JP2021147514A - Copolymer including benzotriazole-based ultraviolet-absorbing unit and composition thereof - Google Patents

Abstract

To provide a copolymer that efficiently absorbs ultraviolet rays having a wavelength of 360-420 nm; exhibits high affinity; and has excellent solubility and dispersibility when combined with water, and a composition of the copolymer.SOLUTION: A copolymer of monomer components according to the present invention contains following monomer (A), monomer (B) and/or monomer (C). Monomer (A): a benzotriazole compound having a monovalent sulfur containing group. Monomer (B): a carboxy group-containing vinyl monomer or a salt thereof. Monomer (C): a hydroxy alkyl group-containing vinyl monomer.SELECTED DRAWING: None

Description

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

The resin member deteriorates due to the action of ultraviolet rays, causing quality deterioration such as discoloration and deterioration of mechanical strength, and hinders long-term use. Further, in terms of health, since the skin and eyes are adversely affected by ultraviolet rays, it is required to control the wavelength of transmitted light, and in recent years, wavelength control of 360 to 420 nm has been demanded.

Conventionally, a benzotriazole skeleton is known as a functional group having an ultraviolet absorbing ability. In Patent Documents 1 to 5, a compound in which an acryloyloxy group having reactivity with a monomer or a resin is introduced into a 2-phenylbenzotriazole skeleton via an alkylene group or an alkylene group in which ether oxygen is introduced at the base end. And (co) polymers using this are disclosed. There is a problem that the absorption efficiency of harmful wavelengths around 360 to 420 nm is low. In addition, there is no description or suggestion regarding the affinity and solubility of the (co) polymer with water.

In particular, the present inventors have a sulfur-containing group as an ultraviolet absorber that efficiently and sufficiently absorbs harmful light from 380 to 400 nm and suppresses absorption of wavelength light having a wavelength of 400 nm or more, which causes initial yellowing. A 2-phenylbenzotriazole derivative having the above was proposed (Patent Documents 6 and 7). Due to its optical properties, this ultraviolet absorber can sufficiently absorb light in the wavelength range of 250 to 400 nm, has a high ultraviolet absorption effect (molar absorption coefficient), and has a wavelength that can be added in a small amount. Light can be absorbed efficiently, and the inclination of the absorption peak at 350 to 390 nm is larger than that of the conventional ultraviolet absorber, and the absorption of wavelength light of about 400 nm or more is suppressed, and the initial yellowing of the compounded member is suppressed. Can be done. In the examples, a compound in which an allyl group is bonded to a 2-phenylbenzotriazole skeleton via a sulfur atom is synthesized, but the reactivity that enables high molecular weight and the solubility of the resin raw material in the monomer are further improved. There was room for. In Patent Document 8, the solubility and reactivity of the resin raw material in the monomer are improved. In the examples, a copolymer with methyl methacrylate, styrene, vinyl acetate, dimethylacrylamide, or hexadiene is synthesized, but in recent years, the stability without using an organic solvent is high from the viewpoint of low environmental load and high safety. Aqueous solutions and dispersions of copolymers having an ability to absorb a wavelength in the vicinity of 360 to 420 nm are required, but these are not described.

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

As described above, the copolymer containing a benzotriazole-based ultraviolet absorbing unit having excellent long-wavelength absorption is based on the viewpoint of efficiently absorbing long-wavelength ultraviolet rays and further showing a high affinity with water. The polymer has not been sufficiently studied.

The present invention has been made in view of the above circumstances, provides a copolymer that efficiently absorbs wavelengths of 360 to 420 nm, exhibits higher hydrophilicity, and is soluble in combination with water. It is an object of the present invention to provide a copolymer having excellent dispersibility and a composition thereof.

In order to solve the above problems, the copolymer of the present invention is characterized by being a copolymer of the following monomer (A) and a monomer component containing the monomer (B) and / or the monomer (C). It is said.
(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 are independent of each other, and 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, and R ¹¹ is substituted independently when m is 2 or more. It represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a group, and R ¹² is the following formula (i-2) :.

(In the formula, R ^12a , R ^12b , and R ^12c each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and A is selected from an ester group, an amide group, and an aromatic group. It represents a divalent group, and X represents a monovalent group represented by a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. l indicates an integer of 0 or 1, and m indicates an integer of 0 to 3. ) Indicates a monovalent group selected from a monovalent sulfur-containing group, 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). ) Is represented by a benzotriazole compound.
(Monomer (B))
Carboxy group-containing vinyl monomer or salt thereof (monomer (C))
Hydroxyalkyl group-containing vinyl monomer

The aqueous composition of the present invention contains the copolymer and water.

The copolymer of the present invention efficiently absorbs ultraviolet rays having a long wavelength of 360 to 420 nm. It shows higher hydrophilicity, good stability in combination with water, and excellent solubility and dispersibility.

It is an ultraviolet-visible absorption spectrum (UV chart) of the copolymer 5 aqueous solution which is an Example of this invention. It is an ultraviolet-visible absorption spectrum (UV chart) of the copolymer 22 methanol solution which is a comparative example.

Hereinafter, the present invention will be described in detail.
(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 is a monovalent or divalent group selected from an aromatic group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom. Groups such as "groups" that can adjust heat resistance, refractive index, melting point, light resistance, compatibility with resin, etc. are included, and examples thereof include the following.

The aromatic group contains an aromatic ring such as a benzene ring, a naphthalene ring, and an anthracene ring, and has preferably 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms. The monovalent aromatic group is not particularly limited, and is, for example, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, and a 2,5-dimethyl group. Phenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 4-biphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 4-fluorophenyl group, 2-tri Examples thereof include fluoromethylphenyl group, 4-trifluoromethylphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthrasenyl group, 2-anthrasenyl group, 9-anthrasenyl group and the like. The divalent aromatic group is not particularly limited, but for example, a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 1,8-naphthylene group, a 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, Examples thereof include a 1,4-anthrasenylene group and a 1,3-anthrasenylene group.

Unsaturated groups are carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds (carbonyl group, aldehyde group, ester group, carboxy group, carbamate group, urea group, amide group, imide group, carbamoyl). Group, urethane group, etc.), carbon-nitrogen double bond (isocyanate group, etc.), carbon-nitrogen triple bond (cyano group, cyanato group, etc.), etc. The number is preferably 1-10, more preferably 1-8. The unsaturated group is not particularly limited, but for example, an acryloyl group, a metachloryl group, a maleic acid monoester group, a styryl group, an allyl group, a vinyl group, an alkenyl group, an alkynyl group, a carbonyl group, an aldehyde group, an ester group and a carboxy group. Examples thereof include a group, a carbamate group, a urea group, an amide group, an imide group, a carbamoyl group, a cyano group, a cyanato group, an isocyanate group and a urethane group.

The nitrogen-containing group contains a cyano group, a nitro group, or a 1-3-class amino group, and has preferably 0 to 10 carbon atoms. The nitrogen-containing group is not particularly limited, but for example, 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, and the like. Imidazole group, amino group, primary amino group, secondary amino group, tertiary amino group, aminoalkyl group, 3,4,5,6-tetrahydrophthalimidinemethyl group, 2- [6- (2H-benzotriazole) -2-yl-) -4- (1,1,3,3-tetramethylbutyl) phenol-yl] -methyl group and the like can be mentioned.

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 has preferably 0 to 10 carbon atoms. .. The sulfur-containing group is not particularly limited, but for example, 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, p. -Methylthiophenoxy group, p-methoxythiophenoxy group, thiophene group, thiazole group, thiol group, sulfo group, sulfide group, disulfide group, thioester group, thioamide group, sulfonyl group, thiocarbonyl group, thiourea group, thiocarbamate group , Dithiocarbamate group and the like.

The oxygen-containing group preferably has 6 to 12 carbon atoms when it contains an aromatic ring group or an alicyclic group, and preferably 0 to 18 carbon atoms when it does not contain an aromatic ring group or an alicyclic group. be. The oxygen-containing group is not particularly limited, but for example, 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, and the like. Examples thereof include 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 morpholin group, a carbamate group, a carbamoyl group and a polyoxyethylene group.

