JP2024030298A - Molding resin composition and molded object - Google Patents

Abstract

[Problem] The present invention aims to provide a molding resin that has excellent heat resistance, good compatibility with various resins, can form molded bodies with good transparency, and can be synthesized more easily than before. . [Solution] Contains an ultraviolet absorbing monomer unit, an N-substituted cyclic imide unit constituting the main chain, and a ring-containing (meth)acrylate unit (however, it does not have an ultraviolet absorbing site), and has a weight average molecular weight of 5, 000 to 60,000. In addition, it is preferable that the methyl methacrylate unit is 20 mass % or less in all monomer units. [Selection diagram] None

Description

The present invention relates to a resin composition for molding and a molded article.

In recent years, electronic components and packaging containers have become lighter and more compact, and in applications that require transparency in particular, components that traditionally were made of glass are being replaced with highly transparent resins. . For example, transparent resins such as polymethyl methacrylate and polycarbonate are being considered for use in liquid crystal displays, optical discs, etc. because they have good moldability and processability, are difficult to break, are lightweight, and are inexpensive. There is. Furthermore, polyolefin resins, polyester resins, polycarbonate resins, and the like are used for packaging containers, packaging films, and the like because of their moldability and visibility. However, these resin materials are degraded by ultraviolet rays, so depending on the application, they are mixed with ultraviolet absorbers. However, general UV absorbers have low molecular weight and poor heat resistance, and if they are simply blended, the UV absorbers will volatilize due to the heat during molding of these transparent resins, causing extruder vents, There was a problem in which the ultraviolet absorber became clogged in the exhaust system. Further, in the film forming process using a T-die, the ultraviolet absorber volatilizes from the molten film when it is discharged from the T-die and adheres to the cooling roll or becomes smudged, causing film defects. Furthermore, some types of transparent resins have poor compatibility with UV absorbers, causing problems such as decreased transparency and elution onto the film surface, making it necessary to use different UV absorbers depending on the type of transparent resin. .

In order to solve these problems, Patent Document 1 discloses a molding resin obtained by copolymerizing an ultraviolet absorbing monomer, an acrylic monomer, and the like. Patent Document 2 discloses a molding resin obtained by copolymerizing an ultraviolet absorbing monomer, 3,4,5,6-tetrahydrophthalimidoethyl acrylate, an acrylic monomer, and the like.

Japanese Patent Application Publication No. 2008-127549 Japanese Patent Application Publication No. 2004-143344

However, although conventional molding resins have solved the problems caused by ultraviolet absorbers, they have had the problem of insufficient heat resistance and yellowing of molded products. In addition, it has poor compatibility with resins other than acrylic resins, and there has been a problem that molded bodies cannot be produced using various resins. Furthermore, since the molding resin of Patent Document 1 is synthesized by bulk polymerization, the manufacturing cost is high, and there is a problem that it is difficult to expand the manufacturing scale.

An object of the present invention is to provide a molding resin that has excellent heat resistance, good compatibility with various resins, can form a molded article with good transparency, and can be synthesized more easily than before.

The molding resin of the present invention contains an ultraviolet absorbing monomer unit, an N-substituted cyclic imide unit constituting the main chain, and a ring-containing (meth)acrylate unit (however, it does not have an ultraviolet absorbing site), and has a weight of The average molecular weight is 5,000 to 60,000.

According to the present invention described above, it is possible to form a molded article having excellent heat resistance, good compatibility with various resins, and good transparency, and it is possible to provide a molding resin that can be synthesized more easily than before. Moreover, the present invention can provide a resin composition for molding and a molded article.

Define terms used in this specification. In this specification, etc., "(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". Moreover, a monomer means an ethylenically unsaturated group-containing compound. The monomer after polymerization is called a monomer unit, and the monomer before polymerization is called a monomer.

The molding resin of the present invention contains an ultraviolet absorbing monomer unit, an N-substituted cyclic imide unit constituting the main chain, and a ring-containing (meth)acrylate unit (however, it does not have an ultraviolet absorbing site), and has a weight of The average molecular weight is 5,000 to 60,000. The molding resin of the present invention is preferably used as a molding resin composition containing a thermoplastic resin. Molding resins have N-substituted cyclic imide units and ring-containing (meth)acrylate units that make up the main chain, so if they are molded with polyolefin resins other than acrylic resins, polyester resins, and polycarbonate resins, the transparency of these resins will be impaired. It is possible to form a molded body without This is because the molding resin of the present invention contains a ring structural unit derived from an N-substituted cyclic imide in the main chain, so the glass transition temperature and softening temperature are increased, and the heat resistance is improved. Therefore, when used together with a resin that requires high-temperature molding, such as a polyester resin or a polycarbonate resin, the molding resin undergoes less heat deterioration and a molded article with good transparency can be formed. In addition, since the molding resin contains ring-containing (meth)acrylate units that are hydrophobic and highly heat resistant, it is assumed that it is highly compatible with low polarity resins such as polyolefin resins and can form molded products with good transparency. do. As described above, the molding resin of the present invention has general-purpose properties that allow it to be used with resins having different properties, such as polyester resins, polycarbonate resins, and polyolefin resins.

<Molding resin>
The molding resin of the present invention contains an ultraviolet absorbing monomer unit, an N-substituted cyclic imide unit constituting the main chain, and a ring-containing (meth)acrylate unit (however, it does not have an ultraviolet absorbing site), and has a weight of The average molecular weight is 5,000 to 60,000.

<Ultraviolet absorbing monomer unit>
The ultraviolet-absorbing monomer unit only needs to have an ultraviolet-absorbing site, and for example, a unit represented by the following general formula (1) is preferable.

General formula (1)

In general formula (1), R ₁₁ represents a hydrogen atom or a methyl group, and U contains one or more hydrocarbon groups or heterocyclic groups that have a skeleton that absorbs ultraviolet rays. It is a part.

<General formula (1)>
R ₁₁ represents a hydrogen atom or a methyl group, and U is a moiety 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 molding resin has ultraviolet absorbing properties.
The monomer unit represented by the general formula (1) is formed by polymerizing the monomer represented by the following general formula (11).

