hindered phenol compound or an organophosphorus compound having a hindered phenol moiety.
PCT/JP2023/000535 2022-01-14 2023-01-12 (meth)acrylic resin composition and molded article using same, and method for producing (meth)acrylic resin composition WO2023136275A1 (en)

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Citations (6)

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JP2001151814A (en) * 1999-11-26 2001-06-05 Nippon Shokubai Co Ltd Method of manufacturing for transparent heat resistant resin and use of the same
JP2002303975A (en) * 2000-12-05 2002-10-18 Nippon Shokubai Co Ltd Photosensitive resin composition and its use
WO2007123253A1 (en) * 2006-04-26 2007-11-01 Nippon Shokubai Co., Ltd. Process for production of alkene having hydroxyl group, and alkene having hydroxyl group
JP2008163187A (en) * 2006-12-28 2008-07-17 Toray Ind Inc Thermoplastic polymer and its production method
JP2014069437A (en) * 2012-09-28 2014-04-21 Nippon Shokubai Co Ltd Stretched film and production method thereof
JP2017082240A (en) * 2017-01-12 2017-05-18 富士フイルム株式会社 Acrylic film and manufacturing method therefor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001151814A (en) * 1999-11-26 2001-06-05 Nippon Shokubai Co Ltd Method of manufacturing for transparent heat resistant resin and use of the same
JP2002303975A (en) * 2000-12-05 2002-10-18 Nippon Shokubai Co Ltd Photosensitive resin composition and its use
WO2007123253A1 (en) * 2006-04-26 2007-11-01 Nippon Shokubai Co., Ltd. Process for production of alkene having hydroxyl group, and alkene having hydroxyl group
JP2008163187A (en) * 2006-12-28 2008-07-17 Toray Ind Inc Thermoplastic polymer and its production method
JP2014069437A (en) * 2012-09-28 2014-04-21 Nippon Shokubai Co Ltd Stretched film and production method thereof
JP2017082240A (en) * 2017-01-12 2017-05-18 富士フイルム株式会社 Acrylic film and manufacturing method therefor

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