JP2003253248A - Ultraviolet absorber and polymer-bonded benzotriazole- based ultraviolet absorber, production method, treated article and treating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet absorber which is a reactive ultraviolet absorber held in an article by being cured by an addition polymerization reaction or an addition bonding reaction caused by an energy line, heat, and actions of a radical polymerization initiator and an ion polymerization initiator, and having excellent long-lasting properties, extraction resistance and heat resistance because of unbleeding properties, and to provide a polymer-bonded benzotriazole- based ultraviolet absorber exhibiting the same effects and maintaining and improving the properties of an article. <P>SOLUTION: The reactive ultraviolet absorber has a 2-(benzotriazolyl) hydroxyphenoxy residue, and an alcoholic hydroxy group or the alcoholic hydroxy group and an epoxy group in the molecule, and is obtained by reacting a compound having an epoxy compound or the alcoholic hydroxy group, and a halogen group, with a 2-(2',4'-dihydroxyphenyl)-2H-benzotriazole-based ultraviolet absorber. The polymer-bonded benzotriazole-based ultraviolet absorber, the production method, the treated article and the treating method are also provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to coating agents such as paints, inks, adhesives, and coating agents, additives for cosmetics, pharmaceuticals, foods, photographic materials, textiles, plastic molding materials, and the like. Is a coating material such as paints, inks, adhesives, coating agents, cosmetics, pharmaceuticals, foods, photographic materials, textile products, plastic molding materials, etc. The present invention relates to a benzotriazole-based UV absorber, a composition thereof, a UV-absorption-treated article, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a large number of benzotriazole-based UV absorbers have been marketed as UV absorbers, and they are added to moldings such as paints, coating agents, inks and plastics to improve light resistance. Used in. However, since these commercially available ultraviolet absorbers are non-reactive low molecular weight compounds, when used in articles such as paints and coating agents, there is a bleed-out phenomenon from the coating film, it is difficult to maintain performance, drying,
May sublime due to heating or heat during molding, and may elute from the coating film when exposed to solvents or chemicals,
As a result, the amount used may not be contained and retained in the article, and it may be difficult to retain the performance. Further, some kinds of ultraviolet absorbers have poor solubility in solvents such as paints and inks and compatibility with resins such as coating agents, so that the amount added during use is limited.

[0003]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present inventors have conducted extensive research to solve the above problems, and as a result, 2-
(2 ′, 4′-Dihydroxyphenyl) -2H-benzotriazoles are obtained by reacting a compound containing one or more epoxy groups or a halogenated alkyl having an alcoholic hydroxyl group, or an alcoholic hydroxyl group or an alcoholic group. Reactive UV absorber containing a hydroxyl group and a reactive group of an epoxy group, and a polymer-bound benzotriazole-based UV absorber obtained from the reactive UV absorber as a raw material shows non-bleeding property, does not sublime, Good elution resistance and heat resistance, and in the synthesis method,
2- (2 ', 4'-dihydroxyphenyl) which is the raw material
The inventors have found that the synthetic reaction of -2H-benzotriazoles with various epoxy compounds or alcoholic hydroxyl group-containing alkyl halides can be obtained by a very easy reaction, and completed the present invention.

[0004]

Means for Solving the Problems A 2- (2 ′, 4′-dihydroxyphenyl) -2H-benzotriazole type ultraviolet absorber is provided with an epoxy compound having at least one epoxy group in the molecule or an alcoholic hydroxyl group. 2- (benzotriazolyl) in the molecule by reacting a compound having at least one halogen group
Reactive UV absorber having a hydroxyphenoxy residue and an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group, a polymer-bound benzotriazole UV absorber obtained from the reactive UV absorber as a raw material, and a method for producing the same And a method of treating articles, more specifically 2- (2 ', 4'-dihydroxyphenyl) -2.
By reacting an H-benzotriazole type ultraviolet absorber with an epoxy compound having at least one epoxy group in the molecule or a compound having an alcoholic hydroxyl group and at least one halogen group, 2
A reactive ultraviolet absorber having a ((benzotriazolyl) hydroxyphenoxy residue, and an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group,
By using the reactive ultraviolet absorber as it is, or by further using the reactive ultraviolet absorber having an unsaturated bond introduced therein, the action of energy rays such as ultraviolet rays, electron beams and visible light, heat and radical polymerization initiators are obtained. Is a reactive ultraviolet absorber which is cured by an addition polymerization reaction or an addition bond reaction due to the action of an ion polymerization initiator and / or an ionic polymerization initiator. -(Benzotriazolyl) hydroxyphenoxy residue obtained by the above method, which comprises a polymer-bonded benzotriazole-based ultraviolet absorber containing a main chain of a polymer molecule and / or having a side chain bonded thereto, and a method for producing the same. And a method for treating an article, which comprises adding an ultraviolet absorber thereof.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to embodiments. First, a reactive ultraviolet absorber, a method for producing the same, and a method for treating an article will be described. The reactive UV absorber is a 2- (2 ′, 4′-dihydroxyphenyl) -2H-benzotriazole UV absorber having an epoxy compound having at least one epoxy group in the molecule or at least 1 having an alcoholic hydroxyl group. It is obtained by reacting a compound containing one halogen group. The obtained molecule is characterized by having a 2- (benzotriazolyl) hydroxyphenoxy residue, and an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group. To a coating agent such as a coating agent, cosmetics, pharmaceuticals, foods, photographic materials, textile products, and plastic molding materials, and a reactive ultraviolet absorbent composition and an article, which are contained by dilution. The present invention relates to a method of performing ultraviolet absorption treatment and an article subjected to ultraviolet absorption treatment by the above-mentioned ultraviolet absorption treatment method.

The 2- (2 ', 4'-dihydroxyphenyl) -2H-benzotriazole type ultraviolet absorber of the present invention means 2- (2', 4'-dihydroxyphenyl) -2.
H-benzotriazole, halogen-substituted 5 '
-Chloro-2- (2 ', 4'-dihydroxyphenyl)
-2H-benzotriazole, 5'-bromo-2-
(2 ′, 4′-dihydroxyphenyl) -2H-benzotriazole or the like, or a benzotriazole group having C _{1 to} C ₅
'-Methyl-2- (2', 4'-dihydroxyphenyl) -2H substituted with one or two alkyl groups up to
-Benzotriazole, 5'-t-butyl-2-
(2 ', 4'-dihydroxyphenyl) -2H-benzotriazole, 5', 6'-dimethyl-2- (2 ',
4′-dihydroxyphenyl) -2H-benzotriazole or the like, or 5′-methoxy-2- (2 ′, in which a benzotriazole group is substituted with an alkoxy group of C _{1 to} C ₅
4'-dihydroxyphenyl) -2H-benzotriazole, 5'-n-butoxy-2- (2 ', 4'-dihydroxyphenyl) -2H-benzotriazole,
One or more of each is used.