The phosphorus-containing group contains 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 when it contains an aromatic ring group or an alicyclic group, the number of carbon atoms is preferable. When 6 to 22, an aromatic ring group or an alicyclic group is not contained, the number of carbon atoms is preferably 0 to 6. The phosphorus-containing group is not particularly limited, but for example, a trimethylphosphine group, a tributylphosphine group, a tricyclohexylphosphine group, a triphenylphosphine group, a tritrylphosphine group, a methylphosphite group, an ethylphosphite group, and a phenylphosphite group. , Phosphonic acid group, phosphinic acid group, phosphoric acid group, phosphoric acid ester group and the like.

The alicyclic group preferably has 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms. The alicyclic group is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a group containing these as a skeleton.

The halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

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

The benzotriazole compound represented by the above formula (I) is a monovalent sulfur represented by the above formula (i-1) at at least one position of ^{R 1 to} R ^{9 bound to the skeleton of the benzotriazole system.} Contains containing groups.

In formula (i-1), R ¹⁰ may have a substituent and has 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3 divalent hydrocarbons. Indicates a hydrogen group.

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 a linear or branched alkylene group, a linear or branched alkaneylene group, a linear or branched alkaneylene group and the like can be mentioned. Although not particularly limited, for example, methylene group, ethane-1,2-diyl group, propane-1,3-diyl group, 1-methylethane-1,2-diyl group, butane-1,4-diyl group, butane- 1,3-diyl group, 2-methylpropane-1,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, hexane-1,6-diyl group, heptane-1, 7-Diyl Group, Octane-1,8-Diyl Group, Nonan-1,9-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 -Il group, nonadecan-1,19-yl group, Eikosan-1,20-yl group and the like can be mentioned. Among these, an alkylene group is preferable, and a linear alkylene group is more preferable. Examples of the alicyclic hydrocarbon group and the aromatic hydrocarbon group include the alicyclic group and the aromatic group exemplified in the above-mentioned [substituents and the like].

When the divalent hydrocarbon group has a substituent, the number of the substituents is not particularly limited, and examples thereof include two or less or one or less.

Specific examples of the substituent include those exemplified in the above-mentioned [Substituents, etc.] column.

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

In the formula (i-1), when ^{m is 2 or more, R 11} may independently have a substituent and has 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 5, and further. It preferably shows 1 to 3 divalent hydrocarbon groups.

Examples of the divalent hydrocarbon group of R ¹¹ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among them, an aliphatic hydrocarbon group is preferable, and the ^{divalent hydrocarbon group of R 10} exemplified above can be mentioned. Among these, an alkylene group is preferable, and a linear alkylene group is more preferable. Examples of the alicyclic hydrocarbon group and the aromatic hydrocarbon group include the alicyclic group and the aromatic group exemplified in the above-mentioned [substituents and the like].

The ^{divalent hydrocarbon group of R 11 is} the monovalent or divalent substituent described above, the hydrogen atom is substituted, at least one of both ends is interrupted, or the carbon-carbon bond is interrupted. In this case, the number of the monovalent or divalent substituents is not particularly limited, and examples thereof include two or less or one or less.

In formula (i-1), m represents an integer of 0 to 3, preferably m is 0 or 1, and more preferably m is 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 the monovalent hydrocarbon group having 1 to 18 carbon atoms include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among them, an aliphatic hydrocarbon group is preferable. Examples of the aliphatic hydrocarbon group include a linear or branched alkyl group, a linear or branched alkenyl group, a linear or branched alkynyl group, and the like. Of these, linear or branched alkyl groups are preferred. Examples of the linear or branched alkyl group include a methyl group, an ethane-1-yl group, a propan-1-yl group, a 1-methylethane-1-yl group, a butane-1-yl group, and a butane-2-yl group. Group, 2-methylpropan-1-yl group, 2-methylpropan-2-yl group, pentane-1-yl group, pentadec-2-yl group, hexane-1-yl group, heptane-1-yl group, Octane-1-yl group, nonan-1-yl group, decane-1-yl group, undecane-1-yl group, dodecane-1-yl group, tridecane-1-yl group, tetradecane-1-yl group, pentadecane Examples thereof include -1-yl group, hexadecane-1-yl group, heptadecane-1-yl group, octadecane-1-yl group and the like. Examples of the alicyclic hydrocarbon group and the aromatic hydrocarbon group include the alicyclic group and the aromatic group exemplified in the above-mentioned [substituents and the like].

Considering the reactivity and solubility of the resin raw material with the monomer, the monovalent hydrocarbon group preferably has 1 to 13 carbon atoms, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 1. be. In a preferred embodiment, (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, and R ^12b and R ^12c are hydrogen atoms. 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, R ^12a , R ^12b , and R ^12c in (1) are hydrogen atoms, or in (2), R ^12a is a monovalent hydrocarbon group having 1 carbon atom, and R ^12b and R ^12c are hydrogen atoms. Alternatively, among (3), those 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 preferable, and from the viewpoint of high reactivity, (1) It is more preferable that R ^12a , R ^12b , and R ^{12c are hydrogen atoms.}

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

The ester group is -C (= O) O- or -OC (= O)-and the amide group is -NHC (= O)-or -C (= O) NH-. Examples of the aromatic group include those exemplified in the above-mentioned [Substituents, etc.] column and may have a substituent, but 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group. Is preferable, and 1,4-phenylene groups are more preferable. Considering the reactivity and solubility of the resin raw material with the monomer, A is preferably an ester group, and among them, from the viewpoint of water solubility and reactivity, -X-OC (= O) in which an oxygen atom is bonded to X )-Ester group is more preferable.

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 by the above-mentioned R 10} divalent hydrocarbon group, and examples of the alicyclic hydrocarbon group and the aromatic hydrocarbon group are exemplified in [Substituents and the like]. Examples include alicyclic groups and aromatic groups.

Among them, an aliphatic hydrocarbon group and an aromatic hydrocarbon group are preferable. Among these, an alkylene group and a phenylene group are preferable, and a linear alkylene group and a phenylene group are more preferable. From the viewpoint of water solubility, the alkylene group preferably has a short 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, and examples thereof include two or less or one or less. Examples of the substituent include those exemplified in the above-mentioned [Substituents, etc.] column.

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

（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, n are synonymous with the 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, n are synonymous with the 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 synonymous with the above.)

The copolymer using the benzotriazole compound represented by the formula (I) as a monomer (unit) has excellent long-wavelength ultraviolet absorption ability of 360 to 420 nm, and the benzotriazole component does not bleed out or elute, and the ultraviolet absorption ability. Can be retained for a long period of time. Further, the copolymer in combination with the following monomer (B) and / or monomer (C) exhibits high hydrophilicity, and obtains a low environmental load, high safety aqueous solution and aqueous dispersion that do not use an organic solvent. be able to.

In the benzotriazole compound represented by the formula (I), ^{at least one of R 1 to} R ⁹ is a monovalent sulfur-containing group represented by the formula (i-1). Among them, high UV absorption is achieved by improving the UV absorption ability, hydrophilicity, ease of actual synthesis, absorption characteristics and cost, heat resistance, and compatibility with other monomers of the copolymer raw material. Considering the point that the ability can be expressed, ^{it is preferable that 1 to 2 of R 1 to} R ⁹ are monovalent sulfur-containing groups represented by the formula (i-1), and one of them is the formula. It is more preferably a monovalent sulfur-containing group represented by (i-1).

The position of the monovalent sulfur-containing group represented by the formula (i-1) in the formula (I) is not particularly limited, and the monovalent sulfur-containing group represented by the formula (i-1) is not particularly limited. It is preferable to have it in any ^{of R 6 to} R ⁹ of the formula (I), and ^{the positions of R 6} and R ⁹ are more preferable.

In the formula (I), when R ^{1 to} R ⁹ are groups other than the monovalent sulfur-containing group represented by the formula (i-1), they may have a hydrogen atom and a substituent and have 1 to 1 carbon atoms. The monovalent group selected from 10 hydrocarbon groups and hydroxy groups is shown.