(General formula 11)

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

<Monomer represented by general formula (11)>
In the monomer represented by 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 one selected from the group consisting of, for example, a benzotriazole skeleton, a triazine skeleton, and a benzophenone skeleton. Among these, from the viewpoint of cost and industrial availability, benzotriazole skeletons and triazine skeletons are preferred, and benzotriazole skeletons are more preferred. The monomers for each skeleton that absorbs ultraviolet light will be explained below.

(monomer containing benzotriazole skeleton)
In general formula (11), when U is a benzotriazole skeleton, examples thereof include monomer units represented by the following chemical formulas (a1-1) to (a1-3-32).

(monomer containing triazine skeleton)
In the general formula (11), when U is a triazine skeleton, examples thereof include monomers represented by the following chemical formulas (a1-4-1) to (a1-4-21). Note that the triazine skeleton is preferably a triphenyltriazine skeleton.

(monomer containing benzophenone skeleton)
In general formula (11), when U is a benzophenone skeleton, the following monomers may be mentioned.
Monomers having a benzophenone skeleton are, 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.

Among the compounds represented by the general formula (1), 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole has excellent polymerization controllability, cost, and ultraviolet absorption. Favorable for balance.

The ultraviolet absorbing monomer units can be used alone or in combination of two or more types.

The content of the ultraviolet absorbing monomer unit is preferably 3 to 60% by weight, more preferably 10 to 50% by weight, even more preferably 15 to 45% by weight based on 100% by weight of the total monomer units. By containing an appropriate amount, it is possible to achieve a high level of ultraviolet absorption, heat resistance, and compatibility with transparent resins.

<N-substituted cyclic imide unit constituting the main chain>
In the N-substituted cyclic imide unit constituting the main chain, carbon-carbon bonds in the N-substituted cyclic imide constitute a part of the main chain. For example, N-substituted cyclic imide units can be formed by copolymerizing N-substituted maleimide with other monomers. The N-substituted cyclic imide unit is an N-substituted cyclic imide unit that constitutes the main chain because the carbon-carbon bond constitutes a part of the main chain.
The heat resistance of the molding resin is dramatically improved by including the N-substituted cyclic imide unit forming the main chain. Moreover, compatibility with various transparent resins can be adjusted by changing the substituent at the N-substituted site.
Among the substituents, hydrocarbon groups include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, amyl group, hexyl group, heptyl group, octyl group. , nonyl group, decyl group, lauryl group, myristyl group, cetyl group, stearyl group, oleyl group, etc.;
The cyclic hydrocarbon group is, for example, a cyclohexyl group;
Aromatic groups include, for example, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 2-fluorophenyl group, o-methoxyphenyl group, m-hydroxyphenyl group, p-tolyl group, Hydroxyphenyl group, p-carboxylphenyl group, benzyl group, etc.;
Examples include, but are not particularly limited to. From the viewpoint of heat resistance and compatibility with the transparent resin, a cyclic hydrocarbon group and an aromatic group are preferred, a cyclohexyl group or a phenyl group is more preferred, and a phenyl group is particularly preferred.

Examples of the N-substituted maleimide include N-phenylmaleimide, N-cyclohexylmaleimide, o-chlorophenylmaleimide, N-(2,4,6-trichlorophenyl)maleimide, N-benzylmaleimide, N-(1-pyrenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-anilinophenyl)maleimide, 4-hydroxyphenylmaleimide, o-methylphenylmaleimide, p-carboxyphenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N -tert-butylmaleimide, N-methoxycarbonylmaleimide, N-(2-hydroxyethyl)maleimide, 3-maleimidopropionic acid, 6-maleimidohexanoic acid, N-propargylmaleimide, N-dodecylmaleimide, 4-(N-maleimide) Methyl) cyclohexanecarboxylic acid N-succinimidyl, 4-maleimidobutyric acid N-succinimidyl, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 6-maleimidohexanoate N-succinimidyl, 3-maleimidobenzoic acid N- Examples include succinimidyl, N-[4-(2-benzimidazolyl)phenyl]maleimide, and the like. Among these, N-phenylmaleimide and N-cyclohexylmaleimide are preferred from the viewpoint of polymerization controllability and heat resistance of the molding resin.

The N-substituted cyclic imide unit constituting the main chain can be formed by polymerizing N-substituted maleimide. Alternatively, maleic anhydride can be used for post-polymerization and the anhydride groups can then be modified to form the N-substituted cyclic imide. Modification of the acid anhydride group is formed by reacting with an amine.

The amines used for forming the N-substituted maleimide unit are, for example, methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine, myristylamine, cetylamine, stearyl. Amine, oleylamine, aniline, o-toluidine, 2-ethylaniline, 2-fluoroaniline, o-anisidine, m-toluidine, m-anisidine, m-phenetidine, p-toluidine, 2,3-dimethylaniline, 5-amino Examples include indane, aspartic acid, glutamic acid, and γ-aminobutyric acid.

The content of N-substituted cyclic imide units constituting the main chain is preferably 3 to 25% by mass, more preferably 3 to 20% by mass, even more preferably 5 to 20% by mass based on 100% by mass of all monomer units. . By containing an appropriate amount, it is possible to achieve a high level of ultraviolet absorption, heat resistance, and compatibility with transparent resins.

<Ring-containing (meth)acrylate unit>
The ring-containing (meth)acrylate unit has a cyclic hydrocarbon group in which Z may be substituted in the (meth)acrylate unit represented by the following general formula (2).
General formula (2)

In the general formula (2), R ₂₁ represents a hydrogen atom or a methyl group, and Z represents a hydrogen atom, a hydroxyl group, a chain hydrocarbon group, a cyclic hydrocarbon group, or other functional group.

Since Z in the ring-containing (meth)acrylate unit is a cyclic hydrocarbon group, heat resistance and compatibility with the transparent resin are further improved. Thereby, the molding resin can improve heat resistance while maintaining its affinity with various transparent resins.