The reaction between the 2- (2 ', 4'-dihydroxyphenyl) -2H-benzotriazole type ultraviolet absorber of the present invention and an epoxy compound having at least one epoxy group will be described. 1 as an epoxy compound
Examples of the organic compound containing epoxy groups include styrene oxide, cyclohexane oxide, 2,3-epoxy-1-chloropropane (epichlorohydrin),
2,3-Epoxy-1-propanol (glycidol), glycidyl alkyl (C ₁ -C ₃₀ ) ether, such as methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, octyl glycidyl ether, 2-ethylhexyl. Glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, octadecyl glycidyl ether, butoxypolyethylene glycol glycidyl ether, phenyl polyethylene glycol glycidyl ether, and glycidyl alkyl ester (C
₁ -C ₃₀₎ esters, such as glycidyl acetate,
Examples thereof include glycidyl butyric acid ester, lauric acid glycidyl ester, and aromatic glycidyl ethers such as phenyl glycidyl ether and pt-butylphenyl glycidyl ether. Examples of unsaturated bond-containing epoxy compounds include glycidyl (meth) acrylate, glycidyl allyl ether, and hydroxystyrene glycidyl ether.

Further, as the organic compound containing two epoxy groups, a diglycidyl ether of (poly) alkylene glycol, for example, ethylene glycol diglycidyl ether, poly (n> 1) ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether. Ether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, and the like, and bisphenol A Epoxy resin, which is an epichlorohydrin adduct of
Examples thereof include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, resorcinol diglycidyl ether, and tetrabromobisphenol A diglycidyl ether. Further, diglycidyl ester of dicarboxylic acid, for example, succinic acid diglycidyl ester, phthalic acid diglycidyl ether and the like can be mentioned.

Examples of the compound containing three or more epoxy groups include glycerin, polyglycerin, trimethylolpropane, trimethylolbutane, pentaerythritol, sorbitol, polyglycidyl ether of cresol novolac, triglycidyl isocyanurate and tetraglycidyl. Diaminophenylmethane, tetraglycidyl metaxylenediamine, etc. are used. Further, a glycidyl group-containing monomer having an unsaturated bond, for example, glycidyl (meth) acrylate, glycidyl allyl ether, hydroxystyrene or the like alone, or another unsaturated bond-containing compound, for example, styrenes, acrylates, methacrylates, acrylamides , Alkanoic acid vinyl esters, acrylonitriles, dicarboxylic acid unsaturated bond compounds and esters thereof, glycidyl group-containing addition polymers copolymerized with vinyl chloride, vinylidene chloride, ethylene, propylene and mixtures thereof.

2- (2 ', 4'-dihydroxyphenyl) -2H-benzotriazoles using these raw materials which are epoxy group-containing compounds and organic compounds containing one or more epoxy groups in the molecule. For the reaction of, a conventionally known method can be used. The solvent, hydroxyl group, carbonyl group, an inert solvent having no active hydrogen such as amino groups, toluene, aromatic hydrocarbons such as xylene, methyl ethyl ketone, ketone solvents such as methyl isobutyl ketone, ethyl acetate, acetic acid Use one or more ester type solvents such as butyl and amyl acetate, ether type solvents such as tetrahydrofuran, dioxane, dioxolane and dimethylethylene glycol, and ether ester type solvents such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. To be done. Further, the reaction proceeds gradually without adding a catalyst, but the reaction is faster when a catalyst is added. For example, boron fluoride ethyl ether complex, quaternary ammonium salt such as triethylbenzylammonium chloride or tetramethylammonium chloride, 2-methyl-4-
Imidazole compounds such as ethylimidazole and 2-methylimidazole, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and quaternary organic phosphorus salts such as ethyltriphenylphosphonium bromide are used for glycidyl compounds. 0.001 mol% to 10 mol%
It is used, and preferably 0.1 mol% to 5 mol%. The reaction temperature is room temperature to 180 ° C, preferably 50 ° C to 150 ° C. Further, when a compound containing an unsaturated bond is used, it may be polymerized by heat. Therefore, 0.0001 to 0.01 of a polymerization inhibitor such as hydroquinone, methoxyhydroquinone, or phenothiazine is used.
% Is preferably added. The reactive ultraviolet absorber thus obtained is obtained by being concentrated, or is further extracted with an organic solvent, and the organic layer is washed with water, saturated saline or diluted sulfuric acid, and the organic layer is further concentrated, It is obtained by recrystallization and purification with an appropriate solvent. The obtained compound can be dried by a conventional method.

The structure of the reactive ultraviolet absorber containing an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group obtained by the above reaction will be described. 2- (2 ', 4'-dihydroxyphenyl) -2H
-When reacted with a compound containing one epoxy group and a benzotriazole, it becomes a reactive ultraviolet absorber containing only an alcoholic hydroxyl group. Also, 2-
When (2 ′, 4′-dihydroxyphenyl) -2H-benzotriazoles are reacted with a compound containing two or more epoxy groups, an alcoholic hydroxyl group, or an ultraviolet ray containing an alcoholic hydroxyl group and an epoxy group An absorbent is obtained. This is because when reacting with an epoxy group in an equivalent amount, a reactive ultraviolet absorber containing only an alcoholic hydroxyl group is obtained, and when an epoxy group is excessively reacted to leave an epoxy group, an alcoholic hydroxyl group and an epoxy group are left. It becomes a reactive ultraviolet absorber containing.

The reaction with the compound containing two or more epoxy groups will be described in more detail.
(2 ', 4'-dihydroxyphenyl) -2H-benzotriazoles are the reaction of the organic compound (polyfunctional epoxy compound) containing two or more epoxy groups described above, and the polyfunctional epoxy compound. Contains n (n = 2 or more) epoxy and m is the 4-position phenolic hydroxyl group of 2- (2 ′, 4′-dihydroxyphenyl) -2H-benzotriazoles, phenolic hydroxyl group When the reaction molar ratio of the epoxy group of the polyfunctional epoxy compound is m / n, and m = n, all of the n epoxy groups are 2- (2 ′, 4′-dihydroxyphenyl) -2H.
-The benzotriazoles react to contain a large number of ultraviolet ray absorbing ability in one molecule. The ultraviolet absorber having all the epoxy groups reacted is a reactive ultraviolet absorber containing only alcoholic hydroxyl groups and has a relatively large molecular weight.

When n> m, m 2- (benzotriazolyl) hydroxyphenoxys are introduced into the molecule, leaving nm epoxy groups, and alcoholic hydroxyl groups as reactive groups. It becomes a reactive ultraviolet absorber containing an epoxy group. This synthetic method is as described above, but in the case where the epoxy group is further in excess, there is a possibility of self-condensation, and at the time of synthesis, the required number of moles of 2- (2 ′,
4′-dihydroxyphenyl) -2H-benzotriazoles were charged to the reaction, the reaction was stopped before the epoxy group was completely reacted, and the remaining 2- (2 ′, 4 It is also possible to wash out the'-dihydroxyphenyl) -2H-benzotriazoles.

Next, the reaction between the 2- (2 ', 4'-dihydroxyphenyl) -2H-benzotriazole type ultraviolet absorber of the present invention and the compound having an alcoholic hydroxyl group containing at least one halogen group will be described. To do. The compound having an alcoholic hydroxyl group containing at least one halogen group used in the present invention is, for example, a monohalogenated monoalcohol, a monohalogenated dialcohol, a dihalogenated monoalcohol, or the like, such as ethylene chlorohydrin. , 2-chloro-propanol, 3
-Chloro-propanol, 2-chloro-butanol, 3
-Chloro-butanol, 4-chloro-butanol, 2-
Chloroethoxy-2-ethanol, 3-chloro-1,2
-Propanediol, 1,3-dichloro-2-propanol, and compounds containing an unsaturated bond include (meth) acrylic acid 3-chloro-2-hydroxypropyl methacrylate and (meth) acrylic acid 2-chloro-3. -Hydroxypropyl methacrylate is used, and fluorinated compounds, brominated compounds and iodide compounds are used instead of the chlorinated compounds. The above halide is 2- (2 ',
It can be reacted with 4'-dihydroxyphenyl) -2H-benzotriazoles according to a conventional method, but is not limited thereto. As an example, any of various organic solvents can be used as the reaction solvent, and 2- (2 ′, 4′-dihydroxyphenyl) -2H-benzotriazoles and alkaline substances such as sodium hydroxide, potassium hydroxide and carbonic acid can be used. It can be obtained by adding potassium or the like to form 2- (2,4-dihydroxyphenyl) 2H-benzotriazoles into a metal phenoxide, adding a halide and carrying out a substitution reaction. Reaction temperature is from room temperature to 15
0 ° C is good, and preferably 80 ° C to 130 ° C. Then, it is obtained by extracting and washing as described above, and purified by recrystallization.

