Resin composition for molding, and molded article

Abstract

To provide a resin composition for molding which contains an ultraviolet absorbing polymer that can be inexpensively purified, has good compatibility with polyolefin, and enables formation of a molded product having good transparency.SOLUTION: A resin composition for molding contains a thermoplastic resin and an ultraviolet absorbing polymer, in which the ultraviolet absorbing polymer is a polymer having a monomer unit represented by the following general formula (1), a monomer unit represented by the following general formula (2) and a thiol-based chain transfer agent residue, and a thiol-based chain transfer agent forming a thiol-based chain transfer movement residue has a thiol group, and one or more sites selected from the group consisting of a carboxyl group, a hydroxyl group and an ester bond.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition for molding.

Background Art

[0002] Conventionally, resin molded articles (hereinafter referred to as molded articles) have been used as packaging materials for pharmaceutical agents, cosmetics, etc. The contents of pharmaceutical agents, cosmetics, etc. are liable to deteriorate by ultraviolet rays, but when an ultraviolet absorber is blended, the ultraviolet absorber may migrate and contaminate the contents. Therefore, Patent Documents 1 and 2 disclose a resin composition for molding in which a polyolefin and an ultraviolet-absorbing monomer are polymerized in a twin-screw extruder. Patent Document 3 discloses a resin composition for molding containing an ultraviolet-absorbing polymer polymerized using 1-dodecanethiol as a chain transfer agent.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the molding resin compositions of Patent Documents 1 and 2 have a problem that the compatibility between the contained materials is low, the haze of the molded body is high, and when the amount of the ultraviolet absorber monomer is increased to enhance the ultraviolet absorptivity, the transparency of the molded body decreases. Further, in the molding resin composition of Patent Document 3, when an inexpensive low-boiling alcohol is used for purification in order to remove low-molecular-weight polymers in the ultraviolet absorber polymer in consideration of pharmaceutical and cosmetic applications, the ultraviolet absorber polymer has a 1-dodecanethiol residue with high hydrophobicity at the molecular terminal, so that the solubility in the alcohol is low and the purification takes a long time. On the other hand, when a non-alcohol solvent is used, there is a problem that the remaining non-alcohol solvent has an adverse effect on the human body such as odor.

[0005] An object of the present invention is to provide a molding resin composition containing an ultraviolet absorber polymer that can be purified inexpensively and efficiently, has good compatibility with polyolefin, and can form a molded body having good transparency.

Means for Solving the Problems

[0006] The molding resin composition of the present invention is a molding resin composition containing a thermoplastic resin and an ultraviolet absorber polymer, wherein the ultraviolet absorber polymer is a polymer having a monomer unit represented by the following general formula (1), a monomer unit represented by the following general formula (2), and a thiol-based chain transfer agent residue, The thiol-based chain transfer agent that forms the thiol-based chain transfer agent residue has a thiol group and at least one site selected from the group consisting of a carboxyl group, a hydroxyl group, and an ester bond.

[0007]

Chemical Formula

[0008] In General Formula (1), R 11 represents any one selected from the group consisting of a hydrogen atom and a methyl group, and U is a hydrocarbon group having a skeleton that absorbs ultraviolet rays and may contain a hetero atom. In general formula (2), R 21 represents any one selected from the group consisting of a hydrogen atom and a methyl group, and Z represents any one selected from the group consisting of a linear hydrocarbon group having 10 or more carbon atoms and a cyclic hydrocarbon group.

Advantages of the Invention

[0009] According to the present invention described above, there can be provided a molding resin composition containing an ultraviolet-absorbing polymer that can be purified inexpensively and efficiently, having good compatibility with polyolefin, and capable of forming a molded article with good transparency, and a molded article.

Embodiments for Carrying Out the Invention

[0010] The terms in this specification and the like are defined. In this specification and the like, "(meth)acrylic", "(meth)acrylate", "(meth)acryloyl", etc. mean "acrylic or methacrylic", "acrylate or methacrylate", "acryloyl or methacryloyl", etc. For example, "(meth)acrylic acid" means "acrylic acid or methacrylic acid". Further, a monomer means a compound containing an ethylenically unsaturated group. The monomer after polymerization is called a monomer unit, and before polymerization, it is called a monomer.

[0011] The molding resin composition of the present invention is a molding resin composition containing a thermoplastic resin and an ultraviolet-absorbing polymer. Hereinafter, each component contained in the composition of the present invention will be described in detail.

[0012] <Thermoplastic resin> Thermoplastic resins include, for example, polyolefins such as polyethylene and polypropylene, polycarbonate, polyacryl such as polymethyl methacrylate, polyester, cycloolefin resin, polystyrene, polyphenylene ether, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamide, polyacetal, polycarbonate, polyvinyl chloride, polyvinylidene chloride, and polyetherimide. Among these, it is particularly preferable to select polyolefins and cycloolefin resins because good moldability and mechanical strength of the molded product can be obtained. Also, polyester, polyacryl, and polycarbonate are preferable. The number average molecular weight of the thermoplastic resin is preferably more than 30,000.

[0013] <Polyolefin> Polyolefins include, for example, polyethylene, polypropylene, polybutene-1, and poly-4-methylpentene, as well as copolymers thereof.

[0014] The weight average molecular weight of the polyolefin is about 30,000 to 500,000, and preferably 30 ,000 to 200,000.

[0015] Polyethylene includes, for example, low-density polyethylene and high-density polyethylene. Polypropylene includes, for example, crystalline or amorphous polypropylene. These copolymers include, for example, random, block or graft copolymers of ethylene-propylene, copolymers of α-olefin and ethylene or propylene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-acrylic acid copolymer, etc. Among these, crystalline or amorphous polypropylene, random, block or graft copolymers of ethylene-propylene are preferable, and propylene-ethylene block copolymer is more preferable. Also, polypropylene is preferable from the viewpoint of being inexpensive and having a small specific gravity, so that the weight of the molded body can be reduced.

