JP2021147515A - Copolymer including benzotriazole-based ultraviolet-absorbing unit and composition thereof - Google Patents

Abstract

To provide a copolymer that efficiently absorbs ultraviolet rays having a long wavelength of 360-420 nm; and provide a copolymer that exhibits high affinity with an organic solvent and has, therefore, high solubility and dispersibility when combined with the organic solvent, offering high stability, and also has excellent strength and light fastness at high temperatures, and a composition of the copolymer.SOLUTION: A copolymer of monomer components according to the present invention contains following monomer (A) and monomer (B). Monomer (A): a benzotriazole compound having a monovalent sulfur containing group. Monomer (B): an ester 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. Further, the solubility and dispersibility of the (co) polymer in an organic solvent and water have not been investigated in detail.

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 was synthesized, but attention was paid to the affinity, light resistance, and glass transition point of the copolymer with various organic solvents. There is no mention of strength. Further, in recent years, it has an ability to absorb wavelengths in the vicinity of 360 to 420 nm, has high strength and long-term stability (light resistance) under high temperature conditions, and has high long-term stability and high affinity for resins. On the other hand, a copolymer composition containing a solvent is required, and an aqueous copolymer composition is also required from the viewpoint of high safety to humans with a low environmental load.

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 highly stable due to its high affinity and dispersibility with an organic solvent from the viewpoint of efficiently absorbing long-wavelength ultraviolet rays. The copolymer and its composition have not been sufficiently studied from the viewpoints of property, strength at high temperature, and light resistance.

The present invention has been made in view of the above circumstances, and is organic due to the provision of a copolymer that efficiently absorbs ultraviolet rays having a long wavelength of 360 to 420 nm, and the high affinity with an organic solvent. It is an object of the present invention to provide a copolymer and a composition thereof, which show high stability from high solubility and dispersibility in combination with a solvent, and further have excellent strength at high temperature and light resistance. On the other hand, it is an issue to provide an aqueous composition from the viewpoint of low environmental load and safety.

In order to solve the above problems, the copolymer of the present invention is characterized by containing the following monomer (A) and the 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 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, where X represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent). Indicates a monovalent group represented by. 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)).
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 contains the copolymer, water and a surfactant.

The copolymer of the present invention and its composition efficiently absorb ultraviolet rays having a long wavelength of 360 to 420 nm. In addition, due to its high affinity with organic solvents, it exhibits high solubility and high stability in combination with organic solvents, and also exhibits excellent strength and light resistance at high temperatures. On the other hand, by using an aqueous composition containing a surfactant, a composition having a low environmental load and high safety can be obtained.

It is an ultraviolet-visible absorption spectrum (UV chart) of the toluene solution of the copolymer 6 which is an Example of this invention. It is an ultraviolet-visible absorption spectrum (UV chart) of the toluene solution of the copolymer 26 which is a comparative example. It is an ultraviolet-visible absorption spectrum (UV chart) of the aqueous dispersion liquid of the copolymer 16 which is an Example of this invention.

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 a 1,4-phenylene group, a 1,3-phenylene group, and a 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, X is oxygen from the viewpoint of dispersibility in an organic solvent, solubility, dispersibility in water, and solubility. An ester group of −X—O—C (= O) − to which an atom is bonded 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. The alkylene group preferably has a short carbon number, preferably 1 to 18, more preferably 1 to 12, from the viewpoint of dispersibility in an organic solvent, solubility, dispersibility in water, and solubility. ~ 6 is more preferable.

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 combined with the following monomer (B) shows solubility and dispersibility in combination with the organic solvent due to its high affinity with the organic solvent, and has good affinity with the resin and is further excellent. Shows strength and light resistance at high temperatures.

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, ultraviolet absorption ability, affinity with organic solvents, strength at high temperature, high light resistance, ease of actual synthesis, absorption characteristics and cost, heat resistance, or with other monomers in the copolymer raw material. Considering that it is possible to develop high ultraviolet absorption ability by making the compatibility good ^{, one or two of R 1 to} R ⁹ are monovalents represented by the formula (i-1). It is preferable that the sulfur-containing group is a monovalent sulfur-containing group represented by the formula (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, it is preferable that the inclination of the absorption peak in the wavelength region of 330 to 390 nm on the long wavelength side is sharp. For example, the copolymer weight when monomer (A) / monomer (B) = 1. When the coalescence concentration (solid content) is 0.04% by mass, the inclination is preferably 0.015 or more, more preferably 0.02 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))
The monomer (B) is an ester group-containing vinyl monomer.
Ester 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, is preferably one but an ester group. Other than an ester 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, 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.