The reactive ultraviolet absorber thus obtained is used as it is or after introducing an unsaturated bond. To introduce this unsaturated bond, 2- (2 ', 4'
-Dihydroxyphenyl) -2H-benzotriazoles can be obtained by the reaction of the unsaturated bond-containing epoxy compound or the unsaturated bond-containing alcoholic hydroxyl group-containing halide. Specifically, for example, 2-
Compound obtained by reaction of (2 ′, 4′-dihydroxyphenyl) -2H-benzotriazole and glycidyl methacrylate Which has the same structure as the reaction product with 3-chloro-2-hydroxypropyl methacrylate. 5-chloro-2
Compound obtained by reaction of-(2,4-dihydroxyphenyl) 2H-benzotriazole and glycidyl acrylate And has the same structure as the reaction product with 3-chloro-2-hydroxypropyl acrylate.

Furthermore, 2- (2 ', 4'-dihydroxyphenyl) -2H-benzotriazoles are reacted with an organic compound containing one epoxy group to obtain 2- (2) containing an alcoholic hydroxyl group. By reacting benzotriazolyl) hydroxyphenoxys with a compound containing an unsaturated bond having a group that reacts with an alcoholic hydroxyl group, a reactive ultraviolet absorber containing an unsaturated bond can be obtained. This is a reactive UV absorber containing an alcoholic hydroxyl group when reacted with 2- (2 ', 4'-dihydroxyphenyl) -2H-benzotriazoles and the compound containing one epoxy group described above. And a group capable of reacting with this alcoholic hydroxyl group, for example, a carboxyl group or a lower alcohol ester thereof, an isocyanate group, an acid halide, an acid anhydride group, an epoxy group, a chlorotriazine group, an isocyanate group, an alkylmethylol group, a carbodiimide group, It can be obtained by reacting with a compound containing an unsaturated bond having an oxazoline group or the like. Examples of the compound containing an unsaturated bond having a group capable of reacting with the alcoholic hydroxyl group include isocyanates such as methacryloyloxyethyl isocyanate, methacryloyl isocyanate, and methylstyrene-p-dimethylmethylisocyanate, urethane bonds, acrylic acid, and methacrylic acid. Acid, maleic acid, maleic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate,
A functional group derived from a carboxylic acid such as acrylic acid chloride or methacrylic acid chloride is reacted with an ester bond or an epoxy group such as glycidyl methacrylate to obtain an ether bond or the like. The reaction between these alcoholic hydroxyl groups and the unsaturated-containing compound having the reactive group can be obtained by a conventionally known method, and the reaction is not limited to this.

The thus obtained molecule has a 2- (benzotriazolyl) hydroxyphenoxy residue, an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group, and further has an unsaturated bond. Paints, inks that cure ultraviolet absorbers by the action of energy rays such as ultraviolet rays, electron rays and visible light, the action of heat and radical polymerization initiators and / or the action of ionic polymerization initiators,
Coating agents such as adhesives and coatings, cosmetics, food,
Reactive when added to articles such as photographic materials, textiles and plastic molding materials, by the action of energy rays such as ultraviolet rays, electron beams and visible light, the action of heat and radical polymerization initiators and / or the action of ionic polymerization initiators Non-bleeding is achieved by incorporating the UV absorber into the system added by an addition polymerization reaction or an addition bonding reaction.

Explaining individually, a coating which cures the reactive ultraviolet absorber having an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group of the present invention by heat or the like,
When added to articles such as inks, adhesives, coating agents such as coating agents, cosmetics, foods, photographic materials, textile products, plastic molding materials, etc., the resins in the articles, alcoholic hydroxyl groups in binders and crosslinking agents A group reactive with, for example, a carboxyl group or a lower alcohol ester thereof, an isocyanate group, an acid halide, an acid anhydride group, an epoxy group, a chlorotriazine group, an isocyanate group, a methylolamino group, an alkylated methylolamino group, a carbodiimide group, an oxazoline. Groups, groups capable of reacting with an epoxy group, such as a carboxyl group, a hydroxyl group,
Amino groups, acid anhydrides, epoxy groups, etc. and the reactive ultraviolet absorber having an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group of the present invention reacts, the ultraviolet absorber is retained and bound in the system, and non-bleeding occurs. To achieve. Conventionally known resins are used as the resin, binder, and cross-linking agent having those reactive groups, and the present invention is not limited to them. However, as an example, the resin or binder may be an ethylene-acrylic acid copolymer. , Ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer, styrene maleic anhydride copolymer, methacrylic acid ester methacrylic acid copolymer There are polymers, styrene acrylic acid copolymers and the like, and as the cross-linking agent, diisocyanates,
Examples thereof include triisocyanates, blocked isocyanate cross-linking agents, methylol melamine, methylated methylol melamine, butylated methylol melamine, and methylol benzoguanamine. The reactive ultraviolet absorber of the present invention is 0.001% to 10%, preferably 0.1 to 10.
3%.

The action of energy rays such as ultraviolet rays, electron rays and visible light is to add the reactive ultraviolet absorber containing an unsaturated bond of the present invention. Conventionally known curable paints and inks that are exposed to light such as ultraviolet rays, electron beams, and visible light. For example, compounds containing unsaturated bonds, urethane acrylates, polyester acrylates, neopentyl triacrylate, trimethylolpropane triacrylate, etc. The functional unsaturated bond-containing monomer or oligomer is mixed with a photopolymerization initiator, for example, benzoyl, benzoin alkyl ether, benzoin dimethyl ketal, 2-ethylthioxanthone, etc., if necessary, with a solvent, a pigment, an additive, etc., An unsaturated bond-containing reactive ultraviolet absorber is added and cured by ultraviolet rays, electron beams, and visible light. It undergoes addition polymerization with a compound containing a saturated bond and reacts in the system. It is held in. The unsaturated bond-containing reactive ultraviolet absorber of the present invention is 0.001% to 10%, preferably 0.1-3%.

Further, the function of heat or radical polymerization initiator and / or the function of ionic polymerization initiator is to add the unsaturated bond-containing reactive ultraviolet absorber of the present invention. For example, unsaturated polyester resins, thermosetting resins such as diallyl phthalate resins and their paints, inks, coating agents, and the like, specifically, unsaturated polyester resins containing maleic acid as a component, diallyl phthalate, the polyfunctional Polymerization initiator such as benzoyl peroxide, methyl ethyl ketone peroxide, and azobisisobutyronitrile, if necessary, with unsaturated unsaturated bond-containing monomer or oligomer, compound containing unsaturated bond, such as styrene or acrylic ester ,
If necessary, the unsaturated bond-containing reactive ultraviolet absorber of the present invention is added and mixed with a pigment, an additive, etc.
The unsaturated bond-containing reactive ultraviolet absorber of the present invention is an unsaturated bond such as the above-mentioned binder when cured by thermal polymerization, radical polymerization or ionic polymerization. It is retained in the system by binding and addition polymerization. The unsaturated bond-containing reactive ultraviolet absorber according to the present invention has a viscosity of 0.
It is 001% to 10%, preferably 0.1 to 3%.