[0016] The melt flow rate (MFR) of the polyolefin is preferably 1 to 100 (g / 10 min). The MFR is a value determined in accordance with JIS K-7210.

[0017] <Polycarbonate> Polycarbonate is a compound synthesized from a divalent phenol and a carbonate precursor by a known method. Examples of the divalent phenol include hydroquinone, resorcinol, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4-hydroxyphenyl) sulfide, etc. Among these, bis(4-hydroxyphenyl) alkane type is preferable, and 2,2-bis(4-hydroxyphenyl)propane, which is called bisphenol A, is more preferable. Examples of the carbonate precursor include phosgene, diphenyl carbonate, dihaloformate of divalent phenol, etc. Among these, diphenyl carbonate is preferable.

[0018] <Polyacrylic> Polyacrylic is a compound obtained by polymerizing monomers such as acrylic acid and methyl methacrylate and / or ethyl methacrylate by a known method. For example, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, etc. can be mentioned. In addition to the above monomers, monomers such as butadiene, α-methylstyrene, maleic anhydride, etc. can be added and polymerized, and the heat resistance, fluidity, and impact resistance can be adjusted according to the monomer amount and molecular weight.

[0019] <Polyester> Polyester is a resin having an ester bond in the main chain of the molecule, and is a polycondensate synthesized from dicarboxylic acid (including its derivatives) and diol (dihydric alcohol or dihydric phenol); a polycondensate synthesized from dicarboxylic acid (including its derivatives) and a cyclic ether compound; a ring-opening polymer of a cyclic ether compound, etc. Polyester includes a homopolymer made of a polymer of dicarboxylic acid and diol, a copolymer using a plurality of raw materials, and a polymer blend obtained by mixing these. Note that the derivative of dicarboxylic acid is an acid anhydride or an esterified product. There are two types of dicarboxylic acids, aliphatic and aromatic, and aromatic ones that improve heat resistance are more preferable.

[0020] <Cycloolefin resin> Cycloolefin resin is a polymer of ethylene or α-olefin and cyclic olefin. The α-olefin is a monomer derived from an α-olefin having 4 to 12 carbon atoms (C4~C12), for example, 1-butene, 1-pentene, 1-hexene, 3-methyl-1- butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, etc. The cyclic olefin is a monomer derived from norbornene, and examples include a substituent of a hydrogen group, a halogen atom, a monovalent or divalent hydrocarbon group. Among these, unsubstituted norbornene is preferable.

[0021] <Vinyl chloride resin> Vinyl chloride resin includes, in addition to a vinyl chloride homopolymer, a copolymer of vinyl chloride and a monomer copolymerizable therewith (hereinafter, also referred to as "vinyl chloride copolymer"), a graft copolymer obtained by graft copolymerizing vinyl chloride onto a polymer other than the vinyl chloride copolymer, etc. Monomers copolymerizable with vinyl chloride include, for example, α-olefins such as ethylene, propylene, and butylene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; esters of acrylic acid or methacrylic acid such as methyl acrylate, ethyl methacrylate, and phenyl methacrylate; aromatic vinyls such as styrene and α-methylstyrene; vinyl halides such as vinylidene chloride and vinyl fluoride; N-substituted maleimides such as N-phenyl maleimide and N-cyclohexyl maleimide, and the like.

[0022] As polymers other than vinyl chloride copolymers, those capable of graft copolymerizing vinyl chloride may be used. For example, ethylene-vinyl acetate copolymers, ethylene-vinyl acetate-carbon monoxide copolymers, ethylene-ethyl acrylate copolymers, ethylene-ethyl acrylate-carbon monoxide copolymers, ethylene-methyl methacrylate copolymers, ethylene-propylene copolymers, acrylonitrile-butadiene copolymers, polyurethanes, and the like can be mentioned.

[0023] Plasticizers can be used in vinyl chloride resins. Examples of plasticizers include phthalate plasticizers such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), and diisodecyl phthalate (DIDP); fatty acid ester plasticizers such as di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), and dibutyl adipate (DBA); epoxidized ester plasticizers such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil fatty acid butyl, and octyl epoxystearate; trimellitate ester plasticizers such as tri-2-ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM); phosphate ester plasticizers such as trimethyl phosphate (TMP) and triethyl phosphate (TEP), and the like. Among these, epoxidized ester plasticizers are preferred from the viewpoints of the moldability and processability of resin sheets.

[0024] The melting point of the thermoplastic resin is preferably 120 to 330°C, more preferably 150 to 300°C.

[0025] <Ultraviolet-absorbing polymer> The ultraviolet-absorbing polymer is a polymer having a monomer unit represented by the following general formula (1), a monomer unit represented by the following general formula (2), and a thiol-based chain transfer agent residue. The thiol-based chain transfer agent that forms the thiol-based chain transfer agent residue has a thiol group and one or more sites selected from the group consisting of a carboxyl group, a hydroxyl group, and an ester bond.

[0026]

Chemical formula

[0027] In general formula (1), R 11 represents any one selected from the group consisting of a hydrogen atom and a methyl group, and U is a hydrocarbon group having a skeleton that absorbs ultraviolet rays and may contain a hetero atom. In general formula (2), R 21 represents any one selected from the group consisting of a hydrogen atom and a methyl group, and Z represents any one selected from the group consisting of a linear hydrocarbon group having 10 or more carbon atoms and a cyclic hydrocarbon group.

[0028] <General formula (1)> R 11 represents any one selected from the group consisting of a hydrogen atom and a methyl group, and U is a site containing one or more hydrocarbon groups or heterocyclic groups having a skeleton that absorbs ultraviolet rays. Since the monomer unit represented by general formula (1) has a skeleton that absorbs ultraviolet rays, the ultraviolet-absorbing polymer has ultraviolet-absorbing properties. The ultraviolet-absorbing properties are derived from the skeleton that absorbs ultraviolet rays. The monomer unit represented by general formula (1) is a unit formed by polymerizing the monomer represented by the following general formula (11).