When R ^{1 to} R ⁹ are monovalent hydrocarbon groups, examples of the monovalent hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among them, an aliphatic hydrocarbon group is preferable, and a linear or branched alkyl group, a linear or branched alkenyl group, a linear or branched alkynyl group and the like can be mentioned. Specifically, for example, methyl group, ethane-1-yl group, propane-1-yl group, 1-methylethane-1-yl group, butane-1-yl group, butane-2-yl group, 2-methyl. Propane-1-yl group, 2-methylpropan-2-yl group, pentan-1-yl group, pentan-2-yl group, 2-methylbutane-1-yl group, hexane-1-yl group, 2-methyl Pentan-1-yl group, 3-methylpentane-1-yl group, heptane-1-yl group, 3-ethylpentane-1-yl group, 2-methylhexane-yl group, 3-methylhexane-yl group, Octane-1-yl group, 2-methylheptane-1-yl group, 3-methylheptane-1-yl group, 4-methylheptane-1-yl group, 2-ethylhexane-1-yl group, 3-Ethylhexane-1-yl group, 1,1,3,3-tetramethylbutylnonane-1-yl group, 3-ethylheptane-1-yl group, 4-ethylheptane-1-yl group, 2 -Methyloctane-1-yl group, 3-methyloctane-1-yl group, 4-methyloctane-1-yl group, decane-1-yl group, 4-propylheptane-1-yl group, 3-ethyl Octane-1-yl group, 4-ethyloctane-1-yl group, undecane-1-yl group, dodecane-1-yl group, 2-methylundecane-1-yl group, 2-ethyldecane-1-yl group, Examples thereof include tridecane-1-yl group, tetradecane-1-yl group, pentadecane-1-yl group, hexadecane-1-yl group, heptane-1-yl group, octadecane-1-yl group and the like. Among these, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 4 carbon atoms is more preferable.

Specific examples of the substituent include those exemplified in the above-mentioned [Substituents, etc.] column.

In formula (I), when R ⁹ at the 5-position has a monovalent sulfur-containing group represented by formula (i-1), it is used as a group other than the monovalent sulfur-containing group represented by formula (i-1). , R ⁶ , R ⁷ and R ⁸ are all preferably hydrogen atoms. Further, a preferable example of the combination of ^{R 1} , R ² , R ³ , R ⁴ , and R ^{5 is as follows.}

[1] 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, and 1 carbon number. With an ether group of ~ 18, 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 substituent thereof. It contains one or more substituents selected from hydrocarbon groups having 1 to 18 carbon atoms in which the hydrogen atom may be substituted, the base end may be interrupted, or the carbon-carbon bond may be interrupted.
[2] In [1], the substituent is at least one selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydroxy group.
[3] In [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 of [1] to [3], the hydrocarbon group of the substituent is a linear or branched alkyl group.
[5] In [4], the substituent is at least one selected from a methyl group, a t-butyl group, and a hydroxy group.
[6] In [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 of [1] to [6], the number of substituents is 2 to 4.
[8] In any of [1] to [7], the substituent is at any position of ^{R 1 to} R ^{4 , and the other R 1 to} R ⁵ are hydrogen atoms.
[9] In any of [1] to [8], the substituent is at any position of ^{R 1} , R ² , and R ^{4 , and the other 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, so that it sharply cuts ultraviolet rays in the vicinity of 360 to 420 nm while suppressing absorption in the range of 430 to 500 nm (visible range) due to its ability to absorb ultraviolet rays. Is possible. Therefore, the copolymer of the present invention and the resin member using the copolymer suppress yellow coloring, have an excellent appearance, and can sufficiently absorb light in the wavelength region of 250 to 420 nm. In order to efficiently absorb the wavelength of 360 to 420 nm, the maximum absorption wavelength of the light of the copolymer is preferably 350 to 390 nm, more preferably 360 to 380 nm, and particularly preferably 360 to 375 nm. Is preferable. Further, in terms of the yellow suppression effect, the inclination of the absorption peak in the wavelength region of 330 to 390 nm on the long wavelength side is preferably sharp, for example, when monomer (A) / monomer (B) = 0.01. When the concentration of the copolymer aqueous solution is 800 mg / L, the inclination is preferably 0.0050 or more, more preferably 0.0060 or more.

The method for producing the benzotriazole compound represented by the formula (I) is not particularly limited, but the disclosure of Examples described later and known techniques are referred to.

(Monomer (B))
In the copolymer of the present invention, the monomer (B) is a carboxy group-containing vinyl monomer or a salt thereof.

Carboxyl group-containing vinyl monomer is represented by ^{R A1 R A2 C = CR A3} R A4, at least one of R ^A1 to R ^A4, preferably one carboxy-containing group. The carboxy group-containing group preferably has 1 to 18 carbon atoms (including carbon of the carboxy group), more preferably 1 to 8, and further preferably 1. Except carboxy group-containing group of R ^A1 to R ^A4 is a hydrogen atom is any group selected from a hydrocarbon group having 1 to 18 carbon atoms. The hydrocarbon group is preferably an alkyl group, and other than the carboxy-containing group, a hydrogen atom and a carbon number of 1 to 4 are preferable, and a hydrogen atom and a carbon number of 1 are more preferable. Preferred embodiments of R ^A1 to R ^A4, except carboxy group-containing group, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

The carboxyl group-containing vinyl monomer is not particularly limited, and examples thereof include unsaturated monos, dicarboxylic acids, and monoesters of unsaturated dicarboxylic acids. Although not particularly limited, for example, acrylic acid, methacrylic acid, 3- (1-naphthyl) acrylic acid, 1,4-phenylenediacrylic acid, vinyl acetic acid, angelica acid, tigric acid, crotonic acid, 3-methylcrotonic acid, 2 -Pentenoic acid, 2-methyl-2-pentenoic acid, 4-methyl-2-pentenoic acid, 2-hexenoic acid, 2-heptenoic acid, 2-octenoic acid, 2-nonenic acid, 2-decenoic acid, 2-dodecene Acids, 2-undecenoic acid, 2-tridecenoic acid, 2-hexadecenoic acid, (2E, 4E) -5-phenyl-2,4-pentadienoic acid, 10-hydroxy-2-decenoic acid, sorbic acid, myristolenic acid, Palmitreic acid, oleic acid, cinnamic acid, 2-methyl cinnamic acid, 3-methyl cinnamic acid, 4-amino cinnamic acid, 4-chloro cinnamic acid, 4- (trifluoromethyl) cinnamon acid, 4-bromo cinnamic acid, 3 -Bromo cinnamic acid, 2-chloro cinnamic acid, 3-chloro cinnamic acid, 2,6-dichloro cinnamic acid, m-kumalic acid, p-kumalic acid, mucon acid, itaconic acid, itaconic acid monoester, maleic acid, malein Examples thereof include acid monoester, fumaric acid, fumaric acid monoester, citraconic acid, and citraconic acid monoester. Among these, methacrylic acid and acrylic acid are preferable.

The monomer (B) imparts high hydrophilicity to the copolymer of the present invention.

The salt of the carboxy group-containing vinyl monomer is not particularly limited, and examples thereof include alkali metal salts, alkaline earth metal salts, ammonium salts, and salts with organic amines. The alkali metal is not particularly limited, and examples thereof include lithium, sodium, and potassium. The alkaline earth metal is not particularly limited, and examples thereof include magnesium and calcium. The organic amine is not particularly limited, and examples thereof include primary amines, secondary amines, tertiary amines, and monomethanol amines, monoethanolamines, monopropanol amines, monoisopropanol amines, monobutanol amines, and monopentanols. Amines, dimethanolamines, diethanolamines, dipropanolamines, diisopropanolamines, dibutanolamines, dipentanolamines, trimethanolamines, triethanolamines, tripropanolamines, triisopropanolamines, tributanolamines, trypentanolamines, etc. Alkanolamine, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine, monobutylamine, dibutylamine, tributylamine, monopentylamine, dipentylamine, tripentylamine. Examples thereof include alkylamines such as alkylamines such as pyrrolidine, piperidine, pyridine, pyrazine, pyrrol, cyclic amines such as morpholin, and polyalkylene amines such as ethylenediamine and diethylenetriamine. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Among these (meth) acrylic acid salts, alkali metal salts, ammonium salts and organic ammonium salts are preferable in consideration of affinity with water and solubility in water, and sodium salts, potassium salts, ammonium salts and alkanolammonium salts. Salts are more preferred, ammonium salts, diethanolammonium salts and triethanolammonium salts are particularly preferred, ammonium salts and triethanolammonium salts are more preferred, and ammonium salts are even more preferred.