The monomer (B) imparts high organic solvent, affinity with resin, excellent strength at high temperature, and light resistance to the copolymer of the present invention.

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

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- Alkoxystyrene such as methoxystyrene; arylstyrene such as p-phenylstyrene; styrenesulfonic acid or a salt thereof, nitrostyrene, aminostyrene, hydroxystyrene, 4- (rimethoxysilyl) styrene and the like can be mentioned.

The acrylamide-based monomer is not particularly limited, but for example, (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-hydroxyputyl (meth) acrylamide, N, N-bishydroxybutyl (meth) ) Acrylamide and the like.

The olefinic monomer is not particularly limited, but for example, 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- Penten, vinylcyclohexane, hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene, 3,4-dichloro-1-butene, butadiene , Hexadiene, isoprene, dicyclopentadiene, norbornene, acetylene and the like.

The vinyl-based monomer is not particularly limited, but for example, 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, metallicyl sulfonic acid and its salts, 2-acrylamide-2-methyl sulfonic acid and its salts, etc., N-vinyl-2-pyrrolidone, ( Meta) Acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazin, N-vinylpyrrole, N-vinylimidazole, acrylic acid, methacrylic acid, vinyl acetate, crotonic acid, cinnamic acid, myristoleic acid, palmitreic acid, oleic acid, itacon Examples thereof include acid, itaconic acid monoester, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, citraconic acid, and citraconic acid monoester.

(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).

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, a main chain in which a vinyl group or an ethynyl group of each type of monomer is polymerized, and a group possessed by these monomers, for example, an ultraviolet absorbing group of the monomer (A), a functional group such as the monomer (B), and a 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 shown below and is not particularly limited, and examples thereof include a solution polymerization method, a massive polymerization method, an emulsion polymerization method, and a suspension polymerization method, and the solution polymerization method is preferable.

In the copolymer of the present invention, the molar ratio (A) / (B) of the monomers (A) and (B) regarding the composition of the monomer components of the copolymer from the viewpoint of affinity with an organic solvent and ability to absorb ultraviolet rays). Is preferably more than 0.01, more preferably more than 0.02, further preferably more than 0.03, and particularly preferably more than 0.04.

When the molar ratio (A) / (B) of the monomers (A) to (B) is less than 0.03, the transparency of the copolymer increases and the viscosity of the composition containing the organic solvent decreases. Improved handling. On the other hand, in the composition of the copolymer and water, the hydrophilicity is increased, and the dispersion and solubility are improved.
In the copolymer of the present invention, the total molar ratio of the monomers (A) and (B) is not particularly limited, but is 90 mol% or more, 80 mol% or more, or 50 mol% or more based on all the monomers. good.

(Composition containing copolymer and organic solvent)
The composition containing the copolymer of the present invention and an organic solvent is a composition of a solution, a dispersion or an emulsion containing the copolymer of the present invention and an organic solvent. The copolymer of the present invention has a high affinity for organic solvents, and can be used as a composition of a solution or a dispersion. The production method is shown below, but is not particularly limited, and examples thereof include a solution polymerization method, a massive polymerization method, an emulsion polymerization method, and a suspension polymerization method, and the solution polymerization method is preferable.

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

The organic solvent used in the composition of the present invention is not particularly limited, and is, for example, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, a ketone solvent, an ester solvent, a glycol ether solvent, and a glycol ether ester solvent. Examples thereof include solvents, terpene-based solvents, alcohol-based solvents, fluorine-based solvents, amide-based solvents, sulfur-based solvents, ether-based solvents and the like.