[0029] (General formula 11) [Chemical]

[0030] In the general formula (11), R 11 and U are the same as those in the general formula (1).

[0031] [Monomer unit represented by the general formula (11)] In the monomer unit represented by the general formula (11), U is a hydrocarbon group having a skeleton that absorbs ultraviolet rays and may contain a heteroatom. The skeleton that absorbs ultraviolet rays is preferably, for example, one selected from the group consisting of a benzotriazole skeleton, a triazine skeleton, and a benzophenone skeleton. Among these, from the viewpoints of cost and industrial availability, the benzotriazole skeleton is preferred. Hereinafter, the monomer unit will be described for each skeleton that absorbs ultraviolet rays.

[0032] [Monomer unit containing a benzotriazole skeleton] In the general formula (11), when U is a benzotriazole skeleton, for example, the monomer units represented by the following chemical formulas (a1-1) to (a1-3-32) can be mentioned.

[0033] [Chemical]

[0034] [Chemical]

[0035] [Chemical]

[0036] [Chemical]

[0037] [Chemical]

[0038] [Chemical formula]

[0039] [Chemical formula]

[0040] [Chemical formula]

[0041] [Chemical formula]

[0042] [Chemical formula]

[0043] (Monomer unit containing a triazine skeleton) In general formula (11), when U is a triazine skeleton, for example, monomer units represented by the following chemical formulas (a1-4-1) to (a1-4-21) can be mentioned. The triazine skeleton is preferably a triphenyltriazine skeleton.

[0044] [Chemical formula]

[0045] [Chemical formula]

[0046] [Chemical formula]

[0047] [Chemical]

[0048] [Chemical]

[0049] [Chemical]

[0050] [Chemical]

[0051] (Monomer unit containing a benzophenone skeleton) In general formula (11), when U is a benzophenone skeleton, the following monomers can be mentioned. Monomers having a benzophenone skeleton include, for example, 4-acryloyloxybenzophenone, 4-methacryloyloxybenzophenone, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-methacryloyloxybenzophenone, 2-hydroxy-4-(2-acryloyloxy)ethoxybenzophenone, 2-hydroxy-4-(2-methacryloyloxy)ethoxybenzophenone, 2-hydroxy-4-(2-methyl-2-acryloyloxy)ethoxybenzophenone, 2,2'-dihydroxy -4-methacryloyloxybenzophenone and the like.

[0052] Among the compounds represented by general formula (1), 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole has polymerization controllability, cost, It is preferable for the balance of ultraviolet absorbency.

[0053] The monomer unit represented by the general formula (1) can be used alone or in combination of two or more.

[0054] The content of the monomer unit represented by the general formula (1) is preferably 3 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 45% by mass in 100% by mass of all monomer units. By containing an appropriate amount, high compatibility between ultraviolet absorbency and polyolefin can be achieved.

[0055] <General formula (2)> In the general formula (2), R 21 represents any one selected from the group consisting of a hydrogen atom and a methyl group, and Z represents any one selected from the group consisting of a linear hydrocarbon group and a cyclic hydrocarbon group having 10 or more carbon atoms.

[0056] General formula (2)

Chemical formula

[0057] The monomer unit represented by the general formula (2) is a unit formed by polymerizing the monomer represented by the following general formula (21). General formula (21)

Chemical formula

[0058] In the general formula (21), R 21 and Z are the same as those in the general formula (2).

[0059] Since Z is any one selected from a linear hydrocarbon group and a cyclic hydrocarbon group having 10 or more carbon atoms, the hydrophobicity is increased. As a result, the ultraviolet-absorbing polymer has improved affinity with highly hydrophobic polyolefin, and thus the compatibility between the two is improved. Although the upper limit of the carbon number of Z is not limited, if forced to mention, it is preferably 30 or less, more preferably 22 or less, and even more preferably 20 or less.​

[0060] In general formula (21), the chain hydrocarbon group having 10 or more carbon atoms may have a straight-chain structure or a branched structure. Examples of the chain hydrocarbon group include alkyl groups such as decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicicosyl group, docosyl group, tricosyl group, and tetracosyl group. The chain hydrocarbon group preferably has a branched structure, and more preferably an isostearyl group. In addition, the carbon number of the hydrocarbon group having a straight-chain structure and a branched structure is preferably 14 or more. The upper limit of the hydrocarbon is not particularly limited as long as it can be polymerized, but is preferably 22 or less.

[0061] Examples of the hydrocarbon group having a cyclic structure (cyclic hydrocarbon group) include alicyclic hydrocarbon groups and polycyclic hydrocarbon groups. The alicyclic hydrocarbon group is a group having one saturated or unsaturated carbon ring without aromaticity, and the polycyclic hydrocarbon group is a group having a plurality of saturated or unsaturated carbon rings without aromaticity.

[0062] Examples of the alicyclic hydrocarbon group include cyclododecyl group, t-butylcyclohexyl group, and the like. Examples of the polycyclic hydrocarbon group include isobornyl group, dicyclopentanyl group, dicyclopentenyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, and the like. These alicyclic hydrocarbon groups and polycyclic hydrocarbon groups are preferably polycyclic hydrocarbon groups, and more preferably dicyclopentanyl group. Thereby, the affinity with highly hydrophobic polyolefin and cycloolefin resin is particularly improved.

[0063] The monomer represented by the general formula (21) includes, for example, lauryl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, etc. Among these, isostearyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate are preferred, and dicyclopentanyl (meth)acrylate is more preferred.

[0064] The monomer unit represented by the general formula (21) can be used alone or in combination of two or more. Since the glass transition temperature of the ultraviolet-absorbing polymer does not drop too much, a combination of a cyclic hydrocarbon group monomer unit, or a linear hydrocarbon group monomer unit and a cyclic hydrocarbon group monomer is preferred. In the above combination, it is preferable to use the linear hydrocarbon group monomer and the cyclic hydrocarbon group monomer in a ratio of 1:1 to 1:3. This can further improve the affinity with polyolefin and cycloolefin resin.

