JP7474613B2 - Aqueous compositions using copolymers containing benzotriazole-based ultraviolet absorbing units - Google Patents

Description

The present invention relates to a copolymer containing a benzotriazole-based ultraviolet absorbing unit and a composition thereof.

Resin components deteriorate due to the action of ultraviolet rays, causing quality deterioration such as discoloration and reduced mechanical strength, which hinders long-term use. In addition, from a health perspective, ultraviolet rays can have adverse effects on the skin and eyes, so there is a need to control the wavelength of transmitted light, and in recent years there has been a demand for wavelength control between 360 and 420 nm.

Conventionally, a benzotriazole skeleton has been known as a functional group with ultraviolet absorbing ability. Patent documents 1 to 5 disclose compounds in which an acryloyloxy group, which is reactive with monomers and resins, has been introduced into a 2-phenylbenzotriazole skeleton via an alkylene group or an alkylene group with ether oxygen introduced at the base end, and (co)polymers using the compounds. There was a problem that the absorption efficiency of harmful wavelengths in the vicinity of 360 to 420 nm was low. In addition, the solubility and dispersibility of the (co)polymer in organic solvents and water have not been examined in detail.

The present inventors have proposed a 2-phenylbenzotriazole derivative having a sulfur-containing group as an ultraviolet absorber that efficiently and sufficiently absorbs harmful light from 380 to 400 nm and suppresses the absorption of light with a wavelength of 400 nm or more, which is a cause of initial yellowing (Patent Documents 6 and 7). This ultraviolet absorber can sufficiently absorb light in the wavelength range of 250 to 400 nm due to its optical properties, and has a high ultraviolet absorption effect (molar extinction coefficient), so that it can efficiently absorb light of that wavelength with the addition of a small amount. Furthermore, the slope of the absorption peak at 350 to 390 nm is larger than that of conventional ultraviolet absorbers, suppressing the absorption of light with a wavelength of around 400 nm or more, and suppressing the initial yellowing of the material to which it is mixed. In the examples, a compound in which an allyl group is bonded to a 2-phenylbenzotriazole skeleton via a sulfur atom is synthesized, but there was room for further improvement in the reactivity that enables high molecular weight and the solubility in the monomer of the resin raw material. In Patent Document 8, the solubility and reactivity in the monomer of the resin raw material were improved. In the examples, copolymers with methyl methacrylate, styrene, vinyl acetate, dimethylacrylamide, or hexadiene are synthesized, but there is no description of the copolymer's affinity with various organic solvents, light resistance, or strength focusing on the glass transition point. In recent years, there has been a demand for copolymer compositions that have the ability to absorb wavelengths around 360 to 420 nm, have high strength and long-term stability (light resistance) under high temperature conditions, and contain organic solvents that are also highly stable over the long term and have a high affinity for resins. On the other hand, there is also a demand for aqueous copolymer compositions that are low environmental impact and highly safe for humans.

JP 2012-25811 A JP 2000-119569 A JP 2001-234072 A JP 2002-226521 A JP 2002-226522 A International Publication No. 2016/021664 International Publication No. 2016/174788 International Publication No. 2019/087983

As described above, copolymers containing benzotriazole-based ultraviolet absorbing units, which have excellent long-wavelength absorption, have not been sufficiently studied from the viewpoints of efficient absorption of long-wavelength ultraviolet light, high affinity with organic solvents, high stability due to dispersibility, strength at high temperatures, and light resistance.

The present invention has been made in view of the above circumstances, and aims to provide a copolymer that efficiently absorbs ultraviolet light with long wavelengths of 360 to 420 nm, and in addition, to provide a copolymer and composition thereof that exhibits high stability due to high solubility and dispersibility when combined with organic solvents due to its high affinity with organic solvents, and further has excellent strength and light resistance at high temperatures. On the other hand, it also aims to provide an aqueous composition from the standpoint of low environmental impact and safety.

In order to achieve the above object, the copolymer of the present invention is characterized by containing the following monomer (A) and monomer (B).
(Monomer (A))
The following formula (I):

（式中、Ｒ¹～Ｒ⁹はそれぞれ独立に、下記式（i－１）：

(In the formula, R ¹ to R ⁹ each independently represent the following formula (i-1):

In formula (i-1), R ¹⁰ represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, R ¹¹ represents, when m is 2 or more, a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ¹² represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and

(wherein R ^12a , R ^12b , and R ^12c each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, A represents a divalent group selected from an ester group, an amide group, and an aromatic group, and X represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.) represents a monovalent group represented by the formula (I), a monovalent group selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and a hydroxy group. At least one of R ¹ to R ⁹ is a monovalent sulfur-containing group represented by the formula (I-1). ) (monomer (B))
Ester Group-Containing Vinyl Monomer The composition of the present invention contains the copolymer and an organic solvent.
The aqueous composition of the present invention comprises the copolymer, water and a surfactant.

The copolymer and composition of the present invention efficiently absorb ultraviolet light with long wavelengths of 360 to 420 nm. In addition, due to their high affinity with organic solvents, they exhibit high stability due to their high solubility and dispersibility when combined with organic solvents, and furthermore, they exhibit excellent strength and light resistance at high temperatures. On the other hand, by forming them into aqueous compositions containing surfactants, it is possible to obtain compositions that are low in environmental impact and highly safe.

1 is an ultraviolet-visible absorption spectrum (UV chart) of a toluene solution of Copolymer 6, which is an example of the present invention. 1 is an ultraviolet-visible absorption spectrum (UV chart) of a toluene solution of Copolymer 26, which is a comparative example. 1 is an ultraviolet-visible absorption spectrum (UV chart) of an aqueous dispersion of Copolymer 16, which is an example of the present invention.

The present invention will be described in detail below.
(Monomer (A))
In the copolymer of the present invention, the monomer (A) is a benzotriazole compound represented by the above formula (I).
[Substituents, etc.]
In the present invention, the substituent includes a group capable of adjusting heat resistance, refractive index, melting point, light resistance, compatibility with resins, and the like, such as "aromatic group, unsaturated group, nitrogen-containing group, sulfur-containing group, oxygen-containing group, phosphorus-containing group, alicyclic group, and a monovalent or divalent group selected from a halogen atom", and examples thereof include the following:

The aromatic group includes an aromatic ring such as a benzene ring, a naphthalene ring, or an anthracene ring, and has preferably 6 to 18 carbon atoms, more preferably 6 to 14. The monovalent aromatic group is not particularly limited, but examples thereof include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,4,5-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a 4-biphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-ethoxyphenyl group, a 3-ethoxyphenyl group, a 4-ethoxyphenyl group, a 2-chlorophenyl group, a 2-fluorophenyl group, a 4-fluorophenyl group, a 2-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, and a 9-anthracenyl group. The divalent aromatic group is not particularly limited, but examples thereof include 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,8-naphthylene group, 2,7-naphthylene group, 2,6-naphthylene group, 1,4-naphthylene group, 1,3-naphthylene group, 9,10-anthracenylene group, 1,8-anthracenylene group, 2,7-anthracenylene group, 2,6-anthracenylene group, 1,4-anthracenylene group, and 1,3-anthracenylene group.

The unsaturated group includes carbon-carbon or carbon-heteroatom unsaturated bonds such as carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds (carbonyl groups, aldehyde groups, ester groups, carboxy groups, carbamate groups, urea groups, amide groups, imide groups, carbamoyl groups, urethane groups, etc.), carbon-nitrogen double bonds (isocyanate groups, etc.), and carbon-nitrogen triple bonds (cyano groups, cyanato groups, etc.), and preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. The unsaturated group is not particularly limited, and examples thereof include acryloyl groups, methacryloyl groups, maleic acid monoester groups, styryl groups, allyl groups, vinyl groups, alkenyl groups, alkynyl groups, carbonyl groups, aldehyde groups, ester groups, carboxy groups, carbamate groups, urea groups, amide groups, imide groups, carbamoyl groups, cyano groups, cyanato groups, isocyanate groups, and urethane groups.

The nitrogen-containing group includes a cyano group, a nitro group, or a primary to tertiary amino group, and preferably has 0 to 10 carbon atoms. The nitrogen-containing group is not particularly limited, but examples thereof include a cyano group, a cyanato group, an isocyanate group, a nitro group, a nitroalkyl group, an amide group, a urea group, a urethane group, an imide group, a carbodiimide group, an azo group, a pyridine group, an imidazole group, an amino group, a primary amino group, a secondary amino group, a tertiary amino group, an aminoalkyl group, a 3,4,5,6-tetrahydrophthalimidylmethyl group, and a 2-[6-(2H-benzotriazol-2-yl-)-4-(1,1,3,3-tetramethylbutyl)phenol-yl]-methyl group.