(Monomer (C))
In the copolymer of the present invention, the monomer (C) is a hydroxyalkyl group-containing vinyl monomer.

A (hyA) _n - hydroxyalkyl group-containing vinyl monomer is represented by ^{R A5 R A6 C = CR A7} R A8, at least one of R ^A5 to R ^A8, preferably is one 1 -R ^B1. R ^B1 is a group selected from -C (= O) O-, -C (= O) N <, and -C (= O) NH-, hyA is a hydroxyalkyl group, and n is an integer of 1 or more. .. Except hydroxyalkyl group-containing group of R ^A5 to R ^A8 is a hydrogen atom is any group selected from a hydrocarbon group having 1 to 18 carbon atoms. n is preferably 1 and R ^B1 is preferably −C (= O) O−.

The hydroxyalkyl group-containing vinyl monomer is not particularly limited, but considering the affinity with water, the number of carbon atoms of the alkylene group in the hydroxyalkyl group is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 4. preferable. Specifically, but not particularly limited, for example, 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy (meth) acrylate. Butyl, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 9-hydroxy (meth) acrylate Nonyl, 10-hydroxydecyl (meth) acrylate, 11-hydrochiundecyl (meth) acrylate, 12-hydroxydodecyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Hydroxybutyl, 2-hydroxypentyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, 2,2-bis (hydroxymethyl) -1,3-propanediyl bismethacrylate, N- (hydroxymethyl) acrylamide , N- (hydroxyethyl) acrylamide, N- (hydroxypropyl) acrylamide, N- (hydroxybutyl) acrylamide, N- (hydroxypentyl) acrylamide, N- (hydroxyhexyl) acrylamide, N- (hydroxyheptyl) acrylamide, N -(Hydroxyoctyl) acrylamide, N- (hydroxynonyl) acrylamide, N- (hydroxydecyl) acrylamide, N- (hydroxydodecyl) acrylamide, N- (hydroxydoundecyl) acrylamide and the like can be mentioned.

(Other monomers)
In addition to the monomers (A), (B), and (C), other monomers can be used in the copolymer of the present invention. Such a monomer is not particularly limited, and examples thereof include the following monomers.

Monomer (D)
Examples thereof include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and fumaronitrile.

Monomer (E)
The monomer (E) is an ester group-containing vinyl monomer.
Ester group-containing vinyl monomer is represented by ^{R A9 R A10 C = CR A11} R A12, at least one of R ^A9 to R ^A12, preferably one but an ester group. Other than an ester group-containing group of R ^A9 to R ^A12 is a hydrogen atom is any group selected from a hydrocarbon group having 1 to 18 carbon atoms. The hydrocarbon group is preferably an alkyl group, preferably a hydrogen atom having 1 to 4 carbon atoms, and more preferably a hydrogen atom and 1 carbon atom, except for an ester group-containing group.

The ester group-containing vinyl monomer is not particularly limited, and is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and 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, octadecyl (meth) acrylate And so on. Considering the affinity with water, the number of carbon atoms of the alkyl moiety in the ester group is preferably 1 to 18, more preferably 1 to 12, further preferably 1 to 8, 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 preferable.

Among the monomers (D) and (E), (D) is preferable from the viewpoint of affinity with water.

Monomer (F)
It is a monomer other than the above. Specific examples thereof include, but are not limited to, styrene-based monomers, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, dimethylacrylamide, hexadiene and the like. The styrene-based monomer is not particularly limited, but for example, styrene, α-methylstyrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, isopropylstyrene, butylstyrene, isobutylstyrene, Alkyl styrene such as t-butyl styrene, s-butyl styrene, pentyl styrene, hexyl styrene, heptyl styrene, octyl styrene; halogenated styrene such as chloro styrene, fluoro styrene, bromo styrene, dibromo styrene, iodo styrene; p-methoxy styrene Such as alkoxystyrene; arylstyrene such as p-phenylstyrene; styrenesulfonic acid or an alkali metal salt thereof, nitrostyrene, aminostyrene, hydroxystyrene, 4 (trimethoxysilyl) styrene and the like. Of these, styrene, vinyl acetate, vinyl propionate, and dimethylacrylamide are preferable.

(Copolymer)
Hereinafter, the copolymer of the present invention will be described.
The copolymer of the present invention is a copolymer of a monomer component containing a monomer (A) and a monomer (B) and / or a monomer (C).

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 structural units derived from each type of monomer, that is, repeating units are bonded. Specifically, the main chain in which the vinyl groups of each type of monomer are polymerized, the groups possessed by these monomers, for example, the ultraviolet absorbing group of the monomer (A), the functional groups such as the monomers (B) and (C), and the side. It has a chain or the like. The copolymer is not particularly limited, and may 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 not particularly limited.

In the copolymer of the present invention, preferable examples in the composition of the monomer component from the viewpoint of affinity with water are as follows.
In the first example, the monomer component comprises a monomer (A) and a monomer (B). In this case, the molar ratio (A) / (B) is preferably 0.7 or less, more preferably 0.5 or less, further preferably 0.09 or less, and particularly preferably 0.05 or less.
In the second example, the monomer component comprises a monomer (A) and a monomer (C). In this case, the molar ratio (A) / (C) is preferably 0.7 or less, more preferably 0.5 or less, further preferably 0.09 or less, and particularly preferably 0.05 or less.
In the third example, the monomer component comprises a monomer (A), a monomer (B), and a monomer (C). In this case, the molar ratio (A) / ((B) + (C)) is preferably 0.7 or less, more preferably 0.5 or less, further preferably 0.09 or less, and particularly preferably 0.05 or less.

On the other hand, a preferable example in the composition of the monomer component from the viewpoint of ultraviolet absorption ability is as follows.
In the first example, the monomer component comprises a monomer (A) and a monomer (B). In this case, the molar ratio (A) / (B) is preferably 0.001 or more, more preferably 0.01 or more, further preferably 0.05 or more, and particularly preferably 0.1 or more.
In the second example, the monomer component comprises a monomer (A) and a monomer (C). In this case, the molar ratio (A) / (C) is preferably 0.001 or more, more preferably 0.01 or more, further preferably 0.05 or more, and particularly preferably 0.1 or more.
In the third example, the monomer component comprises a monomer (A), a monomer (B), and a monomer (C). In this case, the molar ratio (A) / ((B) + (C)) is preferably 0.001 or more, more preferably 0.01 or more, further preferably 0.05 or more, and particularly preferably 0.1 or more. ..

That is, from the viewpoint of both affinity with water and ability to absorb ultraviolet rays, the molar ratios (A) / (B), (A) / (C), (A) of the monomers (A), (B), and (C). ) / ((B) + (C)) is preferably 0.001 or more and 0.7 or less, more preferably 0.01 or more and 0.5 or less, further preferably 0.01 or more and 0.09 or less, and 0.01. More than 0.05 or less is particularly preferable.

Further, when the monomer component contains the monomer (A) and the monomer (B) and contains the salt of the carboxy group of the monomer (B) as in the first and second examples above, the viewpoint of hydrophilicity is taken into consideration. Then, the molar ratio of the carboxy group of the monomer (B) to its salt (carboxy group / salt thereof) is preferably 10 or less, more preferably 1 or less, and further preferably 0.1 or less.

Although not particularly limited, for example, even when a monomer component other than the monomers (A), (B), and (C) such as acrylonitrile, an ester group-containing monomer, and a styrene-based monomer is contained, the affinity with water and / or ultraviolet rays The preferable molar ratios of the monomers (A), (B) and (C) from the viewpoint of absorbability are the same as described above.
In the copolymer of the present invention, the total molar ratio of the monomers (A), (B), and (C) is not particularly limited, but is 90 mol% or more, 80 mol% or more, or 50 mol% based on all the monomers. That may be the above.