Examples of the hydrocarbon group having a cyclic structure (cyclic hydrocarbon group) include an aromatic hydrocarbon group, an alicyclic hydrocarbon group, and a polycyclic hydrocarbon group. An alicyclic hydrocarbon group is a group having one saturated or unsaturated carbon ring without aromaticity, and a polycyclic hydrocarbon group is a group having one saturated or unsaturated carbon ring without aromaticity. It is a group having multiple rings.

Examples of the aromatic hydrocarbon group include phenyl group, xylyl group, trimethylphenyl group, dipropylphenyl group, di(2,2-dimethylpropyl)phenyl group, and naphthyl group.
Examples of the alicyclic hydrocarbon group include a cyclohexyl group, a cyclododecyl group, and a t-butylcyclohexyl group.
Examples of the polycyclic hydrocarbon group include isobornyl group, dicyclopentanyl group, dicyclopentenyl group, 2-methyl-2-adamantyl group, and 2-ethyl-2-adamantyl group. Among these, from the viewpoint of improving compatibility with various resins, alicyclic hydrocarbon groups and polycyclic hydrocarbon groups are preferred, polycyclic hydrocarbon groups are more preferred, and dicyclopentanyl groups are even more preferred. . As a result, a molding resin having a particularly excellent balance between heat resistance and compatibility can be obtained.

Ring-containing (meth)acrylate monomers include, for example, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenyldiethylene glycol (meth)acrylate, 2-hydroxy-3 - phenoxypropyl (meth)acrylate, biphenyl acrylate, biphenyloxyethyl (meth)acrylate, biphenyloxyalkyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, Examples include isobornyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and t-butylcyclohexyl (meth)acrylate.
Among these, from the viewpoint of heat resistance and compatibility with the hydrophobic resin, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate are preferred, and dicyclopentanyl (meth)acrylate is preferred. Acrylates are more preferred.

The ring-containing (meth)acrylate monomer units can be used alone or in combination of two or more.

The content of the ring-containing (meth)acrylate monomer unit is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, and most preferably 20 to 40% by weight based on the total monomer units. By containing an appropriate amount, it is easy to achieve both heat resistance and compatibility with the transparent resin.

In addition to the ultraviolet absorbing monomer unit, the N-substituted cyclic imide unit constituting the main chain, and the ring-containing (meth)acrylate unit, the molding resin contains other (meth)acrylate monomer units (however, those that do not have a ring). ), and may contain other monomer units.

Other (meth)acrylate monomer units are (meth)acrylate units represented by the above general formula (2).
Examples of the (meth)acrylate unit represented by general formula (2) include (meth)acrylic acid ester.
Examples of other monomer units include aromatic vinyl monomer units and other vinyl monomer units.

<Other (meth)acrylate units>
Other (meth)acrylate units are (meth)acrylate units represented by the above general formula (2), such as (meth)acrylic esters having 1 to 30 carbon atoms. Among these, (meth)acrylic acid esters in which Z in general formula (2) has a chain hydrocarbon group having 10 or more carbon atoms are preferred. Thereby, compatibility with hydrophobic resins such as polyolefin resins can be further improved. The upper limit of the number of carbon atoms in Z is not limited, but is preferably 30 or less, more preferably 22 or less.

In general formula (2), the chain hydrocarbon group having 10 or more carbon atoms may have a linear structure or a branched structure. Examples of the chain hydrocarbon group include a decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, and tricosyl group. , a straight chain alkyl group such as a tetracosyl group, and a branched alkyl group such as an isodecyl group, an isolauryl group, an isopalmityl group, an isomyristyl group, and an isostearyl group. The chain hydrocarbon group preferably has a branched structure rather than a straight chain structure, and among these, an isostearyl group is more preferable. Note that the number of carbon atoms in the hydrocarbon group having a linear structure and a branched structure is preferably 14 or more. The upper limit of the number of carbon atoms in the hydrocarbon group is not limited as long as it can be polymerized, but is preferably 22 or less.

Examples of the above-mentioned specific monomers include lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, and behenyl (meth)acrylate. Among these, it is preferable to include a hydrocarbon group with a branched structure from the viewpoint of compatibility and heat resistance, and isostearyl (meth)acrylate is preferable. By using these together, the Tg of the molding resin can be adjusted, and the compatibility with various transparent resins can be significantly improved.

In general formula (2), (meth)acrylic esters in which Z has a chain hydrocarbon group having 9 or less carbon atoms are, for example, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate, etc. ) n-propyl acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, (meth)acrylate ) 2-ethylhexyl acrylate, tert-octyl (meth)acrylate, and the like.

In addition, other (meth)acrylates other than the above include hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerol mono(meth)acrylate. Containing (meth)acrylates, nitrogen-containing (meth)acrylates such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, methylethylaminoethyl (meth)acrylate, 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, Nitrogen-containing heterocyclic (meth)acrylates such as 6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 2-methoxyethyl (meth)acrylate, (meth)acrylic acid 2 -Ethoxyethyl, 2-(2-methoxyethoxy)ethyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, octoxypolyethylene glycol mono(meth)acrylate, and stearoxypolyethylene Examples include alkyleneoxy group-containing (meth)acrylates such as glycol mono(meth)acrylate and ethoxylated o-phenylphenol acrylate.

Among these, from the viewpoint of compatibility with various transparent resins, methyl methacrylate (methyl methacrylate unit) is preferably 20% by mass or less, more preferably 10% by mass or less, and 5% by mass or less based on the total monomer units. % or less, and most preferably no methyl methacrylate units. By setting it as the said range, compatibility especially with a hydrophobic resin can be improved, without reducing heat resistance, and heat resistance and compatibility with various resins can be made compatible. Note that the content of methyl methacrylate units may be 0% by mass.

Furthermore, a molding resin containing a nitrogen-containing heterocycle (meth)acrylate (but not having an ultraviolet absorption site) is preferable because the nitrogen-containing heterocycle improves photostability. The content of the nitrogen-containing heterocyclic (meth)acrylate is preferably 3 to 40% by weight, more preferably 3 to 30% by weight, and even more preferably 5 to 25% by weight based on 100% by weight of the total monomer units. By containing an appropriate amount, it is easy to achieve both photostability and heat resistance.

<Other monomer units>
Examples of other monomer units include aromatic vinyl monomer units and other vinyl monomer units.