The sulfur-containing group includes a thiol group, a thioether group, a sulfide group, a disulfide group, a thioester group, a thioamide group, a sulfonyl group, a sulfo group, a thiocarbonyl group, or a thiourea group, and preferably has 0 to 10 carbon atoms. The sulfur-containing group is not particularly limited, but examples thereof include a thiomethoxy group, a thioethoxy group, a thio-n-propoxy group, a thioisopropoxy group, a thio-n-butoxy group, a thio-t-butoxy group, a thiophenoxy group, a p-methylthiophenoxy group, a p-methoxythiophenoxy group, a thiophene group, a thiazole group, a thiol group, a sulfo group, a sulfide group, a disulfide group, a thioester group, a thioamide group, a sulfonyl group, a thiocarbonyl group, a thiourea group, a thiocarbamate group, and a dithiocarbamate group.

When the oxygen-containing group contains an aromatic ring group or an alicyclic group, the carbon number is preferably 6 to 12, and when the oxygen-containing group does not contain an aromatic ring group or an alicyclic group, the carbon number is preferably 0 to 18. The oxygen-containing group is not particularly limited, but examples thereof include a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, a naphthoxy group, a phenylmethoxy group, a phenylethoxy group, an acetoxy group, an acetyl group, an aldehyde group, a carboxy group, an ether group, a carbonyl group, an ester group, an oxazole group, a morpholine group, a carbamate group, a carbamoyl group, and a polyoxyethylene group.

The phosphorus-containing group includes a phosphine group, a phosphite group, a phosphonic acid group, a phosphinic acid group, a phosphoric acid group, or a phosphoric acid ester group, and if it includes an aromatic ring group or an alicyclic group, the number of carbon atoms is preferably 6 to 22, and if it does not include an aromatic ring group or an alicyclic group, the number of carbon atoms is preferably 0 to 6. The phosphorus-containing group is not particularly limited, but examples thereof include a trimethylphosphine group, a tributylphosphine group, a tricyclohexylphosphine group, a triphenylphosphine group, a tritolylphosphine group, a methylphosphine group, an ethylphosphite group, a phenylphosphite group, a phosphonic acid group, a phosphinic acid group, a phosphoric acid group, and a phosphoric acid ester group.

The alicyclic group preferably has 3 to 10 carbon atoms, more preferably 3 to 8. Examples of the alicyclic group include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and groups containing these groups as the skeleton.

Halogen atoms include, but are not limited to, fluorine, chlorine, bromine, and iodine atoms.

In the present invention, examples of the substituent include groups in which the hydrogen atom bonded to the carbon of the above-listed substituents is replaced with a halogen atom.

The benzotriazole compound represented by the formula (I) contains a monovalent sulfur-containing group represented by the formula (i-1) at least at any one of the positions R ¹ to R ⁹ bonded to the benzotriazole skeleton.

In formula (i-1), R ¹⁰ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms, which may have a substituent.

Examples of the divalent hydrocarbon group of R ¹⁰ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among them, an aliphatic hydrocarbon group is preferable, and examples thereof include a linear or branched alkylene group, a linear or branched alkenylene group, and a linear or branched alkynylene group. Although not particularly limited, examples thereof include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a 1-methylethane-1,2-diyl group, a butane-1,4-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a pentane-1,5-diyl group, a pentane-1,4-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,3-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, a hexane-1,8-diyl group, a hexane-1,9-diyl group, a hexane-2,10-diyl group, a hexane-2,11-diyl group, a hexane-2,12-diyl group, a hexane-2,13-diyl group, a hexane-2,14-diyl group, a hexane-2,15-diyl group, a hexane-2,16-diyl group, a hexane-2,17-diyl group, a hexane-2,18-diyl group, a hexane-2,19 ... ,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-yl group, tetradecane-1,14-yl group, pentadecane-1,15-yl group, hexadecane-1,16-yl group, heptadecane-1,17-yl group, octadecane-1,18-yl group, nonadecane-1,19-yl group, eicosan-1,20-yl group, etc. Among these, alkylene groups are preferred, and linear alkylene groups are more preferred. Examples of the alicyclic hydrocarbon group and aromatic hydrocarbon group include the alicyclic groups and aromatic groups exemplified in the above [Substituent, etc.].

When the divalent hydrocarbon group has a substituent, the number of the substituents is not particularly limited, but examples include 2 or less, or 1 or less.

Specific examples of the substituents include those exemplified in the [Substituents, etc.] column.

In formula (i-1), l is an integer of 0 or 1, and preferably, l is 0.

In formula (i-1), when m is 2 or more, R ¹¹ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms, which may have a substituent.

Examples of the divalent hydrocarbon group of ^R11 include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Among them, aliphatic hydrocarbon groups are preferred, and examples of the divalent hydrocarbon group of ^R10 include those exemplified above. Among these, alkylene groups are preferred, and linear alkylene groups are more preferred. Examples of the alicyclic hydrocarbon group and aromatic hydrocarbon group include the alicyclic groups and aromatic groups exemplified above in [Substituents, etc.].

When the divalent hydrocarbon group of R ¹¹ has a hydrogen atom substituted, at least one of both ends interrupted, or a carbon-carbon bond interrupted by the above-mentioned monovalent or divalent substituent, the number of the monovalent or divalent substituents is not particularly limited, and examples thereof include 2 or less, or 1 or less.

In formula (i-1), m is an integer from 0 to 3, preferably 0 or 1, and more preferably 0.

In formula (i-1), R ¹² is a monovalent group represented by the above formula (i-2).

In formula (i-2), R ^12a , R ^12b and R ^12c each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms.

Examples of monovalent hydrocarbon groups having 1 to 18 carbon atoms include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Of these, aliphatic hydrocarbon groups are preferred. Examples of aliphatic hydrocarbon groups include linear or branched alkyl groups, linear or branched alkenyl groups, and linear or branched alkynyl groups. Of these, linear or branched alkyl groups are preferred. Examples of linear or branched alkyl groups include methyl, ethane-1-yl, propane-1-yl, 1-methylethane-1-yl, butane-1-yl, butane-2-yl, 2-methylpropane-1-yl, 2-methylpropane-2-yl, pentan-1-yl, pentan-2-yl, hexane-1-yl, heptan-1-yl, octan-1-yl, nonane-1-yl, decan-1-yl, undecane-1-yl, dodecane-1-yl, tridecane-1-yl, tetradecane-1-yl, pentadecane-1-yl, hexadecan-1-yl, heptadecane-1-yl, and octadecane-1-yl groups. Examples of alicyclic and aromatic hydrocarbon groups include the alicyclic and aromatic groups exemplified in the above-mentioned [Substituents, etc.].

Considering the reactivity with and solubility of the resin raw material monomer, the monovalent hydrocarbon group preferably has 1 to 13 carbon atoms, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 1. In addition, preferred embodiments are (1) R ^12a , R ^12b , and R ^12c are hydrogen atoms, (2) R ^12a is a monovalent hydrocarbon group having 1 to 3 carbon atoms, R ^12b and R ^12c are hydrogen atoms, and (3) R ^12a is a hydrogen atom, R ^12b is a monovalent hydrocarbon group having 1 to 13 carbon atoms, and R ^12c is a hydrogen atom. In particular, (1) in which R ^12a , R ^12b , and R ^12c are hydrogen atoms, (2) in which R ^12a is a monovalent hydrocarbon group having 1 carbon atom and R ^12b and R ^12c are hydrogen atoms, or (3) in which R ^12a is a hydrogen atom, R ^12b is a monovalent hydrocarbon group having 1 carbon atom, and R ^12c is a hydrogen atom are preferred, and from the viewpoint of high reactivity, (1) in which R ^12a , R ^12b , and R ^12c are hydrogen atoms is more preferred.

In formula (i-2), A represents a divalent group selected from an ester group, an amide group, and an aromatic group.

The ester group is -C(=O)O- or -OC(=O)-, and the amide group is -NHC(=O)- or -C(=O)NH-. The aromatic group may have a substituent, such as those exemplified in the [Substituents, etc.] column above, but 1,4-phenylene, 1,3-phenylene, and 1,2-phenylene groups are preferred, and 1,4-phenylene is more preferred. Considering the reactivity and solubility with the monomer of the resin raw material, A is preferably an ester group, and among these, from the viewpoints of dispersibility and solubility in organic solvents and dispersibility and solubility in water, an ester group of -X-O-C(=O)- in which an oxygen atom is bonded to X is more preferred.

In formula (i-2), X represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Examples of the divalent hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include those exemplified as the divalent hydrocarbon group for ^R10 above, and examples of the alicyclic hydrocarbon group and aromatic hydrocarbon group include the alicyclic groups and aromatic groups exemplified in [Substituents, etc.].