(Aqueous composition)
The aqueous composition of the present invention is a liquid, dispersion or emulsion aqueous composition containing the copolymer of the present invention and water.

The copolymer of the present invention has high water solubility, and can be particularly an aqueous composition of a solution or a dispersion.

The method for producing the aqueous composition of the present invention is not particularly limited, and examples thereof include a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method.

In the case of emulsification and dispersion, a composition containing an organic solvent and a surfactant can be prepared.
The surfactant is not particularly limited, and a general surfactant can be used. As the surfactant, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric ionic surfactant and a silicone-based surfactant can be appropriately selected and used, and these can be used alone. It may be used alone or in combination of two or more.

The cationic surfactant is not particularly limited, and for example, a monoalkyltrimethylammonium salt, a dialkyldimethylammonium salt, an alkylpyridinium salt, an N, N-dialkiloyloxyethyl-N-methyl, or an N-hydroxyethylammonium salt. , Alkylamine salt, stearyldimethylbenzylammonium salt and the like. The monoalkyltrimethylammonium salt is not particularly limited, but for example, 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. Can be mentioned. The dialkyldimethylammonium salt is not particularly limited, and is, for example, dibutyldimethylammonium chloride, dihexyldimethylammonium chloride, dioctyldimethylammonium chloride, didecyldimethylammonium chloride, didodecyldimethylammonium chloride, ditetradecyldimethylammonium chloride, dihexa. Decyldimethylammonium chloride, distearyldimethylammonium chloride, dibutyldimethylammonium chloride, dihexyldimethylammonium bromide, dioctyldimethylammonium bromide, didecyldimethylammonium bromide, didodecyldimethylammonium bromide, ditetradecyldimethylammonium bromide, dihexadecyldimethylammonium Examples thereof include bromide and distearyldimethylammonium bromide. The alkylpyridinium salt is not particularly limited, and examples thereof include 1-hexadecylpyridinium chloride.

The anionic surfactant is not particularly limited, and for example, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfonate, α-olefin sulfonate, alkyl sulfate, alkyl sulfate ester salt, and alkyl ether phosphorus. Acids, N-acylamino acid salts, alkylallyl sulfonates, alkyl ether sulfates, alkylamide sulfates, alkylphosphates, alkylphosphonic acids or salts thereof, alkylamide phosphates, alkylylalkyltaurine salts, fatty acids Salt, polyoxyethylene alkyl ether acetate, coconut oil fatty acid methyl taurine sodium, polyoxyethylene alkyl ether sulfate, phosphate ester salt, polyoxyethylene alkyl ether phosphate, dialkyl sulfosuccinate, perfluoroalkyl phosphate ester , N-acyl-L-glutamate, N-acyl-L-arginine ethyl-DL-pyrrolidone carboxylate and the like. Specifically, but not particularly limited, for example, sodium deoxycholate, sodium dodecylsulfate, sodium laurethsulfate, sodium myristylsulfate, sodium cetylsulfate, sodium oleylsulfate, sodium dodecylbenzenesulfonate, 1,2-dihydroxypropanesulfone. Examples thereof include sodium acid acid, sodium polyoxyethylene lauryl ether acetate, and sodium N-palm oil fatty acid acylglutamate.

The nonionic surfactant is not particularly limited, and is, for example, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, polyoxyethylene hydrogen oxide. Oil / hardened castor oil, polyoxyethylene sterol / hydrogenated sterol, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyethylene glycol fatty acid ester, polyoxyethylene glyceryl isostearate, sorbitan fatty acid ester, glycerin fatty acid ester , Diglycerin fatty acid ester, polyglycerin fatty acid ester.

The polyglycerin fatty acid esters are not particularly limited, but for example, hexaglyceryl monolaurate (HLB14.5), hexaglyceryl monomyristate (HLB11), hexaglyceryl monostearate (HLB9.0), hexaglyceryl monooleate. (HLB9.0), decaglyceryl monolaurate (HLB15.5), decaglyceryl monomyristate (HLB14.0), decaglyceryl monostearate (HLB12.0), decaglyceryl monoisostearate (HLB12.0), mono Decaglyceryl oleate (HLB12.0), decaglyceryl distearate (HLB9.5), decaglyceryl diisostearate (HLB10.0), decaglyceryl pentaisostearate (HLB3.5), decaglyceryl pentaoleate (HLB3.5) ) Etc. can be mentioned.

The polyoxyethylene sorbitan fatty acid esters are not particularly limited, but for example, polyoxyethylene monostearate (hereinafter abbreviated as POE) (5) glyceryl (HLB9.5), POE monostearate (15) glyceryl (HLB13). .5), polyoxyethylene glycerin fatty acid esters such as POE monooleate (5) glyceryl (HLB9.5), POE monooleate (15) glyceryl (HLB14.5), monococonut oil fatty acid POE (20) sorbitan ( HLB16.9), POE monopalmitate (20) sorbitan (HLB15.6), POE monostearate (20) sorbitan (HLB14.9), POE monostearate (6) sorbitan (HLB9.5), tristearic acid POE (20) sorbitan (HLB10.5), monoisostearate POE (20) sorbitan (HLB15.0), monooleate POE (20) sorbitan (HLB15.0), monooleate POE (6) sorbitan (HLB10. 0), POE trioleate (20), sorbitan (HLB11.0), and the like.

The polyoxyethylene sorbit fatty acid ester is not particularly limited, and for example, monolauric acid POE (6) sorbitol (HLB15.5), tetrastearate POE (60) sorbitol (HLB13.0), tetraoleic acid POE (30). ) Sorbitol (HLB11.5), tetraoleic acid POE (40) sorbitol (HLB12.5), tetraoleic acid POE (60) sorbitol (HLB14.0), tetraoleic acid POE (6) sorbitol (HLB8.5), Examples thereof include POE hexastearate (6) sorbitol (HLB3.0).

The polyoxyethylene lanolin, lanolin alcohol, and honey wax derivatives are not particularly limited, and are, for example, POE (10) lanolin (HLB12.0), POE (20) lanolin (HLB13.0), POE (30) lanolin (HLB15). .0), POE (5) lanolin alcohol (HLB12.5), POE (10) lanolin alcohol (HLB15.5), POE (20) lanolin alcohol (HLB16.0), POE (40) lanolin alcohol (HLB17.0) ), POE (20) Solbit Mitsurou (HLB9.5), POE (6) Solbit Mitsurou (HLB7.5) and the like.

The polyoxyethylene castor oil and hardened castor oil are not particularly limited, but for example, POE (20) castor oil (HLB10.5), POE (40) castor oil (HLB12.5), POE (50) castor oil. (HLB14.0), POE (60) castor oil (HLB14.0), POE (20) hardened castor oil (HLB10.5), POE (30) hardened castor oil (HLB11.0), POE (40) hardened castor Oil (HLB13.5), POE (60) Hardened castor oil (HLB14.0), POE (80) Hardened castor oil (HLB16.5), POE (40) Hardened castor oil (100) Hardened castor oil (HLB16.5) ), POE (3) castor oil (HLB3.0) and the like.

The polyoxyethylene sterols and hydrogenated sterols are not particularly limited, but for example, POE (5) phytosterols (HLB9.5), POE (10) phytosterols (HLB12.5), POE (20) phytosterols (HLB15.5). ), POE (30) phytosterol (HLB18.0), POE (25) phytosterol (HLB14.5), POE (30) cholestanol (HLB17.0) and the like.