Next, a polymer-bound benzotriazole-based UV absorber obtained by using the reactive UV absorber as a raw material,
A method for manufacturing the same and a method for treating an article will be described.
The reactive ultraviolet absorber having an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group obtained above, or a reactive ultraviolet absorber having an unsaturated bond is used as a raw material, and the ultraviolet absorber is 2- (2 ′, Does it contain a 2- (benzotriazolyl) hydroxyphenoxy residue derived from a 4'-dihydroxyphenyl) -2H-benzotriazole type ultraviolet absorber in the main chain of the polymer molecule and / or
Alternatively, a polyolefin-based polymer, a polyether-based polymer, a polyester-based polymer, a polyamide-based polymer having an average molecular weight of 1,000 or more, which is bound to a side chain and is contained in a polymer molecule in an amount of 10 to 90% by weight, Polyvinyl polymer,
At least one polymer selected from the group consisting of poly (meth) acryl-based polymers, polysilicone-based polymers, polyurethane-based polymers, polyurea-based polymers, epoxy resin-based resins, and melamine-based resins, or a copolymer thereof. Polymer-bonded benzotriazole-based UV absorber characterized by being bonded in a polymer molecule, a method for producing the same, and coating agents such as paints, inks, adhesives and coating agents, cosmetics, pharmaceuticals, foods A polymer-bonded benzotriazole-based ultraviolet absorber composition characterized by being diluted and contained in a medium used for photographic materials, textiles, and plastic molding materials, and a method for performing ultraviolet absorption treatment on the article, and The present invention relates to an article that has been subjected to ultraviolet absorption treatment by the ultraviolet absorption treatment method.

Polymer-bonded benzotriazole type ultraviolet absorbers can be obtained from these as follows. Three types of polymer-bonded benzotriazoles are prepared from the above-mentioned reactive ultraviolet absorber containing an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group and the above-mentioned reactive ultraviolet absorber having an unsaturated bond introduced therein. A system ultraviolet absorber can be obtained. (I) Unsaturated bond-containing 2- (benzotriazolyl)
A polymer-bonded benzotriazole-based UV absorber which is addition-polymerized by the action of a hydroxyphenoxy compound, another unsaturated bond-containing compound, a radical polymerization initiator and / or an ionic polymerization initiator. By adding this, non-bleeding from the system is achieved. (II) 2- (2 ', 4'-dihydroxyphenyl)-
2H-benzotriazoles and 1 epoxy group or 1
A polymer having a group capable of reacting an alcoholic hydroxyl group-containing 2- (benzotriazolyl) hydroxyphenoxy compound obtained by reacting with a compound having an alcoholic hydroxyl group containing one halogen group A polymer-bound benzotriazole-based ultraviolet absorber having 2- (benzotriazolyl) hydroxyphenoxys introduced into its side chain by reacting with. Non-bleed is achieved by adding it to the article. (III) 2- (2 ', 4'-dihydroxyphenyl)
-2H-benzotriazoles and 1 epoxy group and 1
An organic compound containing one alcoholic hydroxyl group, or 2
2- (benzotriazolyl) hydroxyphenoxys containing two alcoholic hydroxyl groups obtained by reaction with an organic compound containing one epoxy group by addition condensation reaction or condensation polymerization reaction with other polymerizable raw materials The resulting polymer-bound benzotriazole-based UV absorber.
Non-bleed can be achieved by adding this in the article.

Each will be described individually. (I) Unsaturated bond-containing 2- (benzotriazolyl)
In the case of a polymer-bound benzotriazole-based UV absorber which is addition-polymerized by the action of a hydroxyphenoxy compound, another unsaturated bond-containing compound, a radical polymerization initiator and / or an ionic polymerization initiator, an unsaturated bond-containing 2- (benzo Triazolyl) hydroxyphenoxy compounds and other unsaturated bond-containing compounds,
Specifically, styrenes, acrylates, methacrylates, acrylamides, vinyl alkanoates,
At least one selected from the group consisting of acrylonitriles, vinyl chloride, vinylidene chloride, ethylene, propylene, and a mixture thereof is used, and a polymer-bonded benzotriazole-based UV absorber which is addition-polymerized can be obtained. More specifically, examples of the compound having another unsaturated bond include styrenes such as styrene monomer, methylstyrene monomer, vinyltoluene, vinylethylbenzene and vinylnaphthalene, and acrylates and methacrylates include (meth) Aliphatic (C ₁ -C ₃₀ ) alcohol esters such as acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate; ) Cyclohexyl acrylate,
Alicyclic alcohol esters such as benzyl (meth) acrylate and methylcyclohexane (meth) acrylate;
Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate-containing (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. Examples thereof include acrylates, phthalates of hydroxyethyl (meth) acrylate, and glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate. Examples of acrylamides include acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide and N, N-dimethyl acrylamide. Examples of the vinyl alkanoate include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and the like. Also, as acrylonitriles,
Examples thereof include acrylonitrile and methacrylonitrile, and examples of dicarboxylic acid unsaturated bond compounds and esters thereof include maleic acid, maleic anhydride, itaconic acid, fumaric acid, and the like, and half or diesters of its aliphatic alcohol. .

Further, when a glycidyl group-containing (meth) acrylic acid ester such as glycidyl (meth) acrylate is copolymerized, in addition to the functional group derived from the ultraviolet absorbent of the present invention, an epoxy group is added to the copolymerized polymer chain. When used as a UV absorber for paints, coating agents, etc., the polymer-bound benzotriazole-based UV absorber binds as a cross-linking agent component with the binder component used in the article, and is Not just bleed
It forms a mesh structure and becomes non-bleeding. When a hydroxy group-containing (meth) acrylic acid ester such as hydroxyethyl (meth) acrylate or hydroxypropyl is used, the hydroxy group is introduced into the resin,
By reacting with a cross-linking agent used for articles such as coating agents, such as isocyanates and melamine-based cross-linking agents, not only bleeding due to a high molecular weight as described above, but also a network structure can be formed to achieve non-buret. Further, as the unsaturated bond-containing compound, (meth) acrylic acid, maleic acid,
When a carbonyl group-containing monomer such as itaconic acid is used, a carbonyl group is introduced into the polymer chain, and by neutralizing this with an alkaline substance, an aqueous polymer-bound benzotriazole-based UV absorber can be obtained. . This alkaline substance, by using a volatile alkaline substance, when used in paints, coating agents, etc., can improve water resistance, and as the volatile alkaline substance, amines can be mentioned, for example, ammonia, Methylamine, dimethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, 2-aminopropanol and the like can be used. These unsaturated bond-containing compounds and the unsaturated bond-containing 2- (benzotriazolyl) hydroxyphenoxy UV absorbers of the present invention can be prepared by conventionally known polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization. Obtained, but not limited to. The high molecular weight UV absorber is an unsaturated bond-containing 2- (benzotriazolyl) hydroxyphenoxy UV absorber in an amount of 10 to 90% by weight.
And more preferably 30 to 90%. It is used by adding it to paints, inks, adhesives, coating agents such as coating agents, cosmetics, foods, photographic materials, textile products, and plastic molding materials. This is 0.001% to 30% and preferably 0.1 to 10% for each.