Among these, aliphatic hydrocarbon groups and aromatic hydrocarbon groups are preferred. Among these, alkylene groups and phenylene groups are preferred, and linear alkylene groups and phenylene groups are more preferred. From the viewpoint of dispersibility and solubility in organic solvents and dispersibility and solubility in water, the alkylene group preferably has a shorter carbon number, preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 6.

When the divalent hydrocarbon group X has a substituent, the number of the substituents is not particularly limited, but examples include 2 or less, or 1 or less. Examples of the substituents include those exemplified in the [Substituents, etc.] column above.

Particularly preferred examples of the monovalent group represented by formula (i-1) include groups represented by the following formulas (i-1-1), (i-1-2), and (i-1-3) in which l and m are 0 and R ^12c is a hydrogen atom.

（式中、Ｒ^12a、Ｒ^12b、Ａ、ｎは前記と同義である。）

(In the formula, R ^12a , R ^12b , A, and n are as defined above.)

（式中、Ｒ^12a、Ｒ^12b、Ａ、ｎは前記と同義である。）

(In the formula, R ^12a , R ^12b , A, and n are as defined above.)

（式中、Ｒ^12a、Ｒ^12b、Ａは前記と同義である。）

(In the formula, R ^12a , R ^12b and A are as defined above.)

A copolymer containing the benzotriazole compound represented by formula (I) as a monomer (unit) has excellent UV absorption ability for long wavelengths of 360 to 420 nm, and can retain UV absorption ability for a long period of time without the benzotriazole component bleeding out or eluting. In addition, a copolymer combined with the monomer (B) below exhibits solubility and dispersibility in combination with organic solvents due to its high affinity with organic solvents, has good affinity with resins, and also exhibits excellent strength and light resistance at high temperatures.

In the benzotriazole compound represented by formula (I), at least one of R ¹ to R ⁹ is a monovalent sulfur-containing group represented by formula (i-1). Among them, taking into consideration the ultraviolet absorbing ability, affinity with organic solvents, strength at high temperatures, high light resistance, ease of actual synthesis, absorption characteristics, cost, heat resistance, or compatibility with other monomers in the copolymer raw material to improve and thereby enable the expression of high ultraviolet absorbing ability, it is preferable that one or two of R ¹ to R ⁹ are monovalent sulfur-containing groups represented by formula (i-1), and it is more preferable that one is a monovalent sulfur-containing group represented by formula (i-1).

The position of the monovalent sulfur-containing group represented by formula (i-1) in formula (I) is not particularly limited, and the monovalent sulfur-containing group represented by formula (i-1) is preferably located at any one of R ⁶ to R ⁹ in formula (I), and more preferably at R ⁶ or R ⁹ .

In formula (I), when R ¹ to R ⁹ are a group other than the monovalent sulfur-containing group represented by formula (i-1), they represent a monovalent group selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and a hydroxy group.

When R ¹ to R ⁹ are monovalent hydrocarbon groups, examples of the monovalent hydrocarbon group include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, etc. Among these, aliphatic hydrocarbon groups are preferred, and examples thereof include linear or branched alkyl groups, linear or branched alkenyl groups, linear or branched alkynyl groups, etc. Specifically, for example, a methyl group, an ethane-1-yl group, a propane-1-yl group, a 1-methylethane-1-yl group, a butane-1-yl group, a butane-2-yl group, a 2-methylpropane-1-yl group, a 2-methylpropane-2-yl group, a pentan-1-yl group, a pentan-2-yl group, a 2-methylbutane-1-yl group, a hexane-1-yl group, a 2-methylpentane-1-yl group, a 3-methylpentane-1-yl group, a heptan-1-yl group, a 3-ethylpentane-1-yl group, a 2-methylhexane-yl group, a 3-methylhexane-yl group, an octan-1-yl group, a 2-methylheptane-1-yl group, a 3-methylheptane-1-yl group, a 4-methylheptane-1-yl group, a 2-ethylhexane-1-yl group, a 3-ethyl Examples of such an alkyl group include 1-ethylhexan-1-yl group, 1,1,3,3-tetramethylbutylnonan-1-yl group, 3-ethylheptan-1-yl group, 4-ethylheptan-1-yl group, 2-methyloctan-1-yl group, 3-methyloctan-1-yl group, 4-methyloctan-1-yl group, decan-1-yl group, 4-propylheptan-1-yl group, 3-ethyloctan-1-yl group, 4-ethyloctan-1-yl group, undecane-1-yl group, dodecane-1-yl group, 2-methylundecane-1-yl group, 2-ethyldecane-1-yl group, tridecane-1-yl group, tetradecane-1-yl group, pentadecane-1-yl group, hexadecan-1-yl group, heptadecan-1-yl group, and octadecane-1-yl group. Among these, linear or branched alkyl groups having 1 to 8 carbon atoms are preferred, and linear or branched alkyl groups having 1 to 4 carbon atoms are more preferred.

Specific examples of the substituents include those exemplified in the [Substituents, etc.] column.

In formula (I), when ^R9 at the 5-position has a monovalent sulfur-containing group represented by formula (i-1), it is preferable that ^R6 , ^R7 , and ^R8 , which are groups other than the monovalent sulfur-containing group represented by formula (i-1), are all hydrogen atoms. In addition, preferred examples of combinations of ^R1 , ^R2 , ^R3 , ^R4 , and ^R5 are as follows.

[1] Contains one or more substituents selected from a hydrocarbon group having 1 to 18 carbon atoms (including a hydrocarbon group having 2 to 18 carbon atoms, including an alkenyl group and an alkynyl group), a hydroxy group, an aromatic group having 6 to 18 carbon atoms, an ether group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an ester group having 1 to 18 carbon atoms, a (meth)acryloyloxy group, and/or a polyoxyethylene group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms in which a hydrogen atom may be substituted, the base end may be interrupted, or the carbon-carbon bond may be interrupted by such a substituent.
[2] In the above [1], the substituent is at least one selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydroxy group.
[3] In the above [2], the substituent is at least one selected from a hydrocarbon group having 1 to 8 carbon atoms and a hydroxy group.
[4] In any one of [1] to [3], the hydrocarbon group of the substituent is a linear or branched alkyl group.
[5] In the above [4], the substituent is at least one selected from a methyl group, a t-butyl group, and a hydroxy group.
[6] In the formula [5], the substituent is at least one selected from a methyl group, a t-butyl group, and a hydroxy group, and the number of hydroxy groups is one or less.
[7] In any one of [1] to [6], the number of substituents is 2 to 4.
[8] In any one of [1] to [7], R ¹ to R ⁴ have a substituent, and the remaining R ¹ to R ⁵ are hydrogen atoms.
[9] In any one of [1] to [8], R ¹ , R ² and R ⁴ have a substituent, and the remaining R ¹ to R ⁵ are hydrogen atoms.
[10] In [9], R ¹ is a hydroxy group, R ² is a t-butyl group, R ⁴ is a methyl group, and R ³ and R ⁵ are hydrogen atoms.

Monomer (A) has a structure in which a sulfur-containing group is bonded to a benzotriazole skeleton, and therefore, due to its ultraviolet absorbing properties, it is possible to sharply cut ultraviolet rays in the vicinity of 360 to 420 nm while suppressing absorption in the 430 to 500 nm (visible range). Therefore, the copolymer of the present invention and the resin member using the copolymer have suppressed yellow coloring, excellent appearance, and can sufficiently absorb light in the wavelength range of 250 to 420 nm. In order to efficiently absorb wavelengths of 360 to 420 nm, the maximum absorption wavelength of light of the copolymer is preferably 350 to 390 nm, more preferably 360 to 380 nm, and particularly preferably 360 to 375 nm. In terms of the yellow suppression effect, it is preferable that the slope on the long wavelength side of the absorption peak in the wavelength range of 330 to 390 nm is sharp. For example, when the copolymer concentration (solid content) is 0.04 mass% when monomer (A)/monomer (B) = 1, the slope is preferably 0.015 or more, more preferably 0.02 or more.

The method for producing the benzotriazole compound represented by formula (I) is not particularly limited, but the disclosure of the examples below and known techniques may be referred to.

(Monomer (B))
Monomer (B) is an ester group-containing vinyl monomer.
The ester group-containing vinyl monomer is represented by R ^A1 R ^A2 C═CR ^A3 R ^A4 , and at least one of R ^A1 to R ^A4 , preferably one, is an ester group. Of R ^A1 to R ^A4 , other than the ester group-containing group, each is any group selected from a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms. The hydrocarbon group is preferably an alkyl group, and other than the ester group-containing group, a hydrogen atom or a group having 1 to 4 carbon atoms is preferable, and a hydrogen atom or a group having 1 carbon atom is more preferable.