The polyoxyethylene alkyl ethers are not particularly limited, but for example, POE (2) lauryl ether (HLB9.5), POE (4.2) lauryl ether (HLB11.5), POE (9) lauryl ether (HLB14). .5), POE (5.5) cetyl ether (HLB10.5), POE (7) cetyl ether (HLB11.5), POE (10) cetyl ether (HLB13.5), POE (15) cetyl ether (HLB15) .5), POE (20) cetyl ether (HLB17.0), POE (23) cetyl ether (HLB18.0), POE (4) stearyl ether (HLB9.0), POE (20) stearyl ether (HLB18.0) ), POE (7) oleyl ether (HLB10.5), POE (10) oleyl ether (HLB14.5), POE (15) oleyl ether (HLB16.0), POE (20) oleyl ether (HLB17.0), POE (50) oleyl ether (HLB18.0), POE (10) behenyl ether (HLB10.0), POE (20) behenyl ether (HLB16.5), POE (30) behenyl ether (HLB18.0), POE ( 2) (C12-15) alkyl ether (HLB9.0), POE (4) (C12-15) alkyl ether (HLB10.5), POE (10) (C12-15) alkyl ether (HLB15.5), POE (5) Secondary alkyl ether (HLB10.5), POE (7) Secondary alkyl ether (HLB12.0), POE (9) Alkyl ether (HLB13.5), POE (12) Alkyl ether (HLB14.5) , POE (2) stearyl ether (HLB4.0) and the like.

The polyoxyethylene polyoxypropylene alkyl ethers are not particularly limited, but for example, polyoxyethylene (hereinafter abbreviated as POE) (1) polyoxypropylene (hereinafter abbreviated as POP) (4) cetyl ether (HLB9. 5), POE (10) POP (4) cetyl ether (HLB10.5), POE (20) POP (8) cetyl ether (HLB12.5), POE (20) POP (6) decyltetradecyl ether (HLB11. 0), POE (30) POP (6) decyltetradecyl ether (HLB12.0) and the like.

The polyethylene / propylene glycol fatty acid esters are not particularly limited, and for example, polyethylene glycol monolaurate (hereinafter abbreviated as PEG) (10) (HLB12.5), PEG monostearate (10) (HLB11.0), and the like. PEG monostearate (25) (HLB15.0), PEG monostearate (40) (HLB17.5), PEG monostearate (45) (HLB18.0), PEG monostearate (55) (HLB18.0) ), PEG monooleate (10) (HLB11.0), PEG distearate (HLB16.5), PEG diisostearate (HLB9.5), PEG monostearate (2) (HLB4.0), PEG stearate (HLB4.0). 2) (HLB4.5), ethylene glycol monostearate (HLB3.5), self-emulsifying propylene glycol monostearate (HLB4.0) and the like can be mentioned.

The polyoxyethylene glyceryl isostearate is not particularly limited, and for example, PEG (8) glyceryl isostearate (HLB10.0), PEG (10) glyceryl isostearate (HLB10.0), PEG (15) glyceryl isostearate. (HLB12.0), PEG (20) glyceryl isostearate (HLB13.0), PEG (25) glyceryl isostearate (HLB14.0), PEG glyceryl isostearate (30) (HLB15.0), PEG isostearate (40) ) Glyceryl (HLB15.0), PEG (50) glyceryl isostearate (HLB16.0), PEG (60) glyceryl isostearate (HLB16.0) and the like.

The sorbitan fatty acid esters are not particularly limited, and are, for example, sorbitan tristearate (HLB2.0), sorbitan sesquiisostearate (HLB4.5), sorbitan monostearate (HLB4.7), and sorbitan monoisostearate (HLB5. 0), sorbitan monooleate (HLB4.3) and the like.

The glycerin fatty acid esters are not particularly limited, but for example, glyceryl myristate (HLB3.5), glyceryl monostearate (HLB4.0), glyceryl monooleate (HLB2.5), hexaglyceryl tristearate (HLB2). .5), self-emulsifying glyceryl monostearate (HLB4.0), glyceryl monoisostearate (HLB4.0), decaglyceryl pentastearate (HLB3.5) and the like.

The diglycerin fatty acid esters are not particularly limited, and examples thereof include diglyceryl monooleate (HLB5.5). In addition, polyoxyethylene fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, polyoxyethylene cured castor oil fatty acid ester, castor oil fatty acid ester, cured castor oil fatty acid ester, ethylene glycol fatty acid ester, sucrose fatty acid ester , Organic acid monoglyceride, polyethylene glycol fatty acid monoethanolamide, polyoxyethylene lanolin alcohol ether, polyoxyethylene alkyl ether, lauric acid alkanolamide, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil pyroglutamic acid fatty acid diester, pyroglutamic acid Examples thereof include fatty acid glyceryl, polyoxyethylene glyceryl pyroglutamic acid fatty acid diester, and polyethylene-modified silicone.

The amphoteric surfactant is not particularly limited, and is, for example, alkyl betaine, fatty acid amide propyl betaine, lauryl hydroxysulfobetaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lecithin, hydrogenated lecithin. , Alkyloxyhydroxypropyl arginine hydrochloride, laurylhydroxysultaine, lauriminodipropionic acid, undecylhydroxyethylimidazolinium betaine sodium, laurylaminodiphacetate sodium, lauryldimethylaminoacetic acid betaine, N- [3-alkyloxy- 2-Hydroxypropyl] -L-arginine hydrochloride, alkylhydroxysulfobetaine, alkyldimethylamine oxide, sodium alkylaminodipropionate, dihydroxyalkylmethylglycine, sodium lauryldiaminoethylglycine and the like can be mentioned.

The silicone-based surfactant is not particularly limited, and examples thereof include PEG-10 dimethicone, PEG / PPG-20 / 20 dimethicone, polysilicone-13, and laurylpolyglyceryl-3 polydimethylsiloxyethyl dimethicone.

The content (solid content) of the copolymer of the present invention in the aqueous composition of the present invention is preferably 70% by mass or less, more preferably 60% by mass or less, and more preferably 50% by mass, in consideration of the affinity with water. More preferably, it is by mass or less.

Since the copolymer of the present invention described above efficiently absorbs ultraviolet rays having a long wavelength of 360 to 420 nm, it can be used for various purposes, and is not particularly limited, but includes sunlight or ultraviolet rays in particular. It can be used particularly well for applications that may be exposed to light. For example, glass substitutes, windowpanes, glass coating agents and protective agents such as light-collecting glass and light source protective glass, light source members such as fluorescent lamps and mercury lamps that emit ultraviolet light, containers or packaging materials for foods and chemicals, agriculture and industry. Examples thereof include anti-fading agents for sheets, printed materials, dyed products, dyes and pigments, display boards, indicator lamps, cards and the like.

Among them, the copolymer of the present invention and its composition are particularly coated to form an optical material and an optical layer because they can impart ultraviolet absorption ability and high refractive index while maintaining the transparency of the matrix. It can be used as an agent, and is suitable for, for example, a functional optical layer, a film or member having an optical layer, or an optically molded product.

Examples of the film or member having a functional optical layer include a single-layer film, a base film or a substrate, and a multilayer film or a substrate with an optical layer in which one or multiple optical layers are provided according to various uses. Often, when a multi-layer optical layer is provided, the copolymer of the present invention is used for at least one of the optical layers.

Among the films and members having a functional optical layer, the optical film may be a base film provided with a functional layer according to various uses, and is not particularly limited, but for example, various optical disk substrates. Protective film, reflective film, antireflection film, alignment film, polarizing film, polarizing layer protective film, retardation film, light diffusion film, viewing angle improving film, electromagnetic wave shielding film, antiglare film, light shielding film, brightness improving film, etc. Can be mentioned.

As a member having a functional optical layer, at least one of an antireflection 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 provided on the surface of a panel substrate or the like. Examples thereof include members laminated with one layer or multiple layers.

Further, the copolymer of the present invention is suitable for a surface protective film for a solar cell. A solar cell element usually has a configuration in which an active layer that works as a solar cell is provided between a pair of substrates, but a flexible solar cell is made of a polyester material such as a gas barrier film used as a member thereof or an organic material. In a solar cell, the active layer itself absorbs ultraviolet rays and deteriorates, so an ultraviolet-absorbing protective film is required. Further, since the solar cell is installed outdoors for many years, such a protective film is required to have high weather resistance. Further, since a solar cell absorbs light energy and converts it into electric power, such a protective film is required to have high transparency. That is, a protective film for protecting a flexible solar cell is 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. There is.