(II) reacting 2- (2 ', 4'-dihydroxyphenyl) -2H-benzotriazoles with a compound having an alcoholic hydroxyl group containing one epoxy group or one halogen group 2- (benzotriazolyl) containing alcoholic hydroxyl group obtained by
By reacting hydroxyphenoxys with a polymer having a group that reacts with an alcoholic hydroxyl group, 2
In the case of a polymer-bound benzotriazole-based UV absorber having a-(benzotriazolyl) hydroxyphenoxy group introduced into the side chain, this is 2- (2 ', 4'-dihydroxyphenyl) -2.
The alcoholic hydroxyl group-containing 2- (benzotriazolyl) hydroxyphenoxy series obtained by reacting the H-benzotriazoles with the above-mentioned organic compound containing one epoxy group is used as the reactive ultraviolet absorber. A group reactive with an alcoholic hydroxyl group, such as a carboxyl group or a lower alcohol ester thereof, an isocyanate group, an acid halide group, an acid anhydride group, an epoxy group,
Polymer-bonded benzotriazole system in which 2- (benzotriazolyl) hydroxyphenoxys are introduced into the side chain by reacting with a polymer having a known reactive group such as a chlorotriazine group and an alkylmethylol group UV absorber can be obtained. Non-bleed is achieved by adding it to the article.

Specifically, as the polymer having a group capable of reacting with an alcoholic hydroxyl group, a polymer which is an addition polymer of the above unsaturated bond-containing compound or a conventionally known polymer chain is used. Polyolefin chains such as polyethylene chains, polypropylene chains, poly (ethylene-co-propylene) chains, poly (ethylene-co-propylene-co-α-olefin) chains, polypropylene glycol chains, poly (ethylene glycol-co- (Propylene glycol) chain, (polyethylene glycol)
-(Polypropylene glycol) block copolymer chain,
Polyether polymer chains such as polytetramethylene glycol chains, polybutylene adipate chains, aliphatic polyester chains such as polyethylene sebacate chains, polyethylene isophthalate chains, polybutylene terephthalate chains,
Polyester-based polymer chains such as aromatic polyester chains such as polyneopentyl terephthalate chains, polyamide-based polymer chains such as 6-nylon-based chains and 6,6-nylon-based chains, polystyrene chains, styrene copolymer chains, polyvinyl Polyvinyl polymer chains such as butyral chains, acrylic acid ester (co) polymer chains, methacrylic acid ester (co)
(Meth) acrylic (co) polymer chains such as polymer chains and acrylic-styrene copolymer chains, polysilicone polymer chains, polyurethane polymer chains, polyurea polymer chains,
Homopolymer chains selected from epoxy resin chains, melamine resin chains, cellulose polymer chains, chitosan polymer chains, etc., or copolymer chains of the above-mentioned two or more kinds of monomers or polymer chains. And as the reactive group of the polymer, a carboxyl group, an acid halide group, an acid anhydride group, a lower alkyl (C ₁ -C ₃ ) ester group, an epoxy group, an amino group, a chlorotriazine group and an isocyanate. A condensation reaction is carried out from a group consisting of known reactive groups such as groups.

For example, as the polyolefin-based reactive polymer, ethylene-co-acrylic acid copolymer, ethylene-co-methyl acrylate copolymer, ethylene-c
o-methacrylic acid copolymer, ethylene-co-methyl methacrylate copolymer, ethylene-co-vinyl alcohol-co-methacrylic acid copolymer, ethylene-c
O-ethyl acrylate-co-maleic anhydride copolymer, ethylene-co-butyl acrylate-co-maleic anhydride copolymer, ethylene-maleic anhydride graft copolymer, ethylene-co-glycidyl methacrylate copolymer , Polyethylene monocarboxylic acid and the like. In the case of vinyl polymer type, (meth) acrylic polymer type, etc., reactive groups can be introduced by copolymerizing a reactive monomer or by performing a post reaction treatment. For example, the carboxyl group is unsaturated due to the copolymerization of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid, and the acid halide group, the acid anhydride group and the lower alkyl (C ₁ -C ₃ ) ester group are unsaturated. By copolymerizing each derivative of carboxylic acid, epoxy group, chlorohydrin group is glycidyl (meth) acrylate, γ-chloro-β-hydroxypropyl (meth) acrylate is copolymerized, and amino group is N-vinyl. By saponifying a copolymer of acetic acid amide, a chlorotriazine group is obtained by reacting chlortriazine, and an isocyanate group is obtained by copolymerizing methacryloyloxyethyl isocyanate and propenylphenyl isocyanate. For condensation polymers such as polyesters, polyamides, polyurethanes, polyureas, etc., the amount ratio of the monomer raw material having a reactive group may be changed during synthesis, and one of them may be used in a slightly excessive amount or controlled after the reaction. Known to react reactive compounds or to introduce reactive groups into polymers using polyfunctional compounds with different reaction rates such as trimellitic anhydride, pyromellitic anhydride, trimellitic anhydride monochloride, tolylene diisocyanate Is achieved by

As a method for obtaining these, conventionally known methods can be used. More specifically, when the reactive ultraviolet absorber contains an alcoholic hydroxyl group, the reactive group of the polymer is a carboxyl group or a lower ester thereof. , An acid anhydride group, and an isocyanate group, and a conventionally known reaction method can be employed. In the case of a carboxyl group or a lower ester thereof, the reaction is obtained by dehydration or dealcoholization condensation reaction, and a polymer and a reactive ultraviolet absorber, and / or an organic solvent, for example, a high boiling aromatic hydrocarbon such as xylene, and / or Using a catalyst, for example, a titanium-based catalyst such as p-toluenesulfonic acid or tetrabutyl titanate, or an organotin compound such as dibutyltin oxide, a reaction temperature of 80 to 250 ° C.
A dehydration or dealcoholization reaction is carried out at a temperature of 130 ° C., preferably 130 ° C. to 220 ° C., to bind to the polymer. In the case of an acid anhydride, a polymer containing a reactive ultraviolet absorber and an acid anhydride is reacted in a solvent or without a solvent to cause ring-opening condensation. In the case of isocyanate, a polymer, a solvent, a reactive ultraviolet absorber, and / or a tin compound such as dibutyltin dilaurate as a catalyst and an amine compound such as triethylamine are added and reacted at room temperature to 200 ° C. As the reactive polymer that bonds with the alcoholic hydroxyl group, a relatively high molecular weight substance or a high molecular weight substance is used. The average molecular weight of the polymer is about 3,000 to 200,000, preferably about 5,000 to 100,000. The polymer-bonded benzotriazole-based UV absorber thus obtained is added to coating materials such as paints, inks, adhesives, and coating agents, cosmetics, foods, photographic materials and textiles, plastic molding materials, etc. Used,
The amount added is 0.001% to 30%, preferably 0.1 to 10%.