Examples of ester group-containing vinyl monomers include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, and octadecyl (meth)acrylate. Considering affinity with water, the number of carbon atoms in the alkyl portion of the ester group is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 8, and particularly preferably 1 to 4. For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, and t-butyl (meth)acrylate are preferred.

Monomer (B) imparts to the copolymer of the present invention high affinity with organic solvents and resins, as well as excellent strength and light resistance at high temperatures.

In addition to the monomers (A) and (B), other monomers can be used in the copolymer of the present invention. Such monomers include, but are not limited to, styrene-based monomers, acrylamide-based monomers, olefin-based monomers, and vinyl-based monomers.

Examples of styrene-based monomers include, but are not limited to, alkyl styrenes such as styrene, α-methylstyrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, isopropylstyrene, butylstyrene, isobutylstyrene, t-butylstyrene, s-butylstyrene, pentylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; halogenated styrenes such as chlorostyrene, fluorostyrene, bromostyrene, dibromostyrene, and iodostyrene; alkoxy styrenes such as p-methoxystyrene; aryl styrenes such as p-phenylstyrene; styrenesulfonic acid or a salt thereof, nitrostyrene, aminostyrene, hydroxystyrene, and 4-(trimethoxysilyl)styrene.

Examples of acrylamide monomers include, but are not limited to, (meth)acrylamide, N,N-dimethylacrylamide, (meth)N,N-diethylacrylamide, (meth)N,N-dipropylacrylamide, (meth)N,N-diisopropylacrylamide, (meth)acryloylmorpholine, diacetone (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N,N-bishydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N,N-bishydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, N,N-bishydroxypropyl (meth)acrylamide, N-hydroxybutyl (meth)acrylamide, and the like.

The olefin monomer is not particularly limited, but examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-phenyl-1-butene, 6-phenyl-1-hexene, 3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 3 , 3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclohexane, hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene, 3,4-dichloro-1-butene, butadiene, hexadiene, isoprene, dicyclopentadiene, norbornene, acetylene, etc.

Examples of vinyl monomers include, but are not limited to, vinyl acetate, vinyl propionate, vinyl alcohol, allyl alcohol, (meth)acrylonitrile, methacrylonitrile, N-vinylpyrrolidone, vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, vinylidene bromide, vinylidene iodide, vinyl sulfonic acid and its salts, methallylsulfonic acid and its salts, 2-acrylamido-2-methylsulfonic acid and its salts, N-vinyl-2-pyrrolidone, (meth)acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, cinnamic acid, myristoleic acid, palmitoleic acid, oleic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, citraconic acid, citraconic acid monoester, etc.

(Copolymer)
The copolymer of the present invention will now be described.
The copolymer of the present invention is a copolymer of monomer components including monomer (A) and monomer (B).

The copolymer of the present invention is a copolymer in which the monomer component is polymerized with a vinyl group or an alkynyl group. Therefore, it has a structure in which constituent units derived from each type of monomer, that is, repeating units, are bonded. Specifically, it has a main chain in which the vinyl group or ethynyl group of each type of monomer is polymerized, and groups possessed by these monomers, such as the ultraviolet absorbing group of monomer (A) and functional groups and side chains of monomer (B), etc. The copolymer is not particularly limited, and can be a random copolymer, a block copolymer, or a graft copolymer. Typically, it is a random copolymer in which each type of monomer is randomly polymerized.

The method for producing the copolymer of the present invention is shown below and is not particularly limited. For example, the method includes solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc., and the solution polymerization method is preferred.

In the copolymer of the present invention, in terms of affinity with organic solvents and ultraviolet absorbing ability, the molar ratio (A)/(B) of monomers (A) and (B) in the composition of the monomer components of the copolymer is preferably greater than 0.01, more preferably greater than 0.02, even more preferably greater than 0.03, and particularly preferably greater than 0.04.

When the molar ratio (A)/(B) of the monomers (A) and (B) is less than 0.03, the transparency of the copolymer is increased, and the viscosity of the composition containing an organic solvent is decreased, improving the handling, while the hydrophilicity of the composition containing the copolymer and water is increased, improving the dispersion and solubility.
In the copolymer of the present invention, the total molar ratio of monomers (A) and (B) is not particularly limited, but may be 90 mol % or more, 80 mol % or more, or 50 mol % or more based on the total monomers.

(Composition containing copolymer and organic solvent)
The composition containing the copolymer of the present invention and an organic solvent is a solution, dispersion or emulsion composition containing the copolymer of the present invention and an organic solvent. The copolymer of the present invention has high affinity to the organic solvent, and can be made into a solution or dispersion composition in particular. The production method is shown below, but is not particularly limited, and examples thereof include solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization, and solution polymerization is preferred.

The polymerization method is not particularly limited, but for example, a polymerization initiator is added to a solution of a monomer and an organic solvent, and polymerization is carried out to obtain a composition.

The organic solvent used in the composition of the present invention is not particularly limited, but examples thereof include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ketone solvents, ester solvents, glycol ether solvents, glycol ether ester solvents, terpene solvents, alcohol solvents, fluorine solvents, amide solvents, sulfur solvents, and ether solvents.

Examples of aromatic hydrocarbon solvents include, but are not limited to, toluene, xylene, benzene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, methylnaphthalene, etc. Examples of aliphatic hydrocarbon solvents include, but are not limited to, hexane, heptane, cyclohexane, etc. Examples of ketone solvents include, but are not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Examples of ester solvents include, but are not limited to, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, γ-butyrolactone, etc. Examples of glycol ether solvents include, but are not limited to, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ... Examples of glycol ether ester solvents include, but are not limited to, ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl acetate, ethylene glycol mono n-butyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono n-propyl ether acetate, propylene glycol mono n-butyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol mono n-propyl ether acetate, dipropylene glycol mono n-butyl ether acetate, and the like. Examples of the terpene solvent include, but are not limited to, terpineol, dihydroterpineol, terpinyl acetate, dihydroterpinyl acetate, etc. Examples of the alcohol solvent include, but are not limited to, methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutanol, t-butanol, etc. Examples of the fluorocarbon solvent include, but are not limited to, fluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, and examples of the fluoroalcohols include, but are not limited to, Examples of fluoroethers include, but are not limited to, 2,2,3,3-tetrafluoro-1-propanol (TFP), 2,2,3,3,4,4,5,5-octafluoro-1-pentanol (OFP), 2-(perfluorooctyl)ethanol, 1,1,2,2-tetrahydroheptadecafluorodecanol, 1,1,2,2-tetrahydroperfluorodecanol, and 2-(heptadecafluorooctyl)ethanol. Furthermore, examples of fluoroethers include, but are not limited to, hydrofluoroethers (e.g., ethyl nonafluorobutyl ether (C ₄ F ₉ OC ₂ H ₅ ), methyl nonafluorobutyl ether (C ₄ F ₉ OCH ₃ ), methyl tridecafluorohexyl ether (C ₆ F ₁₃ OCH ₃ ), and C ₃ HF ₆ —CH(CH ₃ )O—C ₃ HF ₆ ).

Amide-based solvents include, but are not limited to, dimethylformamide, diethylformamide, dimethylacetamide, N-methylpyrrolidone, tetramethylurea, hexamethylphosphoric acid triamide, etc.

Sulfur-based solvents include, but are not limited to, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfide, diethyl sulfide, dimethyl disulfide, diethyl disulfide, etc.

Ether solvents include, but are not limited to, diethyl ether, diisopropyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, methyl-tert-butyl ether, 1,4-dioxane, 1,3-dioxolane, cyclopentyl methyl ether, etc.

These organic solvents may be used in combination of two or more kinds. In view of the affinity with the copolymer of the present invention and industrial advantages, aromatic hydrocarbon solvents, hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, sulfur solvents, ether solvents, and mixed solvents of two or more kinds thereof are preferred. Among these, aromatic hydrocarbon solvents, mixed solvents of two or more kinds including aromatic hydrocarbon solvents, and ketone solvents are more preferred, aromatic hydrocarbon solvents, mixed solvents of two or more kinds including aromatic hydrocarbon solvents are even more preferred, and aromatic hydrocarbon solvents are particularly preferred.

In the composition containing the organic solvent of the present invention, the content (solid content) of the copolymer of the present invention is preferably 60 mass% or less, more preferably 50 mass% or less, and even more preferably 40 mass% or less, in consideration of affinity with the organic solvent.
(Aqueous Composition)

The aqueous composition of the present invention is an aqueous composition of a dispersion containing the copolymer of the present invention, water, and a surfactant. The method for producing the aqueous composition of the present invention is shown below and is not particularly limited, but examples thereof include a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, and a suspension polymerization method, with the emulsion polymerization method and the suspension polymerization method being preferred, and the emulsion polymerization method being more preferred.