[0065] The content of the monomer unit represented by the general formula (21) is preferably 30 to 85% by mass, more preferably 35 to 80% by mass, and most preferably 40 to 75% by mass in all monomer units. By containing an appropriate amount, it is easy to balance ultraviolet absorption and compatibility with polyolefin.

[0066] <Other monomer units> The ultraviolet-absorbing polymer can contain other monomer units other than the monomer unit represented by the general formula (1) and the monomer unit represented by the general formula (2). The other monomer units can contain, for example, (meth)acrylate ester units, aromatic vinyl monomer units, and other vinyl monomer units.

[0067] (Meth)acrylic acid esters include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, t-octyl (meth)acrylate, acetoxyethyl (meth)acrylate, phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, polyethyleneglycol monomethyl ether (meth)acrylate, polyethyleneglycol monoethyl ether (meth)acrylate, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, tribromophenyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, etc. Examples include tribromophenyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, etc.

[0068] Aromatic vinyl monomers include, for example, styrene, α-methylstyrene, vinyl benzoate, methyl vinyl benzoate, vinyl toluene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (such as a tert-butoxycarbonyl group (t-Boc), etc.).

[0069] Other vinyl monomer units include, for example, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth)acrylamides, vinyl ethers, (meth)acrylonitriles, acidic group-containing monomers, nitrogen-containing heterocyclic monomers, and the like.

[0070] Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

[0071] Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl methoxyacetate.

[0072] Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

[0073] Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

[0074] Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

[0075] (Meth)acrylamides include, for example, (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-n-butyl acrylamide(meth), N-t-butyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, (meth)acryloylmorpholine, diacetone acrylamide, and the like.

[0076] Vinyl ethers include, for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, and the like.

[0077] Acidic group-containing monomers include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, etc. unsaturated dicarboxylic acids or their acid anhydrides; and the like.

[0078] Nitrogen-containing heterocyclic monomers include, for example, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, pentamethylpiperidinyl methacrylate, pentamethylpiperidinyl acrylate, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, and the like.

[0079] An ultraviolet-absorbing polymer containing a nitrogen-containing heterocyclic monomer unit is preferable because the light stability is improved by the nitrogen-containing heterocycle. The nitrogen-containing heterocyclic monomer is preferably 3 to 40% by mass, more preferably 3 to 30% by mass, and still more preferably 5 to 25% by mass in 100% by mass of the monomer mixture. By containing an appropriate amount, it is easy to achieve both light stability and compatibility with polyolefins and cycloolefin resins.

[0080] <Synthesis method> Synthesis methods of ultraviolet-absorbing polymers include, for example, anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. Among these, those synthesized by free radical polymerization are preferable from the viewpoints of cost and productivity.

[0081] The weight average molecular weight (Mw) of the ultraviolet-absorbing polymer is preferably from 3,000 to 150,000, more preferably from 4,000 to 100,000, still more preferably from 5,000 to 80,000, and particularly preferably from 6,000 to 40,000, from the viewpoint of compatibility with polyolefins and cycloolefin resins. When the weight average molecular weight (Mw) of the ultraviolet-absorbing polymer is within the above range the fluidity during molding is further improved. The weight average molecular weight is a value measured by gel permeation chromatography (GPC).

[0082] The molecular weight distribution (Mw / Mn) of the ultraviolet-absorbing polymer is preferably from 1 to 10, more preferably from 1.2 to 5.0, and still more preferably from 1.3 to 3.0. When it is within the above range, the compatibility with polyolefins and cycloolefin resins is improved, and the ultraviolet-absorbing polymer is less likely to bleed out.

[0083] The glass transition temperature (Tg) of the ultraviolet-absorbing polymer is preferably from 60°C to 180°C, more preferably from 70°C to 170°C, and still more preferably from 80°C to 160°C. When it is within the above range, the balance between processability and compatibility with polyolefins and cycloolefin resins is good.

[0084] The thermal decomposition temperature (Td) of the ultraviolet-absorbing polymer is not particularly limited, but for example, 200°C or higher, preferably 220°C or higher, and still more preferably 240°C or higher is preferable. If it is within the above range, yellowing and the like are less likely to occur even during high-temperature molding processing.

[0085] Note that Tg and Td can be measured by, for example, the methods described later.

[0086] <Thiol-based chain transfer agent> The ultraviolet-absorbing polymer has a thiol-based chain transfer agent residue. The thiol-based chain transfer agent residue has a thiol group and at least one site among a carboxyl group, a hydroxyl group, and an ester bond. The effect of the thiol-based chain transfer agent on adjusting the polymer molecular weight is known. In contrast, in this specification, in addition to the above effect, the thiol -based chain transfer agent residue at the end of the ultraviolet-absorbing polymer has at least one site among a carboxyl group, a hydroxyl group, and an ester bond, thereby improving the affinity between the polymer and a lower alcohol that is inexpensive and easy to remove. As a result, it becomes possible to use a lower alcohol in the purification step of removing a low molecular weight polymer, an unreacted thiol-based chain transfer agent, etc. from the ultraviolet-absorbing polymer, and an unexpected effect of enabling low-cost and simple purification is obtained.

[0087] In terms of molecular weight adjustment, the thiol-based chain transfer agent is preferably a monothiol compound rather than a polythiol compound, and more preferably a monothiol compound having a primary thiol group. Thereby, an ultraviolet-absorbing polymer with few impurities can be obtained, which is suitable for uses such as pharmaceutical agents and cosmetics, for example.

[0088] Examples of the thiol-based chain transfer agent having a carboxyl group include α-mercaptopropionic acid, β-mercaptopropionic acid, 2,3-dimercaptopropionic acid, thioglycolic acid, thiolactic acid, o-mercaptobenzoic acid, m-mercaptobenzoic acid, thiomalic acid, o-thiocumaric acid, α-mercaptobutyric acid, β-mercaptobutyric acid, γ-mercaptobutyric acid, 11-mercaptoundecanoic acid, etc.