<Aromatic vinyl monomer unit>
Aromatic vinyl monomers are monomers other than ultraviolet absorbing monomers, N-substituted cyclic imides constituting the main chain, and ring-containing (meth)acrylate units, such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, o- Ethylstyrene, p-tert-butylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenylethylene, isopropenyltoluene, isopropenylethylbenzene, isopropenylpropylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, Examples include isopropenylbenzylbenzene, isopropenylhexylbenzene, isopropenyloctylbenzene, and the like.

<Other vinyl monomer units>
Examples of other vinyl monomer units include crotonate ester, vinyl ester, maleate diester, fumarate diester, itaconate diester, (meth)acrylamide, vinyl ether, (meth)acrylonitrile, acidic group-containing monomers, etc. It will be done.

Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like.

Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, and the like.

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

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

Examples of the itaconic acid diester include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(Meth)acrylamide is, for example, (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Nn-butyl Acrylic (meth)amide, 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.

Examples of the vinyl ether include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

Acidic group-containing monomers include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, and anhydride. Examples include unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride, and mesaconic acid, or acid anhydrides thereof.

Each monomer unit contained in the molding resin may be contained alone or in two or more types.

<Synthesis of molding resin>
The molding resin can be synthesized by methods such as anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. Among these, free radical polymerization is preferred from the viewpoint of cost and productivity.

The weight average molecular weight (Mw) of the molding resin is preferably 5,000 to 60,000, more preferably 6,000 to 50,000, and more preferably 6,500 to 60,000 from the viewpoint of heat resistance and compatibility with the transparent resin. 45,000 is more preferred, and 7,000 to 40,000 is particularly preferred. By setting the weight average molecular weight (Mw) of the molding resin within the above range, an excellent balance between compatibility and heat resistance is achieved, and fluidity during molding is further improved. Note that the weight average molecular weight is a value measured by gel permeation chromatography (GPC).

The molecular weight distribution (Mw/Mn) of the molding resin is preferably 1 to 10, more preferably 1.2 to 5.0, and even more preferably 1.3 to 3.0. Within the above range, the compatibility with the transparent resin is improved and the molding resin is less likely to bleed out.

The glass transition temperature (Tg) of the molding resin is preferably 60°C to 180°C, more preferably 60°C to 120°C, even more preferably 60°C to 110°C. Within the above range, there is a good balance between processability and compatibility with the transparent resin.

The thermal decomposition start temperature (Td) of the molding resin is not particularly limited, but is preferably, for example, 200°C or higher, preferably 220°C or higher, and more preferably 240°C or higher. Within the above range, yellowing is unlikely to occur even during molding at high temperatures. Further, the temperature at which the weight decreases by 50% (Td50) is preferably higher than 330°C, more preferably higher than 340°C, and most preferably higher than 350°C. It can be said that the higher the temperature at which the weight decreases by 50% (Td50), the higher the heat resistance of the molding resin. Note that Tg and Td can be measured, for example, by the method described below.

<Thiol-based chain transfer agent>
It is preferable that the molding resin has a thiol-based chain transfer agent residue. In general, maleic anhydride units have low homopolymerizability, while N-substituted maleimide units have high homopolymerizability. Therefore, by using a thiol-based chain transfer agent, the ultraviolet absorbing monomer and the N-substituted maleimide can be copolymerized more stably, so that heat resistance and compatibility can be further improved. The thiol-based chain transfer agent residue preferably has a thiol group, and one or more moieties among a carboxyl group, a hydroxyl group, and an ester bond. Although the effect of thiol-based chain transfer agents on controlling polymer molecular weight is known, their characteristic odor poses a problem. However, because the thiol-based chain transfer agent residue at the end of the molding resin has one or more sites among carboxyl groups, hydroxyl groups, and ester bonds, the molding resin and lower alcohol, which is inexpensive and easy to remove, can be bonded. Improves affinity. This makes it possible to use lower alcohols in the purification process to remove low molecular weight resins and unreacted thiol-based chain transfer agents from molding resins, an unexpected effect that enables low-cost and simple purification. is obtained.

From the viewpoint 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. As a result, a molding resin with few impurities can be obtained, which is suitable for use in, for example, food packaging, pharmaceutical agents, cosmetic containers, and the like.

Examples of thiol-based chain transfer agents having a carboxyl group include α-mercaptopropionic acid, β-mercaptopropionic acid, 2,3-dimercaptopropionic acid, thioglycolic acid, thiolactic acid, o-mercaptobenzoic acid, and m-mercaptobenzoic acid. acid, thiomalic acid, o-thiocumaric acid, α-mercaptobutanoic acid, β-mercaptobutanoic acid, γ-mercaptobutanoic acid, 11-mercaptoundecanoic acid, and the like.

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

Examples of thiol-based chain transfer agents having an ester bond include thioglycolic acid alkyl esters such as methyl thioglycolate, octyl thioglycolate, and methoxybutyl thioglycolate, methyl mercaptopropionate, octyl mercaptopropionate, and methoxy mercaptopropionate. Examples include butyl, mercaptopropionate alkyl esters such as tridecyl mercaptopropionate, and the like.

The molecular weight of the thiol chain transfer agent is preferably 101 to 300, more preferably 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 by adding a small amount, so that molecular weight control becomes easy.

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

Thiol chain transfer agents can be used alone or in combination of two or more.

The content of the thiol chain transfer agent in the molding resin is preferably 0.01 to 5 parts by mass, preferably 0.05 to 4 parts by mass, based on 100 parts by mass of all monomer units of the molding resin. , more preferably 0.1 to 3 parts by mass. When contained in an appropriate amount, both molecular weight adjustment and affinity with lower alcohols can be achieved at a high level. In addition, since thiol-based chain transfer agents easily undergo Michael addition with electron-withdrawing monomers such as N-substituted maleimide, resulting in impurities, controlling the amount within the above range facilitates polymerization control and improves heat resistance and transparency. A molding resin with excellent properties and low odor can be obtained. Note that the thiol-based chain transfer agent is not included in the total monomer units.