The polymerization method is not particularly limited, but for example, an emulsion is made with a monomer, a surfactant, and water, and a polymerization initiator is added and polymerized to obtain an aqueous composition.

The surfactant contained in the aqueous composition of the present invention is not particularly limited, and a general surfactant can be used. The surfactant can be appropriately selected from cationic surfactants, anionic surfactants, nonionic surfactants, zwitterionic surfactants, and silicone-based surfactants, and among these, cationic surfactants and anionic surfactants are preferred. These surfactants may be used alone or in combination of two or more.

Examples of cationic surfactants include, but are not limited to, monoalkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylpyridinium salts, N,N-dialkyloyloxyethyl-N-methyl, N-hydroxyethylammonium salts, alkylamine salts, stearyldimethylbenzylammonium salts, etc. Examples of monoalkyltrimethylammonium salts include, but are not limited to, butyltrimethylammonium chloride, hexyltrimethylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, stearyltrimethylammonium chloride, butyltrimethylammonium chloride, hexyltrimethylammonium bromide, octyltrimethylammonium bromide, decyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, stearyltrimethylammonium bromide, etc. Examples of dialkyl dimethyl ammonium salts include, but are not limited to, dibutyl dimethyl ammonium chloride, dihexyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, ditetradecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dibutyl dimethyl ammonium chloride, dihexyl dimethyl ammonium bromide, dioctyl dimethyl ammonium bromide, didecyl dimethyl ammonium bromide, didodecyl dimethyl ammonium bromide, ditetradecyl dimethyl ammonium bromide, dihexadecyl dimethyl ammonium bromide, distearyl dimethyl ammonium bromide, etc. Examples of alkyl pyridinium salts include, but are not limited to, 1-hexadecyl pyridinium chloride, etc.

Examples of anionic surfactants include, but are not limited to, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfonates, α-olefinsulfonates, alkyl sulfates, alkyl sulfate ester salts, alkyl ether phosphates, N-acylamino acid salts, alkylarylsulfonates, alkyl ether sulfates, alkylamide sulfates, alkyl phosphates, alkylphosphonic acids or salts thereof, alkylamide phosphates, alkylylalkyl taurine salts, fatty acid salts, polyoxyethylene alkyl ether acetates, sodium coconut oil fatty acid methyl taurine, polyoxyethylene alkyl ether sulfates, phosphate ester salts, polyoxyethylene alkyl ether phosphates, dialkyl sulfosuccinates, perfluoroalkyl phosphate esters, N-acyl-L-glutamates, and N-acyl-L-ethyl arginine DL-pyrrolidone carboxylates. Specific examples include, but are not limited to, sodium deoxycholate, sodium dodecyl sulfate, sodium laureth sulfate, sodium myristyl sulfate, sodium cetyl sulfate, sodium oleyl sulfate, sodium dodecylbenzenesulfonate, sodium 1,2-dihydroxypropanesulfonate, sodium polyoxyethylene lauryl ether acetate, sodium N-coconut oil fatty acid acyl glutamate, etc.

Nonionic surfactants include, but are not limited to, polyglycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, polyoxyethylene lanolin, lanolin alcohol, beeswax derivatives, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sterol, hydrogenated sterol, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyethylene glycol fatty acid esters, polyoxyethylene glyceryl isostearate, sorbitan fatty acid esters, glycerin fatty acid esters, diglycerin fatty acid esters, polyglycerin fatty acid esters, etc.

Examples of polyglycerol fatty acid esters include, but are not limited to, hexaglyceryl monolaurate (HLB 14.5), hexaglyceryl monomyristate (HLB 11), hexaglyceryl monostearate (HLB 9.0), hexaglyceryl monooleate (HLB 9.0), decaglyceryl monolaurate (HLB 15.5), decaglyceryl monomyristate (HLB 14.0), decaglyceryl monostearate (HLB 12.0), decaglyceryl monoisostearate (HLB 12.0), decaglyceryl monooleate (HLB 12.0), decaglyceryl distearate (HLB 9.5), decaglyceryl diisostearate (HLB 10.0), decaglyceryl pentaisostearate (HLB 3.5), decaglyceryl pentaoleate (HLB 3.5), etc.

The polyoxyethylene sorbitan fatty acid esters are not particularly limited, but examples thereof include polyoxyethylene glycerin fatty acid esters such as polyoxyethylene monostearate (hereinafter abbreviated as POE) (5) glyceryl (HLB 9.5), POE (15) monostearate (HLB 13.5), POE (5) glyceryl monooleate (HLB 9.5), POE (15) monooleate (HLB 14.5), etc.; monococonut oil fatty acid POE (20) sorbitan (HLB 16.9), monopalmitic acid POE (20) sorbitan (HLB 16.9), etc. Examples include POE(20) sorbitan monostearate (HLB 15.6), POE(20) sorbitan monostearate (HLB 14.9), POE(6) sorbitan monostearate (HLB 9.5), POE(20) sorbitan tristearate (HLB 10.5), POE(20) sorbitan monoisostearate (HLB 15.0), POE(20) sorbitan monooleate (HLB 15.0), POE(6) sorbitan monooleate (HLB 10.0), and POE(20) sorbitan trioleate (HLB 11.0).

Examples of polyoxyethylene sorbitol fatty acid esters include, but are not limited to, POE(6) sorbitol monolaurate (HLB 15.5), POE(60) sorbitol tetrastearate (HLB 13.0), POE(30) sorbitol tetraoleate (HLB 11.5), POE(40) sorbitol tetraoleate (HLB 12.5), POE(60) sorbitol tetraoleate (HLB 14.0), POE(6) sorbitol tetraoleate (HLB 8.5), and POE(6) sorbitol hexastearate (HLB 3.0).

Polyoxyethylene lanolin, lanolin alcohol, and beeswax derivatives include, but are not limited to, POE(10) lanolin (HLB 12.0), POE(20) lanolin (HLB 13.0), POE(30) lanolin (HLB 15.0), POE(5) lanolin alcohol (HLB 12.5), POE(10) lanolin alcohol (HLB 15.5), POE(20) lanolin alcohol (HLB 16.0), POE(40) lanolin alcohol (HLB 17.0), POE(20) sorbitol beeswax (HLB 9.5), and POE(6) sorbitol beeswax (HLB 7.5).

Polyoxyethylene castor oils and hydrogenated castor oils are not particularly limited, but examples include POE (20) castor oil (HLB 10.5), POE (40) castor oil (HLB 12.5), POE (50) castor oil (HLB 14.0), POE (60) castor oil (HLB 14.0), POE (20) hydrogenated castor oil (HLB 10.5), POE (30) hydrogenated castor oil (HLB 11.0), POE (40) hydrogenated castor oil (HLB 13.5), POE (60) hydrogenated castor oil (HLB 14.0), POE (80) hydrogenated castor oil (HLB 16.5), POE (40) hydrogenated castor oil (100) hydrogenated castor oil (HLB 16.5), POE (3) castor oil (HLB 3.0), etc.

Polyoxyethylene sterols and hydrogenated sterols are not particularly limited, but examples include POE(5) phytosterol (HLB 9.5), POE(10) phytosterol (HLB 12.5), POE(20) phytosterol (HLB 15.5), POE(30) phytosterol (HLB 18.0), POE(25) phytostanol (HLB 14.5), POE(30) cholestanol (HLB 17.0), etc.

Polyoxyethylene alkyl ethers are not particularly limited, but examples thereof include POE (2) lauryl ether (HLB 9.5), POE (4.2) lauryl ether (HLB 11.5), POE (9) lauryl ether (HLB 14.5), POE (5.5) cetyl ether (HLB 10.5), POE (7) cetyl ether (HLB 11.5), POE (10) cetyl ether (HLB 13.5), and P OE(15) cetyl ether (HLB 15.5), POE(20) cetyl ether (HLB 17.0), POE(23) cetyl ether (HLB 18.0), POE(4) stearyl ether (HLB 9.0), POE(20) stearyl ether (HLB 18.0), POE(7) oleyl ether (HLB 10.5), POE(10) oleyl ether (HLB 14.5), POE(15) oleyl ether POE(2)(C12-15) alkyl ether (HLB 9.0), POE(4)(C12-15) alkyl ether (HLB 16.0), POE(20) oleyl ether (HLB 17.0), POE(50) oleyl ether (HLB 18.0), POE(10) behenyl ether (HLB 10.0), POE(20) behenyl ether (HLB 16.5), POE(30) behenyl ether (HLB 18.0), POE(2)(C12-15) alkyl ether (HLB 9.0), POE(4)(C12-15) alkyl ether (HLB 16.0), POE(5) behenyl ...5) behenyl ether (HLB 16.0), POE(5) behenyl ether (HLB 16.0), POE(5) behenyl ether (HLB 16.0), POE(5) behenyl ether (HLB 16.0), POE(5) behenyl ether (HLB 16.0), POE(5) behenyl alkyl ether (HLB 10.5), POE(10) (C12-15) alkyl ether (HLB 15.5), POE(5) secondary alkyl ether (HLB 10.5), POE(7) secondary alkyl ether (HLB 12.0), POE(9) alkyl ether (HLB 13.5), POE(12) alkyl ether (HLB 14.5), POE(2) stearyl ether (HLB 4.0), etc.