(III) 2- (2 ', 4'-dihydroxyphenyl) -2H-benzotriazoles, an organic compound containing one epoxy group and one alcoholic hydroxyl group, or two epoxy groups Polymer bond obtained by addition condensation reaction or condensation polymerization reaction of 2- (benzotriazolyl) hydroxyphenoxys containing two alcoholic hydroxyl groups obtained by reaction with contained organic compound with other polymerizable raw material In the case of a benzotriazole type UV absorber, this is 2- (2 ', 4'-dihydroxyphenyl) -2.
Organic compound containing H-benzotriazoles, one epoxy group and one alcoholic hydroxyl group, or organic compound containing two epoxy groups, or at least one or more containing two alcoholic hydroxyl groups Is a (benzotriazolyl) hydroxyphenoxy compound containing two alcoholic hydroxyl groups, which is obtained by a reaction with an organic compound containing a halogen group of 2- (benzotriazolyl). (B) A polymer-bonded benzotriazole-based ultraviolet absorber obtained by subjecting hydroxyphenoxys as a raw material to an addition copolymerization reaction or a condensation copolymerization reaction with another polymerizable raw material. The compound containing one epoxy group and one alcoholic hydroxyl group is 2,3-epoxy-1-propanol (glycidol) as described above, and 2-
When reacted with (2 ', 4'-dihydroxyphenyl) -2H-benzotriazoles, the epoxy ring opens,
One alcoholic hydroxyl group is produced, and a total of two hydroxyl groups will be contained. The organic compound containing two epoxy groups and the epoxy resin are the same as described above, and are 2- (2 ', 4'-dihydroxyphenyl) -2H
React with benzotriazoles to form two alcoholic hydroxyl groups. In addition, 2- (2 ', 4'-dihydroxyphenyl) -2H-benzotriazoles and 2
An organic compound containing at least one halogen group containing one alcoholic hydroxyl group, such as 1-chloro-2,3-propanediol, is reacted to contain two alcoholic hydroxyl groups. This reaction is as described above, and the diol, which is a reaction product with 2- (2 ′, 4′-dihydroxyphenyl) -2H-benzotriazole thus obtained, is used for addition condensation or condensation polymerization. By doing so, 2- (benzotriazolyl) -hydroxyphenoxys having an ultraviolet absorbing ability are introduced into the polymer. Specifically, a dicarboxylic acid or a lower ester thereof is used as an acid component, and the ultraviolet absorber diol alone or in combination with another diol component, a polyester resin by ester condensation or an organic diisocyanate component and the ultraviolet absorber diol alone. Or a urethane resin obtained by urethane condensation with other low molecular weight diols, polyester polyols, polyether polyols, and polycarbonate diols.

First, the case of polyester resin will be specifically described in detail. The ultraviolet absorbent diol obtained above is used alone or in part, and is obtained by a polycondensation reaction between a conventionally known acid component and an alcohol component. These components are not particularly limited, but the acid component Examples of terephthalic acid, isophthalic acid, dimethylisophthalic acid, phthalic acid, 4,4′-biphenyldicarboxylic acid, 3,3′-methylenedibenzoic acid, 4,4′-methylenedibenzoic acid, 4,4 '-Oxydibenzoic acid, 4,
Aromatic dicarboxylic acids such as 4'-thiodibenzoic acid, 4,4'-carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 1,4-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid; Succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, glutanoic acid, suberic acid, 1,12-dodecanedicarboxylic acid, 1,16-
Hexadecanedicarboxylic acid, 1,20-eicosanedicarboxylic acid, fumaric acid, maleic acid, tartaric acid, oxalic acid,
Malonic acid, pimelic acid, glutaconic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid,
Examples thereof include α, β-diethylsuccinic acid and other aliphatic dicarboxylic acids, and lower alcohol esters thereof. These are used alone or in combination of two or more.

As the alcohol component, for example, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1 , 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonane Aliphatic diols such as diol and neopentyl glycol; Alicyclic glycols such as bishydroxymethylcyclohexane and cyclohexane-1,4-diol; Aromatic diols such as xylylene glycol;
Aliphatic trihydric alcohol such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, tris- (2hydroxyethyl) Examples include polyhydric alcohols such as cyclic trihydric alcohols such as isocyanurate. These are used alone or in combination of two or more.

In order to use the obtained polyester in an aqueous solution, in order to make it self-emulsifying, trimellitic acid,
Trimellitic dianhydride, pyromellitic dianhydride, naphthalene tetracarboxylic dianhydride, diphenylmethane tetracarboxylic dianhydride, polyvalent carboxylic acid such as benzophenone tetracarboxylic dianhydride or its anhydride the above-mentioned acid If necessary, the free carboxylic acid groups remaining after being co-condensed with the components may be converted into known basic substances such as ammonia, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine and N. Amines such as phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, lithium hydroxide,
Neutralize with an inorganic alkaline substance such as sodium hydroxide or potassium hydroxide to enable self-emulsification. Further, for example, an acid or alcohol component substituted with a sulfonic acid group such as an alkali metal salt of sulfoisophthalic acid and a lower alcohol ester thereof can be co-condensed to impart the self-emulsifying property in the same manner as above. As the polycondensation catalyst of the polyester, conventionally known ones are used, and are not particularly limited, and examples thereof include acid compounds such as sulfuric acid and paratoluenesulfonic acid, tetraisopropyl titanate, metal compounds such as dibutyltin oxide, and the weight of the acid component. On the other hand, it is usually used in the range of about 0.001 to 1%. The polycondensation reaction is carried out by a conventionally known method, and is obtained by dehydration or dealcoholization condensation at 150 to 260 ° C. under normal pressure and / or reduced pressure, and is obtained by using the above-mentioned components to make it aqueous. The self-emulsifying polyester can be made into an aqueous dispersion by adding it to water and neutralizing or heating it.

Next, the case of polyurethane resin will be specifically described in detail. In the case of a polyurethane resin, the ultraviolet absorber diol obtained above may be used alone or in part to obtain a conventionally known polyisocyanate compound, a polyol, and optionally a chain extender. The ingredients are not particularly limited. Examples of the polyisocyanate compound include 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, methylene diisocyanate, isopropylene diisocyanate, lysine diisocyanate, 1,5.
Aliphatic diisocyanates such as octylene diisocyanate and dimer acid diisocyanate; 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), hydrogenated tolylene diisocyanate, methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate Alicyclic diisocyanate of 2,4- or 2,
6-tolylene diisocyanate (TDI), 4,4'-
Diphenylmethane diisocyanate (MDI), 1,5
-Naphthylene diisocyanate, xylylene diisocyanate (XDI), triphenylmethane triisocyanate, tris (4-phenylisocyanate) thiophosphate, tolidine diisocyanate, p-phenylene diisocyanate, diphenyl ether diisocyanate-
, Diphenyl sulfone diisocyanate, etc.
An adduct obtained by reacting DI, TDI, HDI, XDI, IPDI, etc. with a divalent or trivalent polyhydric alcohol, HD
Examples thereof include burette bodies such as I and IPDI, uretdione bodies such as TDI, isocyanurate bodies such as TDI, HDI and IPDI, and carbodiimide bodies. These are 1
They may be used alone or in combination of two or more.

As the polyol, polyether polyol, polyester polyol, polyether ester polyol and other polyols are used. As the polyether polyol, for example, a compound having two or more active hydrogen-containing groups (for example, a low molecular weight polyol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, or sucrose,
Glucose, sugar-based alcohols such as fructose, ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, etc. are used as initiators, and ethylene oxide (hereinafter referred to as EO) and propylene oxide (hereinafter referred to as PO and ), Alkylene oxide such as butylene oxide, amylene oxide, alkyl glycidyl ether such as methyl glycidyl ether,
Polyethylene glycol ether, polypropylene ether glycol, polyethylene propylene ether glycol, polytetramethylene ether glycol obtained by addition-polymerizing one or more aryl glycidyl ethers such as phenyl glycidyl ether and cyclic ether monomers such as tetrahydrofuran by a known method. , Polyhexamethylene ether glycol and the like.