Further, the content of the thiol chain transfer agent in the molding resin can also be specifically determined by measuring the amount of sulfur atoms derived from the thiol chain transfer agent using the method described below. Specifically, it is calculated by burning the molding resin and measuring the amount of sulfur-containing gas released. The molding resin preferably contains 0.001 to 0.3 parts by mass of sulfur atoms derived from the thiol chain transfer agent, and 0.001 to 0.25 parts by mass, based on 100 parts by mass of all monomer units. Parts by mass are more preferred, and 0.001 to 0.2 parts by mass are most preferred. When contained in an appropriate amount, both molecular weight adjustment and affinity with lower alcohols can be achieved at a high level.

The molding resin can be synthesized by known polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization, but in this specification, solution polymerization is preferred because it allows easy reaction control.

Further, the polymerization can be appropriately selected from random polymerization, block polymerization, etc., and radical polymerization is preferable among ionic polymerization, radical polymerization, etc.

<Polymerization initiator>
It is preferable to use a polymerization initiator in the synthesis of the molding resin. The polymerization initiator is preferably, for example, an azo compound or a peroxide. 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. Peroxides include, for example, benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate. , t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, diacetyl peroxide, and the like.

The polymerization initiators can be used alone or in combination of two or more.

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.

<Organic solvent>
Organic solvents can be used to synthesize the molding resin. Examples of 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, and ethylene. Examples include glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.
Note that the molding resin is preferably used after being purified. As the solvent used in the purification step, it is preferable to use methanol because the solubility of the molding resin is low, the cost and purity are low, and the solvent can be easily removed from the molding resin.

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

<Molding resin composition>
The molding resin composition includes a molding resin and a thermoplastic resin. Additionally, colorants and additives can be included as necessary. The blending amount of the molding resin is preferably 0.01 to 30 parts by weight, preferably 0.05 to 25 parts by weight, and more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the thermoplastic resin.
<Thermoplastic resin>
Thermoplastic resins include, for example, polyolefins such as polyethylene and polypropylene, polyacrylics such as polycarbonate and polymethyl methacrylate, polyesters, cycloolefin resins, polystyrene, polyphenylene ether, acrylonitrile-butadiene-styrene copolymers (ABS resins), polyamides, Mention may be made of polyacetal, polycarbonate, polyvinyl chloride, polyvinylidene chloride, and polyetherimide. Among these, polyolefins, cycloolefin resins, polyesters, polyacrylics, and polycarbonates are preferably used because they provide good moldability and mechanical strength of molded products. It is preferable that the number average molecular weight of the thermoplastic resin exceeds 30,000.

<Polyolefin>
Examples of the polyolefin include polyethylene, polypropylene polyethylene, polypropylene, polybutene-1, poly-4-methylpentene, and copolymers thereof.

The number average molecular weight of the polyolefin is approximately 30,000 to 500,000, preferably 30,000 to 200,000.

Examples of polyethylene include low density polyethylene and high density polyethylene. Examples of polypropylene include 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 copolymers, and ethylene-methyl acrylate copolymers. , ethylene-ethyl acrylate copolymer, and ethylene-acrylic acid copolymer.
Among these, crystalline or amorphous polypropylene, ethylene-propylene random, block or graft copolymers are preferred, and propylene-ethylene block copolymers are more preferred. Further, polypropylene is preferable from the viewpoint of being inexpensive and having a low specific gravity so that the weight of the molded product can be reduced.

The melt flow rate (MFR) of the polyolefin is preferably 1 to 100 (g/10 minutes). Note that MFR is a value determined in accordance with JISK-7210.

<Polycarbonate>
Polycarbonate is a compound obtained by synthesizing divalent phenol and a carbonate precursor by a known method. Divalent phenols include, for example, hydroquinone, resorcinol, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-3,5-dimethyl) phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4-hydroxyphenyl)sulfide, and the like. Among these, bis(4-hydroxyphenyl) alkanes are preferred, and 2,2-bis(4-hydroxyphenyl)propane, also known as bisphenol A, is more preferred. Examples of the carbonate precursor include phosgene, diphenyl carbonate, dihaloformate of divalent phenol, and the like. Among these, diphenyl carbonate is preferred.

<Polyacrylic>
Polyacrylic is a compound obtained by polymerizing monomers such as acrylic acid and/or methyl methacrylate and/or ethyl methacrylate by a known method. In addition to the above-mentioned monomers, monomers such as butadiene, α-methylstyrene, maleic anhydride, etc. can also be added for polymerization, and heat resistance, fluidity, and impact resistance can be adjusted depending on the monomer amount and molecular weight.

<Polyester>
Polyester is a resin that has 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); ) and a cyclic ether compound; and a ring-opening polymer of a cyclic ether compound. Examples of polyester include homopolymers of dicarboxylic acids and diols, copolymers using a plurality of raw materials, and polymer blends obtained by mixing these. Note that the dicarboxylic acid derivatives are acid anhydrides and esters. Although there are two types of dicarboxylic acids, aliphatic and aromatic, aromatic is more preferable because it improves heat resistance.

<Cycloolefin resin>
Cycloolefin resins are polymers of ethylene or α-olefins and cyclic olefins. α-olefins are monomers derived from C4 to C12 (4 to 12 carbon atoms) olefins, such as 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, Examples include 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, and 1-dodecene. Cyclic olefins are monomers derived from norbornene, and include substituted hydrogen groups, halogen atoms, and monovalent or divalent hydrocarbon groups. Among these, unsubstituted norbornene is preferred.

<Vinyl chloride resin>
Vinyl chloride resins include vinyl chloride homopolymers, copolymers of vinyl chloride and monomers that can be copolymerized (hereinafter also referred to as "vinyl chloride copolymers"), and vinyl chloride copolymers other than vinyl chloride copolymers. Examples include graft copolymers obtained by graft copolymerizing vinyl chloride onto a polymer.
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; acrylic acid , unsaturated carboxylic acids such as 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; vinylidene chloride, fluoride Vinyl halides such as vinyl; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; and the like.