The copolymer and its composition of the present invention include plastic lens elements for eyeglasses, contact lenses, optical pickup lenses, optical lenses such as camera lenses and lenticular lenses, prisms, filters, touch panel substrates, light guide plates, and the like. It can be suitably used for optical substrates, optical fibers, optical layers such as information recording substrates, and optically molded products. Optical lenses include plastic lenses such as lens films such as Fresnel lens films and lenticular lens films, and miniaturized optical functional elements for the purpose of improving light-collecting and light-diffusing properties, and focusing on light-receiving elements of image pickup elements. It is also suitable for a microlens array using a microlens having a small diameter of several μm, which is used for such purposes. Further, as a coating agent, it is also suitable for forming an optical layer for the above-mentioned applications.

Further, the copolymer and the composition thereof of the present invention can be used for display substrates, for example, liquid crystal displays, organic EL displays, plasma displays, field emission displays, flat panel display substrates such as electronic paper, or liquid crystal displays, signals, neon signs. It is also suitable for backlight substrates and the like.

Further, the copolymer of the present invention and its composition have excellent ultraviolet absorbing ability and highly hydrophilic function, and are not particularly limited in the field where stabilization and functionalization are required by the ultraviolet absorbing ability. For example, it can be used for dyes, pigments, pigments, inks, paints, pharmaceuticals, surface coatings, cosmetics, cosmetics, photographic materials, textiles and the like.

In the above applications, the copolymer of the present application and its composition are highly stable in the state of an aqueous solution and an aqueous dispersion without using an organic solvent, are highly safe for humans under a low environmental load, and are useful. Is high.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

1. 1. Monomers The following raw materials were used to synthesize copolymers consisting of each monomer.
Monomers A1 and 2 were synthesized by the method described in WO 2019/087983. Monomers A3 and 4 were synthesized by the methods shown below. Each of the monomers in Tables 1 and 2 is acrylic acid, 2-hydroxyethyl methacrylate, methyl acrylate, acrylonitrile, styrene, 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H. -The reagent of Tokyo Chemical Industry Co., Ltd. was used for benzotriazole, and the reagent of Kanto Chemical Co., Ltd. was used for 28% aqueous ammonia.

Monomer (A)

<Monomer A3>
2- (2-Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole (50 g, 0.16 mol), 3-mercapto-1-propanol (22 g, 0.24 mol), potassium carbonate ( 48 g, 0.35 mol) was heated and stirred in 125 g of DMF for 12 hours. After completion of the reaction, 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 for 3 hours at room temperature. After completion of the reaction, purification was performed to synthesize a pale yellow solid monomer A3.
FT-IR (KBr): 2956cm ^-1 : O-H expansion and contraction vibration 1726cm ^-1 : C = O expansion and contraction vibration 1485, 1392cm ^-1 : Triazole ring expansion and contraction vibration
¹ H-NMR (CDCl ₃ 400MHz): δ 1.49 (S, 9H, -Ph-OH-CH ₃ -C (C H ₃ ) ₃ ), 2.11 (quin, 2H, -O-CH ₂ C H ₂ CH ₂ -S-), 2.39 (s, 3H, -Ph-OH-C H ₃ -C (CH ₃ ) ₃ ), 3.13 (t, 2H, -O-CH ₂ CH ₂ C H ₂ -S-), 4.32 (t, 2H, -OC H ₂ CH ₂ CH ₂ -S-), 5.85 (d, 1H, C H ₂ = CH-C (= O) -O-), 6.14 (quin, 1H, CH ₂ = C H -C (= O) -O-), 6.42 (d, 1H, C H ₂ = 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-O H -CH 3 -C (CH 3) 3)
_{^{13 C-NMR (CDCl 3 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 ( C _arom -S), 139.2 ( C _arom -C (CH ₃ ) ₃ ), 146.7 ( C _arom -OH), 128.3 ( C H ₂ = CH -C (= O) -O-), 131.1 (CH ₂ = C H-C (= O) -O-), 166.1 (CH ₂ = CH- C (= O) -O-)

<Monomer A4>
2- (2-Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole (5.6 g, 18 mmol), 4-hydroxybenzenethiol (2.9 g, 23 mmol), potassium carbonate (5. 4 g, 39 mmol) was heated and stirred in 17 g of DMF for 8 hours. After completion of the reaction, ion-exchanged water was added to precipitate crystals, and the mixture was 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 completion of the reaction, purification was performed to synthesize a pale yellow solid monomer A4.
FT-IR (KBr): 2959cm ^-1 : O-H expansion and contraction vibration 1747cm ^-1 : C = O expansion and contraction vibration 1487, 1403cm ^-1 : Triazole ring expansion and contraction vibration
¹ H-NMR (CDCl ₃ 400MHz): δ 1.48 (s, 9H, -Ph-OH-CH ₃ -C (C H ₃ ) ₃ ), 2.37 (s, 3H, -Ph-OH-C H ₃ -C (CH ₃ ) ₃ ), 6.04 (d, 1H, C H ₂ = CH-C (= O) -O-), 6.34 (quin, 1H, CH ₂ = C H -C (= O) -O-) , 6.61 (d, 1H, C H ₂ = 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-O H -CH ₃ -C (CH ₃ ) ₃ )
_{^{13 C-NMR (CDCl 3 400MHz}} ): δ 20.9 (-Ph-OH- C H 3 -C (CH 3) 3), 29.5 (-Ph-OH-CH 3 - C (CH 3) 3), 29.5 ( -Ph-OH-CH ₃ -C ( C H ₃ ) 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 - C H 3), 128.9 (C arom -S), 137.1 (C _arom -S), 139.2 ( C _arom -C (CH ₃ ) ₃ ), 150.7 ( C _arom -O-), 146.7 ( C _arom -OH), 128.3 ( C H ₂ = CH-C (= O) -O -), 131.0 (CH ₂ = C H-C (= O) -O-), 164.2 (CH ₂ = CH- C (= O) -O-)

Monomer (B)
Monomer B1: Acrylic acid Monomer B2: Ammonium acrylate salt A component (repeating unit) in which the carboxy group of acrylic acid (B1) in the copolymer is ammonium chloride with aqueous ammonia.
Monomer (C)
Monomer C1: 2-Hydroxyethyl methacrylate monomer (D)
Monomer D1: Methyl acrylate monomer (E)
Monomer E1: Acrylonitrile monomer (F)
Monomer F1: Styrene monomer (G)
Monomer G1: 2- [2-Hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole

2. Synthesis of copolymer and aqueous composition <Copolymer 1>
Monomer A1 (4.2 mmol), acrylic acid (42 mmol), isopropyl alcohol: IPA (3.8 g) was added, and after nitrogen substitution, 2,2'-azobis (isobutyronitrile) (0. 18 mmol) was added, and the copolymerization reaction was carried out by heating and stirring at 100 ° C. for 3 hours. After the reaction, IPA was removed in a vacuum dryer to obtain copolymer 1, and ion-exchanged water was added and mixed so that the copolymer had a solid content of 20% by mass, and monomer A1 and monomer B1 were added and mixed. An aqueous composition 1 of a copolymer composed of the above was obtained.

<Copolymers 2, 6-8, 10-18>
In the same manner as in the synthesis of the above-mentioned copolymer 1, the monomers A1 to 4, B1, C1, D1, E1 and F1 shown in Tables 1 and 2 are copolymerized at each molar ratio to further obtain each copolymer. , Ion-exchanged water was added and mixed so as to have the solid content of Tables 1 and 2, and aqueous compositions 2, 6 to 8, 10 to 18 of each copolymer were obtained.

<Copolymer 3>
Monomer A1 (2.1 mmol), acrylic acid (42 mmol), isopropyl alcohol: IPA (3.8 g) was added, and after nitrogen substitution, 2,2'-azobis (isobutyronitrile) (0.18 mmol) was added. , The copolymerization reaction was carried out by heating and stirring at 100 ° C. for 3 hours. After the reaction, IPA was removed with a vacuum dryer, and 28% aqueous ammonia was added and reacted so that the molar ratio of ammonia to 1 mol of the carboxyl group of monomer B1 in the dried copolymer was 0.25 mol. Copolymer 3 (aqueous composition) is obtained, and ion-exchanged water is added and mixed so that the copolymer has a solid content of 20% by mass, and the copolymer weight is composed of monomer A1, monomer B1, and monomer B2. A coalesced aqueous composition 3 was obtained.