Examples of polyester polyols include condensation type polyester polyols, lactone type polyester polyols and polycarbonate polyols.
The condensed polyester polyol is obtained by polycondensing a polybasic acid and a polyhydric alcohol. Examples of polybasic acids include succinic acid, glutaric acid, adipic acid,
Sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, tartaric acid, oxalic acid, malonic acid, pimelic acid, suberic acid, curtaconic acid, azelaic acid, 1,4-cyclohexyldicarboxylic acid, α-hydro Muconic acid, β-hydromuconic acid, α
Examples thereof include dibasic acids such as -butyl-α-ethylglutaric acid and α, β-diethylsuccinic acid, or anhydrides thereof. These are used alone or in combination of two or more. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-
Pentanediol, 1,8-octanediol, 1,9
Aliphatic glycols such as nonanediol and neopentyl glycol, alicyclic glycols such as bishydroxymethylcyclohexane and cyclohexane-1,4-diol, aromatic glycols such as xylylene glycol, C ₁
To glycols such as alkyl dialkanol amines such as C ₁₈ alkyl diethanol amine and the like. These are used alone or in combination of two or more.

Specific examples of the condensation type polyester polyol include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate and the like.
The lactone-based polyester polyol is a polylactone diol or polycaprolactone diol obtained by ring-opening polymerization of a lactone using the diol or the like as an initiator.
Examples thereof include polymethylvalerolactone diol.
The polyether ester polymer is obtained by reacting a mixture with an ether group-containing diol or other glycol with the above dicarboxylic acid or an anhydride thereof, or by reacting a polyester glycol with an alkylene oxide, for example, Examples thereof include poly (polytetramethylene ether) adipate. The ether group-containing diol is used alone or in combination of two or more. Examples of other polyols include polyacrylic polyols, polyolefin polyols, polybutadiene polyols, fat-and-oil modified polyols, and the like. Each of the above polyols is used alone or in combination of two or more. Further, in order to obtain a water-based ultraviolet absorbent polymer, and in order to impart self-emulsifying property to the obtained polyurethane when producing polyurethane, for example, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (Hydroxymethyl) lactic acid, 2,2-bis (hydroxymethyl) valeric acid, 2,2-bis (hydroxymethyl) butyric acid, 2,2-
A carboxylic acid-containing diol such as bis (hydroxymethyl) butanoic acid can be copolymerized, and then, if necessary, the carboxylic acid can be neutralized with the above-mentioned basic substance to be self-emulsifying. As another method, a terminal isocyanate urethane prepolymer is synthesized without using the above-mentioned carboxylic acid-containing diol, and the above-mentioned carboxylic acid-containing diol or 2-carboxy-1,4-as a chain extender.
Examples of the method include chain extension using a carboxylic acid-containing diamine such as phenylenediamine, but the method is not limited to these methods.

After the production of the polyurethane, a polyurethane end stopper may be used, if desired. Examples of the terminal terminator include not only monofunctional compounds such as monoalcohol and monoamine, but also compounds having two kinds of functional groups having different reactivities to isocyanate, such as methyl alcohol and ethyl alcohol. , N
-Propyl alcohol, isopropyl alcohol, n-
Butyl alcohol, isobutyl alcohol, tert-
Monoalcohols such as butyl alcohol; monoamines such as monoethylamine, n-propylamine, diethylamine, di-n-propylamine, di-n-butylamine;
Alkanolamines such as monoethanolamine and diethanolamine can also be used. Among them, alkanolamines are preferable because the reaction can be easily controlled. As a catalyst for polyurethane polymerization, a conventionally known catalyst is used and is not particularly limited, and examples thereof include dibutyltin dilaurate, dibutyltin diacetate, triethylamine,
Triethylenediamine or the like is usually used in the range of about 0.001 to 1% with respect to the weight of the isocyanate component. The polycondensation reaction is carried out by a conventionally known method at room temperature to 250 ° C. in a solvent or without a solvent to form an isocyanate and a hydroxyl group or an amino group and a urethane bond,
Obtain a polyurethane resin. The polymer-bonded benzotriazole-based UV absorber thus obtained is a relatively high molecular weight substance or a high molecular weight substance. The average molecular weight of the polymer is about 3,000 to 200,000, preferably about 5,000 to 100,000.

Since the polymer-bonded benzotriazole type ultraviolet absorbers produced by these three methods are polymers of a relatively high molecular weight or high molecular weight region as described above, they can be used as ordinary low molecular weight functional agents. In comparison, it is superior in safety and hygiene, does not volatilize even when heated during the processing step, storage or use of articles, does not cause blooming phenomenon, and has excellent compatibility, so the required amount can be added. ,
Further, it is a feature that it does not impair the physical properties of the added article.

The method for treating the reactive ultraviolet absorber of the present invention and the article thus obtained will be described.
The reactive ultraviolet absorber of the present invention is added to synthetic resins, textile materials, paper materials, non-woven materials, paints, coating agents, printing agents, printing inks, electrophotographic developers, inkjet inks, adhesives or cosmetics. To improve the function of the article by the ultraviolet absorbing function by each conventionally known processing method such as molding, spinning, papermaking, film formation, coating, printing, printing, electrophotographic recording, inkjet printing or adhesion. It is a thing. Thereby, deterioration of elasticity due to embrittlement due to light exposure due to action of sunlight, especially ultraviolet rays, deterioration of tensile strength, deterioration of resin physical properties such as generation of cracks, deterioration of electrical properties, coloring, pigments, dyes, etc. It solves problems such as discoloration and fading of the dye, and further reduces the function due to evaporation of the functional agent due to evaporation, volatilization, and sublimation, which are the defects of ordinary low-molecular-weight functional agents, and the addition amount due to the limit of compatibility. Limitation, a processing method for improving the function of the article to solve the problem such as the reduction of the effective addition amount due to the blooming phenomenon on the surface and the contamination of other articles and the inhibition of the printability, and the article having the function improved thereby is obtained, In the case of cosmetics, the skin of a person is protected by applying makeup thereto.

Examples of the above-mentioned synthetic resin include thermoplastic molding materials used for conventionally known moldings, sheets, films and the like. For example, polyethylene resins, olefin resins such as polypropylene resins, poly (meth)
Acrylic ester resin, polystyrene resin, styrene-acrylonitrile resin, acrylonitrile-butadiene-styrene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, ethylene-acetic acid Vinyl-based copolymer, ethylene-vinyl alcohol-based resin, polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), liquid crystal polyester resin (LC
P), polyacetal resin (POM), polyamide resin (PA), polycarbonate resin, polyurethane resin and polyphenylene sulfide resin (PPS), or a polymer blend or polymer alloy of two or more kinds of resins. Further, glass fibers, carbon fibers, semi-carbonized fibers, cellulosic fibers in the above-mentioned natural resin,
A thermoplastic molding material containing a filler such as glass beads or a flame retardant is also used. For example, PET, PB
A composite material containing glass fiber of engineering plastic such as T, LCP, POM, PA, PPS or various additives such as a flame retardant, a foaming agent, a bacteriostatic agent, and a crosslinking agent are added. In addition, additives for conventionally used resins, if necessary, for example, polyolefin resin fine powder,
Polyolefin wax, ethylene bisamide wax, metal soap and the like can be used alone or in combination. As the thermosetting resin, epoxy resin,
Melamine resin, unsaturated polyester resin, etc., and thermosetting molding materials containing natural resin, glass fiber, carbon fiber, semi-carbonized fiber, cellulosic fiber, filler such as glass beads, flame retardant and the like. .