The vinyl chloride resin other than the vinyl chloride copolymer may be any resin that can graft copolymerize vinyl chloride, such as ethylene/vinyl acetate copolymer, ethylene/vinyl acetate/carbon monoxide copolymer, ethylene/ethyl Examples include acrylate copolymers, ethylene/ethyl acrylate/carbon monoxide copolymers, ethylene/methyl methacrylate copolymers, ethylene/propylene copolymers, acrylonitrile/butadiene copolymers, polyurethanes, and the like.

A plasticizer can be used for vinyl chloride resin. Examples of plasticizers include phthalate ester plasticizers such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), and diisodecyl phthalate (DIDP); di-2-ethylhexyl adipate ( Fatty acid ester plasticizers such as DOA), diisobutyl adipate (DIBA), and dibutyl adipate (DBA); epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil fatty acid butyl, Epoxidized ester plasticizers such as octyl epoxystearate; trimellitic acid ester plasticizers such as tri-2-ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM); trimethyl phosphate (TMP), Examples include phosphoric acid ester plasticizers such as triethyl phosphate (TEP). Among these, epoxidized ester plasticizers are preferred from the viewpoint of moldability, processability, etc. of the resin sheet.

The glass transition temperature of the thermoplastic resin is preferably 70 to 330°C, more preferably 130 to 300°C.

<Wax>
The molding resin composition can contain wax.

The wax is preferably a low molecular weight polyolefin. Low molecular weight polyolefins are polymers of olefin monomers such as ethylene, propylene, butylene, and may be block, random copolymers, or terpolymers. Specifically, it is a polymer 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.

The number average molecular weight of the wax is preferably 1,000 to 30,000, more preferably 2,000 to 25,000. By being within this range, the wax transfers to the surface of the molded product appropriately, resulting in an excellent balance between sliding properties and bleed-out suppression. Note that the number average molecular weight of the polyolefin of the thermoplastic resin is greater than 30,000.

The melting point of the wax is preferably 60 to 150°C, more preferably 70 to 140°C. Within this range, the processability when melting and kneading the thermoplastic resin and wax becomes good.

Note that the melt flow rate (MFR) of the wax determined according to JIS K-7210 is preferably greater than 100 g/10 minutes.

The amount of wax blended is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the thermoplastic resin contained in the molded article.

The molding resin composition can be manufactured, for example, according to the composition ratio of the molded article. Alternatively, it can also be produced as a masterbatch containing a molding resin at a high concentration. In this specification, it is preferable to use the molding resin in the form of a masterbatch because it can be easily dispersed uniformly in the molded article.
The masterbatch is preferably made by melt-kneading a thermoplastic resin and a molding resin, and then molding the mixture into an arbitrary shape. Next, the masterbatch and a diluted resin (for example, the thermoplastic resin used in the masterbatch) are melt-kneaded to form a molded article of a desired shape. Examples of the shape of the masterbatch include pellets, powders, and plates. In order to prevent agglomeration of the molding resin, it is preferable to manufacture a masterbatch by melting and kneading the molding resin and wax in advance to produce a dispersion, and then melting and kneading the dispersion together with the thermoplastic resin. Preferably, the device used for the dispersion is, for example, a blend mixer or a three-roll mill.
The thermoplastic resin used to create the masterbatch is preferably the same thermoplastic resin as the diluent resin, but other thermoplastic resins may be used as long as there is no problem with compatibility.

When producing a molding resin composition as a masterbatch, the molding resin is preferably blended in 1 to 200 parts by mass, more preferably 5 to 70 parts by mass, per 100 parts by mass of the thermoplastic resin. The mass ratio of the masterbatch (X) to the diluted 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. . If it is within this range, the molding resin will be uniformly dispersed in the molded product, and good ultraviolet absorption and good transparency will be easily obtained.

Examples of melt-kneading include a single-screw kneading extruder, a twin-screw kneading extruder, and a tandem twin-screw kneading extruder. The melting and kneading temperature varies depending on the type of transparent resin, but is usually about 150 to 350°C.

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

<Molded object>
The molded article of the present invention is formed by molding a molding resin composition.
The molded body is preferably used for, for example, food packaging materials, pharmaceutical packaging materials, and display applications. For food packaging materials and pharmaceutical packaging materials, it is preferable to use polyolefin, polyester, or the like as the thermoplastic resin. These molded bodies have improved flexibility and visibility, and can suppress deterioration of the contents. This allows the self-life of medicines, cosmetics, etc. to be extended. Furthermore, for display applications (for example, televisions, personal computers, smartphones, etc.), it is preferable to use, for example, polyacrylic or polycarbonate as the thermoplastic resin. These molded objects can suppress the harmful effects on the eyes by absorbing the ultraviolet rays contained in backlights and the short wavelength range of visible light contained in sunlight. By absorbing light in the wavelength range, it is possible to suppress deterioration of display elements of a display, and furthermore, it is possible to suppress a decrease in transparency due to migration. Furthermore, it can be used in a wide range of applications such as display materials, sensor materials, and optical control materials.

When the molding resin composition is a masterbatch, the molded article contains a diluted resin. When the formulation of the molding resin composition is the same as the composition of the molded article, the molding resin composition is molded as is to produce the molded article.

Examples of the molding method include extrusion molding, injection molding, and blow molding. Examples of extrusion molding include compression molding, pipe extrusion molding, lamination molding, T-die molding, inflation molding, and melt spinning.

The molding temperature is usually 160 to 320°C depending on the softening point of the diluted resin.

Molded objects can be used, for example, for medical drugs, cosmetics, food containers, packaging materials, miscellaneous goods, textile products, pharmaceutical containers, various industrial coatings, automobile parts, home appliances, building materials for housing, toiletries, etc. Can be used for a wide range of purposes. Molded objects include those obtained by pouring resin into a mold, and articles obtained without using a mold, such as plastic films.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples. Note that "part" means "part by mass" and "%" means "% by mass."

[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 equipment, two separation columns were connected in series, and the packing material for both was "TSK-GEL SUPER HZM-N" connected in two series, and the oven temperature was 40℃. The measurement was carried out using THF (tetrahydrofuran) as an eluent at a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent, and 20 microliters of the sample was injected. All molecular weights are polystyrene equivalent values.