<Copolymer solutions 4, 5, 9, 19-22>
After copolymerizing the monomers A1, B1, F1 and G1 shown in Tables 1 and 2 at each molar ratio in the same manner as in the synthesis of the copolymer solution 3, the ratio of the monomers B1 and B2 is shown in Table 1. 28% aqueous ammonia was added and reacted so as to be 2, and each polymer (aqueous composition) was further added and mixed with ion-exchanged water so as to have the solid content shown in Tables 1 and 2, and each copolymer weight was obtained. Combined aqueous compositions 4, 5, 9, 19-22 were obtained.

After the copolymerization reaction of all the copolymers ^{, it was confirmed by 1} H-NMR measurement that the peak of the hydrogen atom attributed to the carbon-carbon double bond of the monomer disappeared and the reaction proceeded.

3. 3. Evaluation of copolymers and aqueous compositions 3-1. Appearance of Aqueous Composition The appearance of the copolymer solution obtained above was observed and shown in Tables 1 and 2.
As the copolymers of Examples 1 to 20 (copolymers 1 to 20), aqueous solutions and dispersions having high hydrophilicity and high stability without precipitation were obtained. The aqueous solution and dispersion of these copolymers were stored in a constant temperature bath at 25 ° C. for one month, and it was confirmed that they did not precipitate and were excellent in stability over time.

On the other hand, under the same conditions, solid content of 40% by mass, monomer (A) / monomer (B) = 0.01, Comparative Examples 1 and 2 (copolymers 21 and 22) were not dissolved and precipitated. In Examples 4 and 5 (copolymers 4 and 5), a uniform transparent aqueous solution was obtained, and the high hydrophilicity of the copolymer of the present application was confirmed.

Further, in Example 1 (copolymer 1) having a solid content of 20% by mass and monomer (A) / monomer (B) = 0.1, the monomer (A) was a cloudy dispersion without precipitation. ) / Monomer (B) = 0.05 in Examples 2 and 3 (copolymers 2 and 3), a uniform transparent aqueous solution can be obtained, and the larger the ratio of the monomer (B), the higher the hydrophilicity. It was suggested.

Further, the molar ratio (A) / (B) or (A) / ((B) + (C)) of the polymer (A), the monomer (B), and the polymer (C) is 0.5 or less and more than 0.09. In Examples 1, 7, 14 (polymers 1, 7, 14: 0.1), a uniform cloudy dispersion without precipitation was used, and the molar ratio (A) / (B) was 0.09 or less, 0.05. Super Example 17 (polymer 17: 0.06) is a uniform transparent aqueous solution, Example 18 (polymer 18: 0.06) is a uniform cloudy liquid without precipitation, molar ratio (A) / Example 2 (polymer 2: 0.05) and 3 (copolymer) in which (B), (A) / (C) or (A) / ((B) + (C)) is 0.05 or less. 3: 0.05), 4 (Copolymer 4: 0.01), 5 (Copolymer 5: 0.01), 6 (Copolymer 6: 0.01), 8 (Copolymer 8: 0.05), 9 (Copolymer 9: 0.05), 10 (Copolymer 10: 0.02), 11 (Copolymer 11: 0.01), 12 (Copolymer 12: 0. 02), 13 (Copolymer 13: 0.02), 15 (Copolymer 15: 0.01), 16 (Copolymer 16: 0.01), 19 (Copolymer 19: 0.02) , 20 (polymer 20: 0.02) are all transparent aqueous solutions, and from the viewpoint of hydrophilicity, it is better that the ratio of the monomers (B) and (C) is large, and the tendency is that B and C. It was suggested that the same was true even if a polymer other than the above was contained.

3-2. Ultraviolet Absorption Characteristics of Copolymers and Aqueous Compositions The aqueous compositions 1 to 20 of each copolymer obtained above are diluted with ion-exchanged water to a solid content of 0.02 to 0.08% by mass, and ultraviolet visible red. The absorption spectrum was measured using an external spectrophotometer (UH4150V manufactured by Hitachi High-Tech Science), and the maximum absorption wavelength was confirmed (Table 1). The spectrum of the aqueous composition (0.08% by mass aqueous solution) of the copolymer 5 is shown in FIG.

Further, the absorption spectrum of the sample obtained by dehydrating the water of the copolymer 22 (aqueous composition) under heating and reduced pressure and dissolving it in methanol at 0.08% by mass was measured in the same manner (Table 2), and the spectrum is shown in FIG. show.

The copolymers 1 to 20 of the present invention in which the monomer (A) (monomer A1 to A4) containing the above formula (i-1) is introduced into the benzotriazole group and the aqueous composition thereof are the conventional ultraviolet absorbing monomers (G). ) (Monomer G1) was introduced into the copolymer 22, and the maximum absorption wavelength was shifted to 360 to 380 nm in the long wavelength region, and it was confirmed from the wavelength of FIG. 1 that the absorption of ultraviolet rays in the vicinity of 360 to 420 nm was excellent.

Further, from the absorption spectra of the aqueous composition of the copolymer 5 of FIGS. 1 and 2 and the methanol solution of 22, the absorption spectrum on the long wavelength side at the absorption peak at 330 to 390 nm and the baseline (absorption spectrum at 380 to 500 nm). The absolute value of the slope of the absorption peak in the wavelength region of 330 to 390 nm on the long wavelength side was obtained by the following equation, with the intersection with the line with the slope of 0) as the peak end (example: FIG. 1).
| Inclination of absorption peak in wavelength region of 330 to 390 nm on the long wavelength side | = | (Absorbance of peak end-absorbance of absorption peak in wavelength region of 330 to 390 nm) / (Absorption wavelength of peak end -330 to 390 nm The wavelength of the absorption peak in the wavelength region of) |

The absorption peak on the long wavelength side in the wavelength region of 330 to 390 nm is sharper in the copolymer 5 than in the copolymer 22, and the inclination of the absorption peak in the wavelength region of 330 to 390 nm on the long wavelength side is 0. It was 0061 (the inclination of the copolymer 22 was 0.0048). It was confirmed that the copolymer and the aqueous composition of the present invention have few cuts in the range of 430 to 500 nm (visible region) and are excellent in the effect of suppressing yellowing.

Claims (10)

A copolymer of the following monomer (A) and a monomer component containing the monomer (B) and / or the monomer (C).
(Monomer (A))
The following formula (I):

(In the formula, R ^{1 to} R ⁹ are independent of each other, and 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, and R ¹¹ is substituted independently when m is 2 or more. It represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a group, and R ¹² is the following formula (i-2) :.

(In the formula, R ^12a , R ^12b , and R ^12c each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and A is selected from an ester group, an amide group, and an aromatic group. It represents a divalent group, and X represents a monovalent group represented by a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. l indicates an integer of 0 or 1, and m indicates an integer of 0 to 3. ) Indicates a monovalent group selected from a monovalent sulfur-containing group, 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). ) Is represented by a benzotriazole compound.
(Monomer (B))
Carboxy group-containing vinyl monomer or salt thereof (monomer (C))
Hydroxyalkyl group-containing vinyl monomer The copolymer according to claim 1, wherein the monomer component contains the monomer (A) and the monomer (B). The copolymer according to claim 1, wherein the monomer component contains the monomer (A) and the monomer (C). The copolymer according to claim 1, wherein the monomer component comprises the monomer (A), the monomer (B), and the monomer (C). The copolymer according to any one of claims 1 to 4, further containing acrylonitrile as a monomer component. The copolymer according to any one of claims 1 to 5, further comprising an ester group-containing vinyl monomer as a monomer component. The copolymer according to any one of claims 1 to 6, further comprising a styrene-based monomer as a monomer component. The copolymer according to any one of claims 1 to 7, wherein l in the formula (i-1) is 0. The copolymer according to any one of claims 1 to 8, wherein X in the formula (i-2) is an alkylene group − (CH ₂ ) _n − (n represents an integer of 1 or more) or a phenylene group. Combined. An aqueous composition containing the copolymer according to any one of claims 1 to 9 and water.

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