Polyoxyethylene polyoxypropylene alkyl ethers include, but are not limited to, polyoxyethylene (hereinafter abbreviated as POE) (1) polyoxypropylene (hereinafter abbreviated as POP) (4) cetyl ether (HLB 9.5), POE (10) POP (4) cetyl ether (HLB 10.5), POE (20) POP (8) cetyl ether (HLB 12.5), POE (20) POP (6) decyl tetradecyl ether (HLB 11.0), POE (30) POP (6) decyl tetradecyl ether (HLB 12.0), etc.

The polyethylene propylene glycol fatty acid esters are not particularly limited, but examples thereof include polyethylene glycol monolaurate (hereinafter abbreviated as PEG) (10) (HLB 12.5), PEG monostearate (10) (HLB 11.0), PEG monostearate (25) (HLB 15.0), PEG monostearate (40) (HLB 17.5), PEG monostearate (45) (HLB 18.0), and monostearate. Examples include PEG monooleate (55) (HLB 18.0), PEG monooleate (10) (HLB 11.0), PEG distearate (HLB 16.5), PEG diisostearate (HLB 9.5), PEG monostearate (2) (HLB 4.0), PEG stearate (2) (HLB 4.5), ethylene glycol monostearate (HLB 3.5), and self-emulsifying propylene glycol monostearate (HLB 4.0).

Examples of polyoxyethylene glyceryl isostearate include, but are not limited to, PEG (8) glyceryl isostearate (HLB 10.0), PEG (10) glyceryl isostearate (HLB 10.0), PEG (15) glyceryl isostearate (HLB 12.0), PEG (20) glyceryl isostearate (HLB 13.0), PEG (25) glyceryl isostearate (HLB 14.0), PEG glyceryl (30) isostearate (HLB 15.0), PEG (40) glyceryl isostearate (HLB 15.0), PEG (50) glyceryl isostearate (HLB 16.0), and PEG (60) glyceryl isostearate (HLB 16.0).

Sorbitan fatty acid esters include, but are not limited to, sorbitan tristearate (HLB 2.0), sorbitan sesquiisostearate (HLB 4.5), sorbitan monostearate (HLB 4.7), sorbitan monoisostearate (HLB 5.0), sorbitan monooleate (HLB 4.3), etc.

Glycerol fatty acid esters include, but are not limited to, glyceryl myristate (HLB 3.5), glyceryl monostearate (HLB 4.0), glyceryl monooleate (HLB 2.5), hexaglyceryl tristearate (HLB 2.5), self-emulsifying glyceryl monostearate (HLB 4.0), glyceryl monoisostearate (HLB 4.0), decaglyceryl pentastearate (HLB 3.5), etc.

Diglycerin fatty acid esters include, but are not limited to, diglyceryl monooleate (HLB 5.5), for example. Other examples include polyoxyethylene fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, castor oil fatty acid esters, hydrogenated castor oil fatty acid esters, ethylene glycol fatty acid esters, sucrose fatty acid esters, organic acid monoglycerides, polyethylene glycol fatty acid monoethanolamides, polyoxyethylene lanolin alcohol ethers, polyoxyethylene alkyl ethers, lauric acid alkanolamides, polyoxyethylene glycerin fatty acid esters, polyoxyethylene hydrogenated castor oil pyroglutamic acid fatty acid diesters, pyroglutamic acid fatty acid glyceryl, polyoxyethylene glyceryl pyroglutamic acid fatty acid diesters, polyether modified silicones, etc.

Examples of amphoteric surfactants include, but are not limited to, alkyl betaines, fatty acid amidopropyl betaines, lauryl hydroxysulfobetaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lecithin, hydrogenated lecithin, alkyloxyhydroxypropyl arginine hydrochloride, lauryl hydroxysultaine, lauriminodipropionic acid, sodium undecylhydroxyethyl imidazolinium betaine, sodium laurylaminodiacetate, lauryl dimethylaminoacetate betaine, N-[3-alkyloxy-2-hydroxypropyl]-L-arginine hydrochloride, alkyl hydroxysulfobetaines, alkyl dimethylamine oxides, sodium alkylaminodipropionate, dihydroxyalkylmethylglycine, sodium lauryldiaminoethylglycine, etc.

Silicone surfactants are not particularly limited, but examples include PEG-10 dimethicone, PEG/PPG-20/20 dimethicone, polysilicone-13, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, etc.

From the viewpoint of the stability of the dispersion liquid, cationic surfactants and anionic surfactants are preferred among the above surfactants.

If an organic solvent is used, the ones listed above can be used.

In the aqueous composition of the present invention, the content (solid content) of the copolymer of the present invention is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, taking into consideration the stability of the dispersion.

From the viewpoint of the stability of the dispersion of the aqueous composition, the molar ratio (A)/(B) of the monomers (A) and (B) in the composition of the monomer components of the copolymer is preferably less than 0.10, more preferably less than 0.05, even more preferably less than 0.03, and particularly preferably 0.02 or less. From the viewpoint of ultraviolet absorption capacity, (A)/(B) is preferably 0.005 or more, more preferably 0.01 or more, and even more preferably 0.02 or more. From the viewpoint of both stability and ultraviolet absorption capacity, (A)/(B) is more preferably 0.005 or more and less than 0.05, even more preferably 0.005 or more and less than 0.03, and particularly preferably 0.005 or more and less than 0.02.

(Application)
The copolymer of the present invention described above efficiently absorbs ultraviolet light with a long wavelength of 360 to 420 nm, and therefore can be used in various fields, and is particularly suitable for use in applications where there is a possibility of exposure to sunlight or light containing ultraviolet light. Examples of the copolymer include glass substitutes, coating agents and protective agents for glass such as window glass, lighting glass and light source protection glass, light source members that emit ultraviolet light such as fluorescent lamps and mercury lamps, containers or packaging materials for food and medicine, agricultural and industrial sheets, anti-fading agents for printed matter, dyed matter, dyes and pigments, display boards, indicator lights, cards, etc.

The copolymer and composition of the present invention can be used in particular in optical materials and coating agents that form optical layers, since they can impart ultraviolet absorption ability and a high refractive index while maintaining the transparency of the matrix. For example, they are suitable for functional optical layers, films and components that have optical layers, and optical molded products.

Films or members having a functional optical layer may be single-layer films, or multi-layer films or substrates with optical layers in which one or more optical layers are provided on a base film or substrate according to various applications. When multiple optical layers are provided, the polymer of the present invention is used in at least one of the layers.

Of the films and components having functional optical layers, optical films may be those in which a functional layer is provided on a base film according to various applications, and are not particularly limited. Examples include, but are not limited to, various optical disk substrate protective films, reflective films, anti-reflective films, alignment films, polarizing films, polarizing layer protective films, retardation films, light diffusion films, viewing angle improving films, electromagnetic wave shielding films, anti-glare films, light shielding films, and brightness improving films.

Examples of components having a functional optical layer include components in which at least one of an anti-reflection layer, a hard coat layer, an antistatic layer, an adhesion stabilizing layer, a protective layer, an electromagnetic wave shielding layer, an infrared cut layer, etc. is laminated in one or multiple layers on the surface of a panel substrate, etc.

The copolymer of the present invention is also suitable for a surface protective film for solar cells. A solar cell element is usually configured with an active layer that functions as a solar cell between a pair of substrates. Flexible solar cells require a protective film that absorbs ultraviolet light because polyester materials such as gas barrier films used as components of the solar cell, and the active layer itself in organic solar cells, absorb ultraviolet light and deteriorate. In addition, solar cells are installed outdoors for many years, so such protective films are required to have high weather resistance. Furthermore, solar cells absorb light energy and convert it into electricity, so such protective films are required to have high transparency. In other words, protective films for protecting flexible solar cells are required to have high transparency, high ultraviolet absorption ability, high weather resistance, and flexibility, and the copolymer of the present invention is suitable for such applications.