The aromatic hydrocarbon solvent is not particularly limited, but for example, toluene, xylene, benzene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexyl. The aliphatic hydrocarbon solvent such as benzene and methylnaphthalene is not particularly limited, and the ketone solvent is not particularly limited, for example, hexane, heptane, cyclohexane and the like, but for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. The ester solvent such as cyclohexanone is not particularly limited, and the glycol ether solvent such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate and γ-butyrolactone is not particularly limited, but for example. , 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 ether, propylene glycol mono n-propyl ether, The glycol ether ester solvent is not particularly limited, such as propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono n-propyl ether, and dipropylene glycol mono n-butyl ether. For example, 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, Examples thereof include 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. The terpene solvent is not particularly limited, but the alcohol solvent is not particularly limited, for example, tarpineol, dihydroterpineol, tarpinyl acetate, dihydroterpinyl acetate, etc., but is not particularly limited, for example, methanol, ethanol, n-propanol. , 2-Propanol, n-butanol, isobutanol, t-butanol and the like, and the fluorocarbon solvent is not particularly limited. Is not particularly limited, but for example, 2,2,3,3-tetrafluoro-1-propanol (TFP), 2,2,3,3,4,5,5-octafluoro-1-pentanol. (OFP), 2- (perfluorooctyl) ethanol, 1,1,2,2-tetrahydroheptadecafluorodecanol, 1,1,2,2-tetrahydroperfluorodecanol, 2- (heptadecafluorooctyl) Ethanol is not particularly limited as the fluoroethers, but for example, hydrofluoroether (for example, ethyl nonafluorobutyl ether (C ₄ F ₉ OC ₂ H ₅ )) and methyl nona fluorobutyl ether (C ₄ F ₉ OCH _3). ), Methyltridecafluorohexyl ether (including C ₆ F ₁₃ OCH ₃ ), C ₃ HF _6- CH (CH ₃ ) OC _{3 HF 6} ) and the like.

The amide-based solvent is not particularly limited, and examples thereof include dimethylformamide, diethylformamide, dimethylacetamide, N-methylpyrrolidone, tetramethylurea, and hexamethylphosphoric acid triamide.

The sulfur-based solvent is not particularly limited, and examples thereof include dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfide, diethyl sulfide, dimethyl disulfide, diethyl disulfide, and the like.

The ether solvent is not particularly limited, but for example, diethyl ether, diisopropyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, methyl-tert-butyl ether, 1,4-dioxane, 1,3-dioxolane, and the like. Cyclopentyl methyl ether and the like can be mentioned.

In addition, two or more of these organic solvents may be used in combination, and from the viewpoint of affinity with the copolymer of the present invention and industrial superiority, aromatic hydrocarbon solvents, hydrocarbon solvents, and ketones may be used. A system solvent, an ester solvent, an alcohol solvent, an amide solvent, a sulfur solvent, an ether solvent, and a mixed solvent in which two or more of them are combined are preferable. A mixed solvent of two or more kinds including a hydrogen solvent and a ketone solvent are more preferable, and a mixed solvent of two or more kinds of a combination of an aromatic hydrocarbon solvent and an aromatic hydrocarbon solvent is more preferable. The system solvent is particularly preferable.

The content (solid content) of the copolymer of the present invention in the composition containing the organic solvent of the present invention is preferably 60% by mass or less, preferably 50% by mass or less, in consideration of the affinity with the organic solvent. More preferably, 40% by mass or less is further preferable.
(Aqueous composition)

The aqueous composition of the present invention is an aqueous composition of a dispersion liquid containing the copolymer, water and a surfactant of the present invention. The method for producing the aqueous composition of the present invention is shown below and is not particularly limited, and examples thereof include a solution polymerization method, a massive polymerization method, an emulsion polymerization method, and a suspension polymerization method. Is preferable, and the emulsion polymerization method is more preferable.

The polymerization method is not particularly limited, but for example, it is emulsified 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. 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, among which cations can be used. Sexual surfactants and anionic surfactants are preferable. These may be used individually by 1 type, and may be used in combination of 2 or more type.

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 and the like.

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.

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

When an organic solvent is used, those listed above can be used.

The content (solid content) of the copolymer of the present invention in the aqueous composition of the present invention is preferably 60% by mass or less, more preferably 50% by mass or less, and 40% by mass in consideration of the stability of dispersion. % Or less is more preferable.

Regarding the composition of the monomer component of the copolymer from the viewpoint of the stability of the dispersion liquid of the aqueous composition, the molar ratio (A) / (B) of the monomers (A) to (B) is preferably less than 0.10. Less than 0.05 is more preferable, less than 0.03 is further preferable, and 0.02 or less is particularly preferable. Further, from the viewpoint of ultraviolet absorption ability, (A) / (B) is preferably 0.005 or more, more preferably 0.01 or more, and further preferably 0.02 or more. From the viewpoint of both stability and ultraviolet absorption ability, (A) / (B) is more preferably 0.005 or more and less than 0.05, further preferably 0.005 or more and less than 0.03, and 0.005 or more and 0. 0.02 or less is particularly preferable.

(Use)
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 in various fields, and in particular, applications that may be exposed to sunlight or light including ultraviolet rays. It can be used particularly preferably. 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 polymer 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 an excellent ultraviolet absorbing ability, and are not particularly limited in the field where stabilization and functionalization are required by the ultraviolet absorbing ability, but for example, dyes, pigments, and the like. It can also be used for 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 have a high affinity for an organic solvent, for example, a resin or the like, while the aqueous composition of the present application uses an organic solvent. It is highly stable in the state of an aqueous dispersion, is highly safe for humans with a low environmental load, and is highly useful. Further, it has high strength at high temperature, and is suitable when the copolymer of the present application is used at high temperature in the above-mentioned applications, and when it has high light resistance and is exposed to light for a long period of time.