[0089] Examples of the thiol-based chain transfer agent having a hydroxyl group include mercaptomethanol, 1-mercaptoethanol, 2-mercaptoethanol, 1-mercaptopropanol, 3-mercaptopropanol, 1-mercapto-2,3-propanediol, 1-mercapto-2-butanol, 1-mercapto-2,3-butanediol, 1-mercapto-3,4-butanediol, 1-mercapto-3,4,4'-butanetriol, 2-mercapto-3- Examples include butanol, 2-mercapto-3,4-butanediol, 2-mercapto-3,4,4'-butanetriol, thioglycerol, and the like.

[0090] Examples of the thiol-based chain transfer agent having an ester bond include alkyl thioglycolates such as methyl thioglycolate, octyl thioglycolate, and methoxybutyl thioglycolate, and alkyl mercaptopropionates such as methyl mercaptopropionate, octyl mercaptopropionate, methoxybutyl mercaptopropionate, and tridecyl mercaptopropionate.

[0091] The molecular weight of the thiol-based chain transfer agent is preferably from 101 to 300, more preferably from 150 to 250. By using a thiol-based chain transfer agent within this range, the volatility of the thiol-based chain transfer agent itself can be suppressed, and a chain transfer effect can be obtained with a small amount of addition, making it easier to control the molecular weight.

[0092] Among these, compounds having a primary thiol group are particularly preferred because they have a high chain transfer agent effect and are easy to adjust the molecular weight. In particular, from the balance between odor and ease of molecular weight adjustment, β-mercaptopropionic acid, thioglycerol, octyl thioglycolate, methoxybutyl thioglycolate, octyl mercaptopropionate, and methoxybutyl mercaptopropionate are preferred.

[0093] The thiol-based chain transfer agent can be used alone or in combination of two or more.

[0094] The content of the thiol-based chain transfer agent is preferably from 0.01 to 5 parts by mass, more preferably from 0.05 to 4 parts by mass, and still more preferably from 0.1 to 3 parts by mass, based on 100 parts by mass of all monomer units of the ultraviolet-absorbing polymer. When contained in an appropriate amount, it can highly balance molecular weight adjustment and affinity with lower alcohols. Note that the thiol-based chain transfer agent is not included in all monomer units.

[0095] The ultraviolet-absorbing polymer is based on 100 parts by mass of all monomer units, and the above-mentioned thiol-based chain transfer Preferably, it contains 0.001 to 0.3 parts by mass of a sulfur atom derived from a thiol-based chain transfer agent, more preferably 0.001 to 0.25 parts by mass, and even more preferably 0.001 to 0.2 parts by mass. When contained in an appropriate amount, it can highly balance molecular weight adjustment and affinity with lower alcohols. The content of the sulfur atom derived from the thiol-based chain transfer agent in the above ultraviolet-absorbing polymer can be measured by the method described later. Specifically, it is calculated by burning the ultraviolet-absorbing polymer and measuring the amount of sulfur-containing gas released.

[0096] The ultraviolet-absorbing polymer can be synthesized by known polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. In this specification, solution polymerization, which is easy to control the reaction, is preferred.

[0097] Also, for the polymerization, random polymerization, block polymerization, etc. can be appropriately selected, and radical polymerization is preferred among ionic polymerization, radical polymerization, etc.

[0098] <Polymerization initiator> For the synthesis of the ultraviolet-absorbing polymer, it is preferable to use a polymerization initiator. Preferred polymerization initiators include, for example, azo compounds and peroxides. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), or 2,2'-azobis[2-(2-imidazolin-2-yl)propane], etc. Examples of peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, or diacetyl peroxide, etc.

[0099] The polymerization initiator can be used alone or in combination of two or more.

[0100] The polymerization temperature is preferably about 40 to 150 °C, more preferably 50 to 110 °C. The reaction time is preferably about 3 to 30 hours, more preferably 5 to 20 hours.

[0101] <Organic solvent> The synthesis of the ultraviolet-absorbing polymer can use organic solvents. Examples of the organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol monobutyl ether acetate, etc. In addition, as for the solvent used in the purification process of the ultraviolet-absorbing polymer, it is preferable to use methanol because the solubility of the ultraviolet-absorbing polymer is low, the cost and purity are suitable, and it is easy to remove the solvent from the ultraviolet-absorbing polymer.

[0102] The organic solvents can be used alone or in combination of two or more.

[0103] <Molding resin composition> The molding resin composition contains a thermoplastic resin and an ultraviolet-absorbing polymer. Optionally, it can contain a coloring agent and additives. The blending amount of the ultraviolet-absorbing polymer is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 25 parts by mass, and even more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

[0104] <Wax> The molding resin composition can contain wax. The wax consists of low molecular weight polyolefins. These are polymers of olefin monomers such as ethylene, propylene, and butylene, and can be block, random copolymers or terpolymers. Specifically, they are polymers of α-olefins such as low density polyethylene (LDPE), high density polyethylene (HDPE), and polypropylene (PP). These can be used alone or in combination of two or more.

[0105] The number average molecular weight of the wax is preferably from 1,000 to 30,000, more preferably from 2,000 to 25,000. When the number average molecular weight is within this range, the wax appropriately migrates to the surface of the molded article, so that the balance between slidability and bleed-out suppression is excellent.

[0106] The melting point of the wax is preferably from 60 to 150°C, more preferably from 70 to 140°C. When the melting point is within this range, the processability during melt-kneading of the thermoplastic resin and the wax becomes good.

[0107] Note that the melt flow rate (MFR) of the wax determined in accordance with JIS K-7210 is preferably greater than 100 g / 10 minutes.

[0108] The compounding amount of the wax is preferably from 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin contained in the molded body.