The copolymer and composition of the present invention can be suitably used for optical lenses such as plastic lens elements for spectacles, contact lenses, optical pickup lenses, camera lenses, and lenticular lenses, prisms, filters, optical substrates such as touch panel substrates and light guide plates, optical layers of optical fibers, information recording substrates, and optical molded products. As optical lenses, they are also suitable for plastic lenses such as lens films such as Fresnel lens films and lenticular lens films, and microlens arrays using microlenses with a diameter of several μm, which are used for the purpose of increasing the light collecting and light diffusing properties of miniaturized optical functional elements and for the purpose of collecting light on the light receiving elements of image sensors. They are also suitable as coating agents for forming optical layers for the above-mentioned applications.

The copolymers and compositions of the present invention are also suitable for use as display substrates, for example, substrates for flat panel displays such as liquid crystal displays, organic EL displays, plasma displays, field emission displays, and electronic paper, or substrates for backlights such as liquid crystal displays, traffic signals, and neon signs.

The copolymers and compositions of the present invention have excellent ultraviolet absorbing properties and can be used in fields where stabilization and functionality are required due to ultraviolet absorbing properties, including, but not limited to, dyes, pigments, dyes, inks, paints, pharmaceuticals, surface coatings, cosmetics, perfumes, photographic materials, textiles, etc.

In the above applications, the copolymer and composition of the present application have high affinity to organic solvents, for example, high affinity to resins, while the aqueous composition of the present application has high stability in the state of an aqueous dispersion without using organic solvents, has low environmental load, is highly safe for humans, and is highly useful. In addition, it has high strength at high temperatures, and is suitable for use at high temperatures in the above applications, and also has high light resistance and excellent stability when exposed to light for long periods of time.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
1. Monomers Copolymers were synthesized using the following monomers.
Monomer A1 was synthesized by the method described in International Publication No. 2019/087983. Monomers A2 and A3 were synthesized by the method described below. For each monomer in Tables 1 to 4, Tokyo Chemical Industry Co., Ltd.'s reagents methyl methacrylate and 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole were used.
Monomer (A)

<Monomer A2>
2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (50 g, 0.16 mol), 3-mercapto-1-propanol (22 g, 0.24 mol), and potassium carbonate (48 g, 0.35 mol) were heated and stirred in 125 g of DMF for 12 hours. After the reaction was completed, ion-exchanged water was added, and the mixture was filtered and purified to obtain intermediate 1 as a yellow solid.

The obtained intermediate 1 (59 g, 0.16 mol), pyridine (16 g, 0.21 mol) and acrylic acid chloride (17 g, 0.19 mol) were reacted in 100 g of toluene at room temperature for 3 hours. After the reaction was completed, the product was purified to synthesize Monomer A2 as a pale yellow solid.
FT-IR (KBr): 2956cm ^-1 : O-H stretching vibration 1726cm ^-1 : C=O stretching vibration 1485, 1392cm ^-1 : Triazole ring stretching vibration
^1H -NMR ( _CDCl3 400MHz): δ 1.49 (s, 9H, -Ph-OH- _{CH3 -} C( CH3 ) ₃ ), 2.11 (quin, 2H, -O- _CH2CH2CH2- S-), 2.39 (s _, 3H, -Ph-OH- CH3 _- C( _CH3 ) ₃ ), 3.13 (t _, 2H , -O _- CH2CH2CH2-S-), 4.32 (t , 2H, _{-OCH2CH2CH2 -} S-), 5.85 ₍ d, 1H, CH2 =CH _- C(=O)-O-), 6.14 ₍ quin, 1H, _CH2 =CH-C(=O)-O-), 6.42 ₍ d, 1H, CH2 =CH- C (=O ) -O- _). =CH-C(=O)-O-), 7.17 (s, 1H), 7.40 (d, 1H), 7.76 (s, 1H), 7.82 (d, 1H), 8.05 (s, 1H), (insg.5arom. C H ), 11.58 (s, 1H, -Ph-OH -CH ₃ -C(CH ₃ ) ₃ )
^13C -NMR ( _CDCl3 400MHz): δ 20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 28.0 (-Ph-OH-CH ₃ -C (CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( C H ₃ ) ₃ ), 29.9 (-O-CH ₂ C H ₂ CH ₂ -S), 35.4 (-O-CH ₂ CH ₂ C H ₂ -S), 62.8 (-O- C H ₂ CH ₂ CH ₂ -S), 114.6, 117.8, 119.3, 128.9, 129.4 ( C H _arom ), 125.4, 141.4, 143.3 ( C _arom ), 128.3 ( C _arom - C H ₃ ), 136.8 ( Carbon _-S ), 139.2 ( Carbon _-C ( _CH3 ) ₃ ), 146.7( Carbon _-OH ), 128.3 ( C _H2 =CH-C(=O)-O-), 131.1 ( _CH2 = CH -C(=O)-O-), 166.1 ( _CH2 =CH- C (=O)-O-)

<Monomer A3>
2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (5.6 g, 18 mmol), 4-hydroxybenzenethiol (2.9 g, 23 mmol), and potassium carbonate (5.4 g, 39 mmol) were heated and stirred in 17 g of DMF for 8 hours. After the reaction was completed, ion-exchanged water was added to precipitate crystals, which were then filtered and purified to obtain intermediate 2 as a yellow solid.

The obtained intermediate 2 (7.2 g, 18 mmol), pyridine (1.8 g, 23 mmol) and acrylic acid chloride (1.9 g, 21 mmol) were reacted in 20 g of toluene at room temperature for 3 hours. After the reaction was completed, the product was purified to synthesize Monomer A3 as a pale yellow solid.
FT-IR (KBr): 2959cm ^-1 : O-H stretching vibration 1747cm ^-1 : C=O stretching vibration 1487, 1403cm ^-1 : Triazole ring stretching vibration
^1H -NMR ( _CDCl3 400MHz): δ 1.48 (s, 9H, -Ph-OH- _{CH3 -} C( CH3 ) ₃ ), 2.37 (s, 3H, -Ph-OH- CH3 -C( _CH3 ) ₃ ), _6.04 (d, 1H, CH2 ₌ CH-C(=O)-O-), 6.34 (quin, 1H, _CH2 =CH- C (=O)-O- _{), 6.61 (d, 1H, CH2} = CH-C(=O)-O-), 7.17-7.19 (m, 3H), 7.35 (d, 1H), 7.50 (d, 2H), 7.71 (s, 1H), 7.82 (d, 1H), 8.04 (s, 1H), (insg.9arom. CH), 11.55 (s, 1H, -Ph-OH- CH3 _- C( _CH3 ) ₃ )
^13C -NMR ( _CDCl3 400MHz): δ 20.9 (-Ph- OH - _CH3 -C( _CH3 ) ₃ ), 29.5 (-Ph-OH- _CH3 - C ( _CH3 ) ₃ ), 29.5 (-Ph-OH- _CH3 -C( CH3 _{) 3} ),
116.9, 118.1, 119.4, 129.0, 129.7, 125.3, 133.9 ( C H _arom ), 125.3, 141.7, 143.2 ( C _arom ), 128.2 ( C _{arom -CH3} ), 128.9 ( C _arom -S), 137.1 ( C _arom -S), 139.2 ( C _arom -C( _CH3 ) ₃ ), 150.7( C _arom -O-), 146.7( C _arom -OH), 128.3 ( C _H2 =CH-C(=O)-O-), 131.0 ( _CH2 = CH -C(=O)-O-), 164.2 ( _CH2 =CH- C (=O)-O-)

Monomer (B)
Monomer B: Methyl methacrylate

Monomer (C)
Monomer C: 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole

2. Synthesis of copolymers and copolymer compositions <Copolymer 1>
Monomer A1 (20 g, 42 mmol), methyl methacrylate (4.2 g, 42 mmol), and methyl ethyl ketone: MEK (36 g) were mixed and substituted with nitrogen. Then, 1,1′-azobis(cyclohexane-1-carbonitrile) (0.2 g, 1 mmol) was added as a polymerization initiator, and the mixture was heated and stirred at 70 to 76° C. for 6 hours to carry out a copolymerization reaction, thereby obtaining a composition of Copolymer 1 consisting of Monomer A1 and Monomer B.

<Copolymers 2 to 15, 22 to 32>
In the same manner as in the synthesis of the copolymer 1, the monomers A1 to A3, B, and C corresponding to Tables 1, 2, and 4, respectively, were copolymerized in the respective molar ratios and amounts of the organic solvent, to obtain copolymer compositions 2 to 15 and 22 to 32.

<Copolymer 16>
Monomer A1 (10 g, 21 mmol), Monomer B (90 g, 899 mmol), anionic surfactant: sodium dodecyl sulfate (6 g, 21 mmol), and ion-exchanged water (150 g) were mixed and emulsified using a homogenizer at 1200 rpm for 45 minutes. After nitrogen replacement, potassium persulfate (0.4 g, 1.5 mmol) was added to the emulsion as a polymerization initiator, and the mixture was heated and stirred at 80° C. for 3 hours to polymerize, thereby obtaining an aqueous composition of copolymer 16.