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

[Glass transition temperature (Tg)]
The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC VESTA manufactured by Rigaku Co., Ltd.). Using alumina as a reference, weigh approximately 2 mg of each of the test sample and alumina on an aluminum pan, set the aluminum pan on a DSC measurement holder, and measure the DSC curve obtained under the heating conditions of 5°C/min. Tg was obtained by reading the baseline shift (inflection point) to the endothermic side.

[Thermogravimetric analysis/differential thermal analysis]
The TG-DTA curve was measured by raising the temperature from 40°C to 500°C at a heating rate of 10°C/min in the air using a differential thermal/thermogravimetric simultaneous measurement device (TG-DTA8122 model manufactured by Rigaku Co., Ltd.). . The temperature at which the measurement sample loses 50% in weight was defined as Td50, and a comparison was made. The higher the Td50 temperature, the better the heat resistance.
◎: 350℃ or higher (excellent)
〇: 340℃ or more - less than 350℃ (good)
△: 330℃ or more to less than 340℃ (practical range)
×: Less than 330℃ (not practical)

[Examples of manufacturing resin for molding (B-1) to (B-18)]
(Molding resin (B-1))
In a four-necked separable flask equipped with a thermometer, stirrer, dropping funnel, and condenser, 250 parts of methyl ethyl ketone and 2-[2-hydroxy-5-[2-(methacryloyloxy)] as an ultraviolet absorbing monomer unit were added. 40 parts of ethyl]phenyl]-2H-benzotriazole, 5 parts of N-phenylmaleimide as an N-substituted cyclic imide unit constituting the main chain, 5 parts of methyl methacrylate as other (meth)acrylate monomer units, 25 parts of isostearyl acrylate and 25 parts of dicyclopentanyl methacrylate were charged, and the mixture was stirred for 30 minutes under a nitrogen stream. Thereafter, 1 part of 2-ethylhexyl 3-mercaptopropionate was added as a thiol-based chain transfer agent, followed by 1.0 part of 2,2'-azobis(methyl isobutyrate), and the temperature was raised to 80°C while refluxing. Polymerization reaction was started. After 2 hours had elapsed after the temperature was raised, 0.1 part of 2,2'-azobis(methyl isobutyrate) was added every hour, and the reaction was continued for a total of 8 hours. Thereafter, sampling was performed to confirm that the conversion rate was 98% or more, and after cooling, the solution 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 placed in a 1 L beaker and stirred at 1,000 rpm using a disper, to which 100 parts of resin solution b-1 was added dropwise over 1 hour. Thereafter, vacuum suction was carried out using a Buchner funnel with a diameter of 150 mm using qualitative filter paper (manufactured by ADVANTEC, product name No. 2), and the white precipitate formed was filtered. The time required for 200 g of filtrate to escape was less than 1 minute, and there was no problem with filtration. Vacuum suction was continued for another 30 minutes, and it was confirmed that no 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.

As shown in Table 1 below, molding resins (B-2) to (B-15) were prepared in the same manner as molding resin (B-1) except that the monomers and chain transfer agent used were changed. , (B-17) and (B-18) were obtained.

(Molding resin (B-16))
A four-necked separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser was charged with 20 parts of methyl ethyl ketone, and the mixture was stirred for 30 minutes under a nitrogen stream. Next, 40 parts of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole as an ultraviolet absorbing monomer unit was added to the dropping funnel, and 40 parts of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole was added to the dropping funnel, and 40 parts of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole was added to the N-substituted main chain. A monomer solution in which 10 parts of N-phenylmaleimide, 25 parts of isostearyl acrylate, and 25 parts of dicyclopentanyl methacrylate were dissolved in 86 parts of methyl ethyl ketone as a cyclic imide unit was charged. Next, while heating the separable flask to 80°C and refluxing it, a monomer solution was added from the dropping funnel, and an initiator solution containing 10 parts of 2,2'-azobis(methyl isobutyrate) dissolved in 23 parts of methyl ethyl ketone was added. The agent solution was added dropwise over 3 hours to carry out a polymerization reaction. One hour after the completion of the dropwise addition, 0.1 part of 2,2'-azobis(methyl isobutyrate) was added every hour, and the reaction was continued for a total of 8 hours. Thereafter, sampling was performed to confirm that the conversion rate was 98% or more, and after cooling, the solution was diluted with methyl ethyl ketone to produce a resin solution b-16 with a nonvolatile content of 30%.
Next, 300 parts of methanol was placed in a 1 L beaker and stirred at 1,000 rpm using a disper, and 100 parts of resin solution b-16 was added dropwise over 1 hour. Thereafter, vacuum suction was carried out using a Buchner funnel with a diameter of 150 mm using qualitative filter paper (manufactured by ADVANTEC, product name No. 2), and the white precipitate formed was filtered. The time required for 200 g of filtrate to escape was less than 1 minute, and there was no problem with filtration. Vacuum suction was continued for another 30 minutes, and it was confirmed that no filtrate came out. Then, the obtained white precipitate was dried in a vacuum dryer at 50° C. for 12 hours to produce a polymer (B-16). The nonvolatile content of the obtained polymer (B-16) was 99% or more.

<Workability of molding resin manufacturing process>
The filterability and drying properties were evaluated in the same manner as for molding resin (B-1). Specifically, filtration performance was determined by suctioning 400 g of the slurry solution 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 time required for 200 g of filtrate to drain was measured, and a case in which the time required was less than 1 minute was considered good, and a case in which the time required was 1 minute or more or a clean slurry could not be obtained was judged as poor. The drying property was determined by drying the white precipitate of the molding resin in a vacuum dryer at 50° C. under reduced pressure and heating at a pressure of 15 kPa (A), and measuring the time it took for the nonvolatile content to reach 99% or more. Those whose required time was less than 12 hours were considered good, and those whose required time was 12 hours or more or whose non-volatile content did not reach 99% were considered poor.