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. Monomer A copolymer was synthesized using the following monomer.
Monomer A1 was synthesized by the method described in WO 2019/087983. Monomers A2 and 3 were synthesized by the methods shown below. For each of the monomers in Tables 1 to 4, the reagents methyl methacrylate and 2- [2-hydroxy-5-[2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole of Tokyo Chemical Industry Co., Ltd. were used. board.
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), 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 A2.
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 A3>
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 A3.
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 _arom ), 125.3, 141.7, 143.2 ( C _arom ), 128.2 ( C _arom -CH 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 B: Methyl methacrylate

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

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

<Copolymers 2-15, 22-32>
By the same method as the synthesis of the above-mentioned copolymer 1, the monomers A1 to 3, B, and C corresponding to Tables 1, 2 and 4, respectively, are copolymerized at each molar ratio and the amount of the organic solvent charged ratio. , Compositions 2 to 15 and 22 to 32 of each copolymer were obtained.

<Copolymer 16>
Monomer A1 (10 g, 21 mmol), monomer B (90 g, 899 mmol), anionic surfactant: sodium dodecyl sulfate (6 g, 21 mmol), ion-exchanged water (150 g) are mixed and homogenized at 1200 rpm for 45 minutes. , Emulsified. After substitution with nitrogen, 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 carry out polymerization to obtain an aqueous composition of the copolymer 16. rice field.

<Copolymers 17-21>
By the same method as the synthesis of the above-mentioned copolymer 16, the copolymerization reaction was carried out at the molar ratios of the monomers A1 to 3 and the monomers B and the surfactant corresponding to Table 3, respectively, and the compositions 17 to 21 of the respective copolymers were carried out. Got

In each of the copolymers, ¹ H-NMR measurement confirmed that the peak of the hydrogen atom assigned to the carbon-carbon double bond of the monomer disappeared and the reaction proceeded.

3. 3. Evaluation of copolymers and copolymer compositions 3-1. Appearance of Copolymer Composition In Examples 1 to 14 (copolymers 1 to 14), a cloudy dispersion without precipitation and a transparent solution were obtained, whereas Comparative Examples 1 to 5 (polymers 24 to 14) were obtained. In 28), precipitation occurred immediately after the synthesis, and it was confirmed that the copolymer of the present invention had a high affinity for the organic solvent. 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 at 25 ° C. for 1 month without precipitation (Table 1). ). Regarding the molar ratio (A) / (B) of the monomer (A) to the monomer (B), Examples 16 to 21 (copolymer 16 to) of the monomer (A) / monomer (B) = 0.02. 21) becomes cloudy (dispersed in water), monomer (A) / monomer (B) = 0.03, Example 4 (copolymer 4) becomes slightly cloudy, and monomer (A) / monomer (B) = 0. Examples 1 to 3, 5 to 14 (copolymers 1 to 3, 5 to 14) of .04 or more became transparent, suggesting that the higher the ratio of the monomer (A), the higher the affinity for the organic solvent. rice field. On the other hand, the lower the ratio of the monomer (A), the lower the viscosity was observed.

3-2. Ultraviolet absorption characteristics of the copolymer and the copolymer composition The compositions 1 to 14 (Examples 1 to 14) and the copolymer 26 (Comparative Example 3) of the respective copolymers obtained above have a solid content of 0. It was diluted with the solvent used in the synthesis to 04 to 0.05% by mass, and the absorption spectrum was measured using an ultraviolet visible infrared spectrophotometer (UH4150V manufactured by Hitachi High-Tech Science) (Table 1). The spectrum of the 0.04 mass% toluene solution of the copolymer 6 is shown in FIG. 1, and the spectrum of the 0.04 mass% toluene solution of the copolymer 26 is shown in FIG.

The copolymers 1 to 14 of the monomer (A) into which the above formula (i-1) was introduced into the benzotriazole group and the compositions thereof (Examples 1 to 14) were compared with the copolymer 26 (Comparative Example 26). It was confirmed that the maximum absorption wavelength was shifted to 360 to 380 nm in the long wavelength region, and that the absorption of ultraviolet rays in the vicinity of 360 to 420 nm was excellent from the wavelength of the copolymer 6 composition of FIG.