[0109] The resin composition for molding can be produced, for example, at the composition ratio of the molded body. Alternatively, it can also be produced as a masterbatch containing a high concentration of an ultraviolet-absorbing polymer. In this specification, the masterbatch is preferable in terms of easy uniform dispersion of the ultraviolet-absorbing polymer in the molded body. The masterbatch is preferably produced, for example, by melt-kneading a thermoplastic resin and an ultraviolet-absorbing polymer and then molding them into an arbitrary shape. Next, the masterbatch and a diluent resin (for example, the thermoplastic resin used for the masterbatch) are melt-kneaded to form a molded body of a desired shape. Examples of the shape of the masterbatch include pellet shape, powder shape, plate shape, etc. Note that in order to prevent aggregation of the ultraviolet-absorbing polymer, it is preferable to produce a dispersion obtained by previously melt-kneading the ultraviolet-absorbing polymer and the wax, and then melt-kneading it together with the thermoplastic resin to produce the masterbatch. Examples of the apparatus used for the dispersion include a blend mixer, a three-roll mill, etc. The thermoplastic resin used for producing the masterbatch is preferably the same thermoplastic resin as the diluent resin (Y), but other thermoplastic resins may be used as long as there is no problem with compatibility.

[0110] When producing the resin composition for molding as a masterbatch, it is preferable to blend 1 to 200 parts by mass, more preferably 5 to 70 parts by mass of the ultraviolet-absorbing polymer with respect to 100 parts by mass of the thermoplastic resin. The mass ratio of the masterbatch (X) to the diluent resin (Y) that becomes the base resin of the molded body is preferably X / Y = 1 / 1 to 1 / 100, more preferably 1 / 3 to 2 / 100. When within this range, the ultraviolet-absorbing polymer is uniformly dispersed in the molded body, and good ultraviolet absorption and light transmittance are easily obtained.

[0111] Examples of the melt kneading include a single-screw kneading extruder, a twin-screw kneading extruder, a tandem twin-screw kneading extruder, etc. The melt kneading temperature varies depending on the type of polyolefin, but is usually about 150 to 250°C.

[0112] The resin composition for molding can further contain, if necessary, an antioxidant, a light stabilizer, a dispersant, etc.

[0113] <Molded body> The resin composition for molding is preferably used, for example, for food packaging materials, pharmaceutical packaging materials, and display applications. For food packaging materials and pharmaceutical packaging materials, it is preferable to use, for example, polyolefins or polyesters for the thermoplastic resin. These molded bodies have improved flexibility and visibility and can suppress the deterioration of the contents. Thereby, the shelf life of pharmaceuticals, cosmetics, etc. can be extended. Also, for display applications (e.g., TVs, personal computers, smartphones, etc.), it is preferable to use, for example, polyacryl or polycarbonate for the thermoplastic resin. These molded bodies can suppress the adverse effects on the eyes by absorbing the ultraviolet rays and the light in the short wavelength region of visible light contained in the backlight, and can also suppress the deterioration of the display elements of the display by absorbing the ultraviolet rays and the light in the short wavelength region of visible light contained in sunlight, and further can suppress the decrease in transparency due to migration. Furthermore, it can be widely used in applications such as display materials, sensor materials, and optical control materials.

[0114] When the resin composition for molding is a masterbatch, the molded article contains a diluent resin (Y). The molded article is produced by molding the resin composition for molding.

[0115] Examples of the molding method include extrusion molding, injection molding, blow molding, etc. Examples of extrusion molding include compression molding, pipe extrusion molding, laminate molding, T-die molding, inflation molding, melt spinning, etc.

[0116] The molding temperature is usually 160 to 280°C according to the softening point of the diluent resin.

[0117] The molded article can be widely used in applications such as medical drugs, cosmetics, food containers, packaging materials, miscellaneous goods, textile products, pharmaceutical containers, various industrial coating materials, automotive parts, household appliances, building materials for houses, toiletries, etc. Note that the molded article is obtained by introducing resin into a mold. Note that the molded article includes those obtained by introducing resin into a mold and articles obtained without using a mold such as plastic films.

Examples

[0118] Hereinafter, the present invention will be described in more detail by experimental examples, but the present invention is not limited to the experimental examples. Note that "parts" means "parts by mass" and "%" means "% by mass".

[0119] (Molecular weight) The number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8320GPC (manufactured by Tosoh Corporation) was used as the apparatus, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was connected in two for both fillers and used. The oven temperature was 40°C, a THF solution was used as the eluent, and the measurement was performed at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of the above eluent and 20 microliters were injected. All molecular weights are polystyrene conversion values. The sample was dissolved in a solvent consisting of the above eluent and 20 microliters were injected. All molecular weights are polystyrene conversion values.

[0120] (Non-volatile content) The nonvolatile content was calculated from the weight ratio before and after drying for 10 minutes in an electric oven at 200 °C in an aluminum container after weighing 0.5 g of the sample. Nonvolatile content % = (weight after drying) / (weight before drying) × 100

[0121] [Production Examples (B-1) to (B-11) of Ultraviolet Absorbing Polymers] (Ultraviolet Absorbing Polymer (B-1)) Into a four-neck separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser, 250 parts of methyl ethyl ketone, 30 parts of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole as the monomer represented by the general formula (1), 35 parts of isostearyl acrylate as the monomer represented by the general formula (2), 35 parts of dicyclopentanyl methacrylate, and 1 part of 2-ethylhexyl 3-mercaptopropionate as a thiol-based chain transfer agent were charged, and stirred for 30 minutes under a nitrogen stream. Then, 1.0 part of 2,2'-azobis(isobutyric acid methyl) was charged, the temperature was raised to reflux to initiate the polymerization reaction. After the temperature was raised, when 2 hours had elapsed, 0.1 part of 2,2'-azobis(isobutyric acid methyl) was added every 1 hour, and the reaction was carried out for a total of 8 hours. Then, sampling was performed to confirm that the conversion rate was 98% or more. After cooling, it was diluted with methyl ethyl ketone to produce a resin solution b-1 with a nonvolatile content of 30%. Next, 300 parts of methanol was charged into a 1 L beaker, and stirred at 1,000 revolutions using a disperser. Then, 100 parts of the resin solution b-1 was added dropwise over 1 hour. Then, using a Buchner funnel with a diameter of 150 mm and qualitative filter paper (manufactured by ADVANTEC, product name No. 2), suction was performed under reduced pressure to filter the generated white precipitate. The time required for 200 g of the filtrate to pass through was less than 1 minute, and the filterability was not a problem. Further, suction under reduced pressure was continued for 30 minutes to confirm that no more filtrate came out. Then, the obtained white precipitate was dried in a vacuum dryer at 50 °C for 12 hours to produce polymer (B-1). The nonvolatile content of the obtained polymer (B-1) was 99% or more.