Note that the terms in Tables 1-1 and 1-2 are as follows.
Monomer unit represented by general formula (1) Benzotriazole skeleton: 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazoletriazine skeleton: Compound (a1-4-1 )
Benzophenone skeleton: 4-acryloyloxybenzophenone OTG: 2-ethylhexyl 3-mercaptopropionic acid 1TG: 3-mercapto-1,2-propanediol

(Example 1)
[Manufacture of molding resin composition (masterbatch)]
As a thermoplastic resin, 100 parts of Iupilon S-3000 (polycarbonate resin, manufactured by Mitsubishi Engineering Plastics, amorphous resin, glass transition temperature 145°C, MFR 15g/10min (300°C/1.2kg), and molding resin (B -1) 20 parts were supplied from separate supply ports, melted and kneaded at 280°C using a twin-screw extruder (manufactured by Japan Steel Works), cooled, and cut into pellets using a pelletizer to form a master. A batch was produced.

[Film molding]
The above-mentioned master produced for 100 parts of Iupilon S-3000 (polycarbonate resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., amorphous resin, glass transition temperature 145°C, MFR 15g/10min (300°C/1.2kg) as a diluent resin) 10 parts of the batch were mixed. Then, using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.), the mixture was melted and mixed at a temperature of 300° C., and a film with a thickness of 250 μm was molded.

The thermoplastic resin shown below was used as the thermoplastic resin of Example 1, and a molding resin composition was produced in the same manner by changing the molding temperature as appropriate, and then film molding was performed.

The thermoplastic resin used in this example is shown below.
PMMA: Polymethacrylic resin (Acrypet MF, MFR=14g/10min (230°C/3.8kg), manufactured by Mitsubishi Rayon Co., Ltd.)
PET: Polyester resin (Polyester MA-2101M, MFR45g/10min (280°C/2.16kg), manufactured by Unitika)
PP::Polypropylene resin (Prime Polypro J226T, MFR=20g/10min (230°C/3.8kg), manufactured by Prime Polymer Co., Ltd.)

(Examples 2 to 16, Comparative Examples 1 and 2)
A masterbatch and a film were produced in the same manner as in Example 1, except that the materials used in Example 1 were changed to the materials and blending amounts shown in Table 2.

The following items were evaluated regarding the obtained film. Items other than transparency were evaluated using a film using polycarbonate resin.

[Ultraviolet absorption]
The transmittance of the formed film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). The transmittance was determined by measuring the spectral transmittance against a white standard plate. It was evaluated whether the following conditions were satisfied. The evaluation criteria are as follows.
◎: 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 the wavelength range of 290 to 360 nm. Practical range.
×: Light transmittance in the wavelength range of 290 to 360 nm is 2% or more over the entire region. Not practical.

[Retention heat resistance test]
As the thermoplastic resin, in Example 1, 100 parts of Iupilon S-3000 (polycarbonate resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., amorphous resin, glass transition temperature 145 ° C., MFR 15 g / 10 min (300 ° C. / 1.2 kg)) 10 parts of the prepared masterbatch were mixed.Next, using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.), they were melt-mixed at a temperature of 300°C for 1 minute, and then allowed to stay in the T-die molding machine as it was. A film with a thickness of 250 μm was formed at intervals of time, and the transparency of the film was visually evaluated.The residence time was 0 minutes and 5 minutes. The retention test was evaluated in the same manner as in Example 1, except that the masterbatch was changed.
The evaluation criteria are as follows. Visual evaluation was confirmed by five monitors.
◎: There is no difference in the presence or absence of retention, and no turbidity is observed (all monitors judged that there was no turbidity). Are better.
○: There is a slight difference depending on the presence or absence of retention, and almost no turbidity is observed (one monitor judged it to be turbid). Good.
△: Slight turbidity is observed before and after retention (2 to 4 monitors judged it to be turbid). Practical range.
×: Turbidity is clearly observed before and after retention (all monitors judge that it is cloudy). Not practical.

[transparency]
The permeability of the formed film was visually evaluated. The evaluation criteria are as follows.
Visual evaluation was confirmed by five monitors.
◎: No turbidity observed at all (all monitors judged that there was no turbidity). Are better.
○: Almost no turbidity observed (one monitor judged it to be turbid). Good.
△: Slight turbidity is observed (2 to 4 monitors judged it to be turbid). Practical range.
×: Cloudiness is clearly observed (all monitors judge that it is cloudy). Not practical.

[Odor evaluation]
The formed film was cut into 10 cm square pieces, placed in an aluminum vapor deposition bag, sealed, and allowed to stand at 40° C. for 24 hours. Afterwards, the odor was confirmed by five monitors.
◎: Almost no odor is observed (all monitors do not perceive any odor). Good.
○: Slight odor is observed. (1 to 3 monitors sense the odor). Practical range.
×: Odor is clearly observed (4 or more monitors sense odor). Not practical.

From the results in Table 2, molded products using the molding resins (B-1 to B-16) of the present invention have excellent heat resistance and good compatibility with various thermoplastic resins. Transparency was good. Comparative Example 1 had poor heat resistance because the molding resin did not contain an N-substituted cyclic imide unit constituting the main chain. Although Comparative Example 2 contains N-substituted maleimide units, it does not contain ring-containing (meth)acrylate units, so it cannot solve the problem of poor compatibility with polypropylene resins and good compatibility with various resins.

Claims (7)

Contains an ultraviolet absorbing monomer unit, an N-substituted cyclic imide unit constituting the main chain, and a ring-containing (meth)acrylate unit (but does not have an ultraviolet absorbing site), and has a weight average molecular weight of 5,000 to 60. 000 molding resin. The molding resin according to claim 1, further comprising a methyl methacrylate unit, and the methyl methacrylate unit accounts for 20% by mass or less of all monomer units. The molding resin according to claim 1, further comprising a thiol chain transfer agent residue. The molding resin according to claim 3, which contains 0.01 to 5 parts by mass of the thiol-based chain transfer agent residue based on 100 parts by mass of total monomer units. The molding resin according to claim 1, which contains 3 to 25% by mass of N-substituted cyclic imide units constituting the main chain based on the total monomer units. A molding resin composition comprising the molding resin according to any one of claims 1 to 5 and a thermoplastic resin. A molded article obtained by molding the molding resin composition according to claim 6.