Further, from the absorption spectra of the compositions of the copolymers 6 and 26 in FIGS. 1 and 2, the absorption spectrum on the long wavelength side at the absorption peak at 330 to 390 nm and the baseline (the slope of the absorption spectrum at 380 to 500 nm is 0). With the intersection with the line) as the peak end (example: FIG. 1), the absolute value of the inclination of the absorption peak in the wavelength region of 330 to 390 nm on the long wavelength side was obtained by the following formula.
| 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 of the wavelength region of 330 to 390 nm is sharper in the copolymer 6 than in the copolymer 26, the monomer (A) / monomer (B) is 1.00, and the copolymer concentration. When the (solid content) was 40% by mass, the inclination of the absorption peak in the wavelength region of 330 to 390 nm on the long wavelength side was 0.0277 (monomer (C) / monomer (B) = 1.00. The inclination of the copolymer 26 having a copolymer concentration (solid content) of 40% by mass is 0.0101).
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.

4. Measurement of Glass Transition Temperature of Copolymer For each of the copolymer compositions 15, 29 and 30 (Example 15, Comparative Examples 6 and 7) obtained in 2 above, the organic solvent was distilled off by heating and reducing pressure. A copolymer was obtained and measured using a differential scanning calorimeter (DSC7020 manufactured by SII) under the conditions of a heating rate of 10 ° C./min and a measurement range of 25 to 265 ° C., and the copolymer glass was measured from DDSC. The transition temperature was read (Table 2). As a result, there is a relationship of copolymer 15: 129 ° C> copolymer 29: 124 ° C> copolymer 30: 105 ° C, and the copolymer 15 containing the monomer (A) has high strength at high temperature. It was confirmed.

5. Evaluation of Aqueous Composition of Copolymer by Emulsification Polymerization Method Above 2. It was confirmed that the aqueous dispersions of the copolymers 16 to 21 obtained by the emulsion polymerization method were dispersed at 25 ° C. for 1 month in a stable state without precipitation. Further, in the same manner as in 3-2, the absorption spectrum was measured by diluting to 0.04% by mass with ion-exchanged water (Table 3, FIG. 3: Spectrum of copolymer 16), and the maximum absorption wavelength was 360 to 380 nm. In addition, it was confirmed that the absorption of ultraviolet rays in the vicinity of 360 to 420 nm was excellent, including the spectrum of FIG.

6. Evaluation of light resistance of copolymers The copolymer compositions 22, 23, 31, and 32 shown in 2 above are thinned with a spin coater (MS-B150 manufactured by Mikasa) at a rotation speed of 1500 rpm for 10 seconds, and an organic solvent is applied. Distilled off to prepare a copolymer thin film. The ultraviolet-visible transmission spectrum of the thin film was measured with an ultraviolet-visible-infrared spectrophotometer (UH4150V manufactured by Hitachi High-Tech Science), and the initial (before irradiation) ultraviolet transmittance (%) of 380, 390, 400, and 410 nm was determined to be A. I read it. Then, using an ultraviolet irradiation device (Atlas weatherometer Ci3000 + w), the ultraviolet-visible transmission spectrum was measured after irradiating with ultraviolet rays for 100 hours under the conditions of a wavelength of 300 to 400 nm, an illuminance of 42 W / m ^{2, and a black panel temperature of 63 ° C.} and the transmittance of 380,390,400,410Nm (%): reads B, the difference in the transmittance before and after irradiation delta ₁₀₀ T: calculated B-a (percent) (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, the copolymers 22 and 23 of the present invention composed of the monomers (A) and (B) (monomers A1 and monomer B) are compared with the copolymers composed of the monomers (B) and (C) from the initial stage. It was suggested that the change was small and the light resistance was excellent.

Claims (8)

A copolymer of a monomer component containing the following monomer (A) and monomer (B).
(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, where X represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent). Indicates a monovalent group represented by. 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)).
Ester group-containing vinyl monomer The copolymer according to claim 1, wherein l in the formula (i-1) is 0. The copolymer according to claim 1 or 2, 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. The copolymer according to claims 1 to 3, wherein the molar ratio (A) / (B) of the monomer (A) to the monomer (B) is more than 0.03. A composition containing the copolymer according to any one of claims 1 to 4 and an organic solvent. An aqueous composition containing the copolymer, water and surfactant according to any one of claims 1 to 4. The aqueous composition according to claim 6, wherein the surfactant is anionic or cationic. The method for producing an aqueous composition according to claim 6 or 7, wherein the aqueous composition is obtained by an emulsion polymerization method.

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