[0122] As shown in Table 1 below, ultraviolet-absorbing polymers (B-2) to (B-10) were obtained in the same manner as the ultraviolet-absorbing polymer (B-1), except that the monomers and chain transfer agents used were changed.

[0123] (Ultraviolet-absorbing polymer (B-11)) Into a four-necked separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser, 250 parts of methyl ethyl ketone, 30 parts of 2-[2-hydroxy-5 -[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole as a monomer unit represented by the general formula (1), 70 parts of dicyclopentanyl methacrylate as a monomer unit represented by the general formula (2), and 1 part of 1-dodecanethiol as a thiol-based chain transfer agent were charged, and the mixture was stirred for 30 minutes under a nitrogen stream. Then, 1.0 part of 2,2'-azobis(isobutyronitrile) was charged, the temperature was raised to reflux to initiate the polymerization reaction. After the temperature was raised, when 2 hours had passed, 0.1 part of 2,2'-azobis(isobutyronitrile) was added every 1 hour, and the reaction was carried out for a total of 8 hours. Thereafter, sampling was performed to confirm that the polymerization yield was 98% or more. After cooling, it was diluted with methyl ethyl ketone to produce a resin solution b-11 having a non-volatile content of 30%. Next, 300 parts of hexane was charged into a 1 L beaker and stirred at 1,000 revolutions using a disperser. Then, 100 parts of the resin solution b-11 was added dropwise over 1 hour. For the polymer (B-11), the precipitate became gummy, and a small amount of resin adhered to the disperser and the container. Thereafter, using a qualitative filter paper (product name No. 2, manufactured by ADVANTEC) in a Buchner funnel with a diameter of 150 mm, suction filtration was performed under reduced pressure to filter the generated white precipitate. The time required for 200 g of the filtrate to pass through was more than 1 minute, indicating poor filterability. Further, suction filtration under reduced pressure was continued for 30 minutes, and it was confirmed that no more filtrate came out. The obtained white precipitate was dried in a vacuum dryer at 50°C for 12 hours. Since the non-volatile content did not reach 99% or more, it was further dried in a vacuum dryer at 50°C for 12 hours. After confirming that the non-volatile content reached 99%, the polymer (B-11) was obtained.

[0124] <Filterability> 400 g of the slurry solution of the ultraviolet absorber polymer was suctioned under reduced pressure using a Buchner funnel with a diameter of 150 mm and qualitative filter paper (manufactured by ADVANTEC, product name No. 2). At this time, the filtrate 2 The time required for 00 g to escape was measured. Good: The required time is less than 1 minute Bad: The required time is 1 minute or more

[0125] <Drying property> The white precipitate of the ultraviolet absorber polymer was dried under reduced pressure by heating at 50 °C and a pressure of 15 kPa (A) using a vacuum dryer, and the time required for the non-volatile content to reach 99% or more was measured. Good: The required time is less than 12 hours Bad: The required time is 12 hours or more

[0126] <Measurement of sulfur atom concentration derived from thiol-based chain transfer agent residue> 0.1 g of the obtained ultraviolet absorber polymer was placed in a sample boat for a combustion device, and heated at 100 °C for 5 minutes using a combustion device ( Automatic sample combustion device manufactured by Dain Instruments Co., Ltd., model "AQF-100"). At this time, the gas generated from the ultraviolet absorber polymer was passed through 10 mL of hydrogen peroxide solution (absorbing solution) with a concentration of 30 ppm, and the sulfur-containing gas (H2S, SO2, etc.) contained in the generated gas was converted to SO4 2- and collected. After passing the generated gas through pure water was added to the absorbing solution to adjust the volume to 20 mL, and quantitative analysis of SO4 2- was performed using an ion chromatograph (manufactured by Dionex Corporation, product name "DX-320") to determine the sulfur atom concentration contained in the ultraviolet absorber polymer. The sulfur atom concentration obtained from these measurements is derived from the thiol-based chain transfer agent residue incorporated into the ultraviolet absorber polymer or the thiol-based chain transfer agent that could not be removed by purification.

[0127]

Table 1

[0128] The terms in Table 1 are as follows. Monomer unit represented by the general formula (1) Benzotriazole skeleton: 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl phenyl]-2H-benzotriazole Triazine skeleton: Compound (a1-4-1) Benzophenone skeleton: 4-acryloyloxybenzophenone

[0129] (Example 1) [Production of molding resin composition (masterbatch)] As the thermoplastic resin, 100 parts of polyethylene (Suntech LD M2270, MFR = 7 g / 10 min, manufactured by Asahi Kasei Chemicals Corporation) and 20 parts of ultraviolet-absorbing polymer (B-1) were supplied from separate supply ports, melt-kneaded at 180 °C using a twin-screw extruder (manufactured by Nippon Steel Works, Ltd.), then cooled, and cut into pellets using a pelletizer to produce a masterbatch.

[0130] [Film forming] 10 parts of the produced masterbatch was mixed with 100 parts of the above polyethylene (Suntech LD M2270, MFR = 7 g / 10 min, manufactured by Asahi Kasei Chemicals Corporation) as the diluting resin. Then, using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.), it was melt-mixed at a temperature of 180 °C to form a film with a thickness of 250 μm.

[0131] (Examples 2 to 22, 27, 28, Comparative Example 1) Masterbatch and film were produced in the same manner as in Example 1, except that the materials and compounding amounts shown in Table 2 were used instead of the materials used in Example 1.