<Copolymers 17 to 21>
In the same manner as in the synthesis of Copolymer 16, copolymerization reactions were carried out using the molar ratios of Monomers A1 to A3, Monomer B, and surfactant corresponding to those in Table 3, to obtain Copolymer Compositions 17 to 21.

In all the copolymers, ¹ H-NMR measurement revealed that the peaks of hydrogen atoms assigned to the carbon-carbon double bonds of the monomers had disappeared, confirming that the reaction had progressed.

3. Evaluation of copolymers and copolymer compositions 3-1. Appearance of copolymer compositions In Examples 1 to 14 (copolymers 1 to 14), cloudy dispersions and transparent solutions without precipitation were obtained, whereas in Comparative Examples 1 to 5 (polymers 24 to 28), precipitation occurred immediately after synthesis, confirming that the copolymers of the present invention have high affinity for organic solvents. It was confirmed that the cloudy dispersions and transparent solutions of Examples 1 to 14 (copolymers 1 to 14) were dispersed and dissolved in a stable state without precipitation for one month at 25°C (Table 1). In addition, with respect to the molar ratio (A)/(B) of monomer (A) and monomer (B), Examples 16 to 21 (copolymers 16 to 21) with monomer (A)/monomer (B)=0.02 were cloudy (dispersible in water), Example 4 (copolymer 4) with monomer (A)/monomer (B)=0.03 was slightly cloudy, and Examples 1 to 3 and 5 to 14 (copolymers 1 to 3 and 5 to 14) with monomer (A)/monomer (B)=0.04 or more were transparent, suggesting that the higher the ratio of monomer (A), the higher the affinity for organic solvents. On the other hand, the lower the ratio of monomer (A), the lower the viscosity was observed.

3-2. UV absorption properties of copolymers and copolymer compositions The copolymer compositions 1 to 14 (Examples 1 to 14) and copolymer 26 (Comparative Example 3) obtained above were diluted with the solvent used in synthesis to a solid content of 0.04 to 0.05% by mass, and the absorption spectrum was measured using a UV-visible-infrared spectrophotometer (UH4150V manufactured by Hitachi High-Tech Science) (Table 1). The spectrum of a 0.04% by mass toluene solution of copolymer 6 is shown in Figure 1, and the spectrum of a 0.04% by mass toluene solution of copolymer 26 is shown in Figure 2.

Copolymers 1 to 14 and their compositions (Examples 1 to 14) of monomer (A) in which the above formula (i-1) has been introduced into the benzotriazole group have a maximum absorption wavelength shifted to 360 to 380 nm, a longer wavelength region, compared to copolymer 26 (Comparative Example 26), and it has been confirmed that they have excellent ultraviolet absorption in the vicinity of 360 to 420 nm, based on the wavelengths of copolymer 6 composition in Figure 1.

From the absorption spectra of the compositions of Copolymers 6 and 26 in FIGS. 1 and 2, the intersection point between the absorption spectrum on the long wavelength side of the absorption peak in the wavelength region of 330 to 390 nm and the baseline (the line where the absorption spectrum in the wavelength region of 380 to 500 nm has a slope of 0) was defined as the peak end (e.g., FIG. 1), and the absolute value of the slope on the long wavelength side of the absorption peak in the wavelength region of 330 to 390 nm was calculated by the following formula.
|Slope of the long wavelength side of the absorption peak in the wavelength region of 330 to 390 nm| = |(peak end absorbance - absorbance of the absorption peak in the wavelength region of 330 to 390 nm) / (peak end absorption wavelength - wavelength of the absorption peak in the wavelength region of 330 to 390 nm)|

The absorption peak on the long wavelength side of the wavelength region of 330 to 390 nm was sharper for copolymer 6 than for copolymer 26, and when the monomer (A)/monomer (B) ratio was 1.00 and the copolymer concentration (solid content) was 40% by mass, the slope of the long wavelength side of the absorption peak in the wavelength region of 330 to 390 nm was 0.0277 (the slope of copolymer 26 with monomer (C)/monomer (B)=1.00 and a copolymer concentration (solid content) of 40% by mass was 0.0101).
It was confirmed that the copolymer and the aqueous composition of the present invention have little cutoff in the range of 430 to 500 nm (visible range) and are excellent in the yellowing suppression effect.

4. Measurement of glass transition temperature of copolymers The copolymer compositions 15, 29, and 30 (Example 15, Comparative Examples 6 and 7) obtained in 2 above were heated and reduced pressure to remove the organic solvent to obtain each copolymer, and measured using a differential scanning calorimeter (manufactured by SII, DSC7020) at a temperature rise rate of 10°C/min and a measurement range of 25 to 265°C, and the glass transition temperature of the copolymer was read by DDSC (Table 2). As a result, the relationship was copolymer 15: 129°C > copolymer 29: 124°C > copolymer 30: 105°C, and it was confirmed that copolymer 15 containing monomer (A) had high strength at high temperatures.

5. Evaluation of aqueous composition of copolymer by emulsion polymerization method It was confirmed that the aqueous dispersion of copolymers 16 to 21 obtained by the above 2. emulsion polymerization method was stable and dispersed without precipitation for one month at 25 ° C. In addition, similarly to 3-2, it was diluted with ion-exchanged water to 0.04 mass % and the absorption spectrum was measured (Table 3, Figure 3: spectrum of copolymer 16). It was confirmed that the maximum absorption wavelength was 360 to 380 nm, and that the ultraviolet absorption around 360 to 420 nm was excellent, including the spectrum of Figure 3.

6. Evaluation of light resistance of copolymers Copolymer compositions 22, 23, 31, and 32 shown in 2 above were formed into a thin film using a spin coater (MS-B150 manufactured by Mikasa) at a rotation speed of 1500 rpm for 10 seconds, and the organic solvent was distilled off to prepare a thin film of copolymer. The thin film was measured for ultraviolet-visible transmission spectrum using a UV-Visible Infrared Spectrophotometer (UH4150V manufactured by Hitachi High-Tech Science), and the initial (before irradiation) UV transmittance (%): A at 380, 390, 400, and 410 nm was read. Thereafter, using an ultraviolet irradiation device (Atlas Weather-O-Meter Ci3000+w), ultraviolet light was irradiated for 100 hours under conditions of a wavelength of 300-400 nm, an illuminance of 42 W/ ^m2 , and a black panel temperature of 63°C. After that, the ultraviolet-visible transmission spectrum was measured, and the transmittance (%):B at 380, 390, 400, and 410 nm was read, and the difference in transmittance before and after irradiation, _Δ100T :B-A (%), was calculated (Table 4).
.

その結果、モノマー（Ａ）、（Ｂ）（モノマーＡ１、モノマーＢ）からなる本発明の共重合体２２、２３は、モノマー（Ｂ）、（Ｃ）からなる共重合体に比べ、初期からの変化が小さく、耐光性に優れていることが示唆された。

As a result, it was suggested that copolymers 22 and 23 of the present invention composed of monomers (A) and (B) (monomer A1, monomer B) showed less change from the initial stage and had better light resistance than copolymers composed of monomers (B) and (C).

Claims (5)

An aqueous composition comprising a copolymer of monomer components including the following monomer (A) and monomer (B), water, and a surfactant.
(Monomer (A))
The following formula (I):

(In the formula, R ¹ to R ⁹ each independently represent the following formula (i-1):

In formula (i-1), when m is 2 or more, R ¹¹ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ¹² represents the following formula (i-2):

(wherein R ^12a , R ^12b , and R ^12c each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, A represents a divalent group selected from an ester group, an amide group, and an aromatic group, and X represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.) m represents an integer of 0 to 3. ) represents a monovalent group selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and a hydroxy group. At least one of R ¹ to R ⁹ is a monovalent sulfur-containing group represented by formula (i-1). ) (monomer (B))
The following formula:

(wherein at least one of R ^A1 to R ^A4 represents an alkyl ester group having 1 to 18 carbon atoms in the alkyl portion, and among R ^A1 to R ^A4 other than the alkyl ester group , each represents a group selected from a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms). 2. The aqueous composition according to claim 1, wherein X in formula (i-2) is an alkylene group --(CH ₂ ) _n -- (n is an integer of 1 or more) or a phenylene group. The aqueous composition according to claim 1 or 2, wherein the molar ratio (A)/(B) of the monomer (A) to the monomer (B) is greater than 0.03. The aqueous composition according to any one of claims 1 to 3, wherein the surfactant is anionic or cationic. A method for producing the aqueous composition according to any one of claims 1 to 4, comprising obtaining the aqueous composition by an emulsion polymerization method.