[0132] (Examples 23 to 26) The materials used in Example 1 were changed to the materials and compounding amounts shown in Table 2, and further the molding temperature was changed to 270 °C. Masterbatch and film were produced in the same manner as in Example 1.

[0133] The thermoplastic resins and plasticizers used in this example are shown below. (A-1): Polyethylene (Suntech LD M2270, MFR = 7 g / 10 min, manufactured by Asahi Kasei Chemicals Corporation) (A-2): Polyethylene (Novatech UJ790, MFR = 50 g / 10 min, manufactured by Japan Polyethylene Corporation) (A-3): Polypropylene (Novatech PP FA3EB, MFR = 10.5 g / 10 min, manufactured by Japan Polypro Co., Ltd.) (A-4): Polypropylene (Prime Polypro J226T, MFR = 20 g / 10 min, manufactured by Prime Polymer Co., Ltd.) (A-5): Polycarbonate (Iupilon S3000, MFR = 15 g / 10 min, manufactured by Mitsubishi Engineering Plastics Corporation) (A-6): Polymethacrylic resin (Acrypet MF, MFR = 14 g / 10 min, manufactured by Mitsubishi Rayon Co., Ltd.) (A-7): Polyester (Mitsui Pet SA135, manufactured by Mitsui Chemicals, Inc.) (A-8): Cycloolefin resin (TOPAS5013L-10, manufactured by Mitsui Chemicals, Inc.) (A-9): Polyvinyl chloride (SCB200JA, manufactured by Sun Arrow Kasei Kogyo Co., Ltd.) (A-10): Polyvinylidene chloride (Sarantex L574A, manufactured by Asahi Kasei Chemicals Corporation) Plasticizer: Epoxidized soybean oil (Adeka Sizer O-130P, manufactured by ADEKA Corporation)

[0134] Regarding the films obtained in the above Examples and Comparative Examples, the following items were evaluated.

[0135] [Workability of the purification process] In the purification process of the ultraviolet-absorbing polymer, productivity was evaluated regarding filterability and dryability. Performed. Good: There are no particular problems in the filtration process and the drying process. Poor: A decrease in workability is observed in either the filtration process or the drying process.

[0136] [Ultraviolet absorbability] The transmittance of the formed film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). The transmittance was measured as the spectral transmittance with respect to a white standard plate. It was evaluated whether the following conditions were satisfied. The evaluation criteria are as follows. ◎: The light transmittance in the wavelength range of 290 to 360 nm is less than 2% over the entire region. Good. ○: There is a region where the light transmittance is 2% or more in part of the wavelength range of 290 to 360 nm. Practical range. ×: The light transmittance in the wavelength range of 290 to 360 nm is 2% or more over the entire region. Not practical.

[0137] [Light resistance test] The formed film was exposed for 1500 hours in a xenon weather meter under the condition that the illuminance of light with a wavelength of 300 to 400 nm was 60 W / m 2 . The evaluation criteria are as follows. ◎: No yellowing is observed at all. Good. ○: Slight yellowing is observed. Practical range. ×: Obvious yellowing is observed. Not practical.

[0138] [Transparency] The transparency of the formed film was visually evaluated. The evaluation criteria are as follows. ◎: No turbidity is observed at all. Excellent. ○: Almost no turbidity is observed. Good. △: Slight turbidity is observed. Practical range. ×: Obvious turbidity is observed. Not practical.

[0139] [Odor evaluation] The formed film was cut into a 10 cm square, placed in an aluminum vapor-deposited bag, sealed, and left standing at 40 °C for 24 hours. Then, the odor was confirmed by 5 monitors. ◎: Almost no odor is observed (none of the monitors feel the odor). Good. ○: A slight odor is observed. (1 to 3 monitors feel the odor). Practical range. ×: An obvious odor is observed (4 or more monitors feel the odor). Not practical.

[0140]

Table 2

[0141] As shown in Table 2, a molding resin composition containing an ultraviolet-absorbing polymer using a thiol-based chain transfer agent having one or more sites of a carboxyl group, a hydroxyl group, and an ester bond is inexpensive and can be efficiently purified with less odor, has good compatibility with a thermoplastic resin, particularly polyolefin, and can form a molded article with good transparency.

Claims

1. A resin composition for molding, comprising a thermoplastic resin and an ultraviolet-absorbing polymer, wherein the ultraviolet-absorbing polymer is a polymer having a monomer unit represented by the following general formula (1), a monomer unit represented by the following general formula (2), and a thiol-based chain transfer agent residue, the thiol-based chain transfer agent that forms the thiol-based chain transfer agent residue has a thiol group and at least one site selected from the group consisting of a carboxyl group, a hydroxyl group, and an ester bond, the resin composition for molding. 【Chemical 1】 (In general formula (1), R 11 represents any one selected from the group consisting of a hydrogen atom and a methyl group, U is a hydrocarbon group having a skeleton that absorbs ultraviolet rays and may contain a heteroatom, and is one selected from the group consisting of a benzotriazole skeleton, a triazine skeleton, and a benzophenone skeleton, In the general formula (2), R 21 represents any one selected from the group consisting of a hydrogen atom and a methyl group, and Z represents any one selected from the group consisting of a linear hydrocarbon group having 10 or more carbon atoms and a cyclic hydrocarbon group.)

2. The resin composition for molding according to claim 1, containing 0.001 to 0.3 parts by mass of sulfur atoms derived from the thiol-based chain transfer agent with respect to 100 parts by mass of all monomer units of the ultraviolet-absorbing polymer.

3. The resin composition for molding according to claim 1 or 2, containing 30 to 85% by mass of the monomer unit represented by the general formula (2) in 100% by mass of all monomer units of the ultraviolet-absorbing polymer.

4. The resin composition for molding according to any one of claims 1 to 3, wherein the weight average molecular weight of the ultraviolet-absorbing polymer is 3,000 to 150,000.

5. A molded article formed by molding the resin composition for molding according to any one of claims 1 to 4.

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