The reactive ultraviolet absorber of the present invention can be optionally added to the above synthetic resin, but is preferably about 0.05 to 20 parts, preferably about 0 to 100 parts of the above resin. It is recommended to add 1 part to 10 parts. Also,
Depending on the function of the functional agent portion as a reactive ultraviolet absorber and the purpose of use, in addition to the reactive ultraviolet absorber of the present invention, a similar function such as a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber. It is also a preferred embodiment to use two or more kinds of agents including a combination of agents or a combination of different functional agents such as an ultraviolet absorber and a light stabilizer so as to bring about a synergistic effect. The reactive ultraviolet absorber of the present invention, for synthetic resins, is used alone or in combination with the above resins, and is kneaded with a mixing roll, a Banbury mixer, a kneader or the like and cut into a sheet-shaped master batch, or a pelletizer. It is made into a masterbatch pellet with a Henschel mixer, a supermixer, a tumbler, etc. according to a conventional method together with the above-mentioned resin, and molded by a mixing roll, an injection molding machine, an extrusion molding machine, an inflation molding machine, etc. . Known fiber materials can be used as the fiber material. Examples thereof include polyethylene terephthalate fiber, polyamide fiber, polypropylene fiber, acrylonitrile fiber, polyurethane fiber, polyethylene fiber, polyvinyl chloride fiber, and polyvinylidene chloride fiber. The processing methods are also performed according to conventionally known spinning methods. The reactive ultraviolet absorber of the present invention is preferably added in an amount of about 0.1 to 5 parts with respect to 100 parts of the resin.

Paper materials, non-woven fabric materials, paints, coating agents, printing agents, printing inks, and adhesives can be prepared according to conventionally known methods. As a processing method, conventionally known processing methods such as paper making, film formation, coating, printing and printing are used. As the paint, conventionally known acrylic melamine-based, alkyd melamine-based, polyester melamine-based, acrylic isocyanate-based, two-component polyurethane-based oily solvent type, acrylic melamine-based, alkyd melamine-based aqueous solution type, acrylic resin emulsion-based, Aqueous dispersion type such as fluororesin emulsion type, powder coating such as acrylic isocyanate type, polyester isocyanate type, polyester epoxy type, etc., UV curing of urethane acrylate type, epoxy acrylate type, polyester acrylate type, etc., electron beam curing coating, etc. Is mentioned. In use,
For metal plates, especially for automobiles, coil coating, building materials, woodworking, etc. The coating agent and the adhesive agent also include the same dry type and wet type. Examples of the printing agent include conventionally known acrylic resin emulsion type, acrylic styrene resin emulsion type, and synthetic rubber type. Examples of the printing ink include conventionally known offset inks such as rotary printing and sheet-fed inks, gravure inks for plastic films / sheets, aluminum foils, building materials / decorative boards, metal plate inks, flexo inks and the like. . Examples of the electrophotographic developer and inkjet ink include conventionally known full-color, mono-color and monochrome dry developers, wet developers, water-based, oil-based, and solid-type inkjet inks. In particular, developers and inks used for full-color image applications such as advertisements, signboards, and exterior coatings can be mentioned.

The amount of the reactive ultraviolet absorber added to each of the above materials varies depending on the intended use and purpose, but as one standard, the amount added as a functional agent component to 100 parts of the resin solid content is about 0. It is preferable to add 1 part to 10 parts. Further, it is also preferable to use two or more kinds of the reactive ultraviolet absorbers having the same kind of function or different kinds of functions depending on the purpose in the same manner as described above to bring about a synergistic effect. Generally, when the product is thin like a film or thin like a thread, or the material is easily deteriorated,
When it is exposed to a harsh environment like outdoor paint and long-term durability is expected,
It is desirable to use the larger proportion of the added amount. Examples of the wet dissolution processing method include a heating stirring reaction tank, a mixing stirring reaction tank, and a dissolver mixing method, and examples of the processing method by wet dispersion include a mixing roll mill, a kneader, a ball mill, an attritor, a sand mill, a horizontal medium disperser, and a vertical type. A medium disperser, a continuous horizontal medium disperser, a continuous vertical medium disperser or the like is used. As the dry dissolution and dispersion processing method, the methods and processing machines described above for the synthetic resin can be used. Synthetic resin coloring, paints, printing agents, printing inks,
As a coloring matter used when coloring an article such as an electrophotographic developer or an inkjet ink, a commonly used organic pigment, inorganic pigment and extender pigment, and a dye are used. Specifically, for example, soluble azo pigments, insoluble azo pigments, polyazo pigments, azomethine azo pigments, anthraquinone pigments, phthalocyanine pigments, quinacridone pigments, perinone-perylene pigments, azomethine pigments, isoindolinone pigments. Inorganic pigments, isoindoline pigments, pyrrolopyrrole pigments, organic pigments such as fluorescent pigments, carbon black pigments, titanium oxide pigments, yellow iron oxide, red iron oxide, chromium oxide, ultramarine blue, complex oxide pigments, zinc sulfide, etc. Examples thereof include pigments, extenders such as calcium carbonate, talc, kaolin, barium sulfate, disperse dyes and oil-soluble dyes, and are not particularly limited.

As a method of using the reactive ultraviolet absorber of the present invention in combination for improving the durability of the dye against discoloration, fading, etc., a coloring composition for synthetic resin, paint, printing agent, printing ink, electrophotographic development And a method of adding it at the time of preparation of a coloring composition such as an agent or an inkjet ink, or a method of preparing a processed product of a dye by previously mixing and coating the dye in a dye manufacturing process. Depending on the purpose, it is also effective to use and treat other light stabilizers in combination, to process into fine polymer beads in the case of coating treatment, or to fix it by crosslinking treatment. Furthermore, the reactive UV absorbers of the present invention are used in sunscreen products for cosmeceuticals. Highly safe for the skin, UV that is harmful to the skin
-A (320 to 400 nm) and UV-B (290 to 3)
It has the ability to effectively absorb 20 nm), can be uniformly blended with bases such as creams, emulsions, oils, lotions, etc., is difficult to run off in a sweat or water bath, and has good stability. As the blending amount, the condition of skin exposure,
It is not generally decided depending on the purpose of use and the material used, but it is approximately 1 to 20% in terms of the material of the ultraviolet absorber.
Used in place.

[0045]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, "parts" or "%" in the text are based on weight. <Synthesis example 1> 2-benzotriazol-2-yl-5
-(4'-Hydroxybutoxy) -phenol (reactive UV absorber-1) synthesis Stirrer, backflow condenser, thermometer, nitrogen introduction tube, a reactor equipped with a dropping device, dimethylsulfoxide (DMSO) 150 parts Charge, 2- (2 ', 4'-dihydroxyphenyl) -2H-benzotriazole 4
5.4 parts were dissolved. 50 parts of methanol and 11.2 parts of potassium hydroxide were dissolved in another container and added to the DMSO solution. Then, the mixture was heated to 100 ° C., methanol was distilled off, and 21.7 parts of 4-chloro-1-butanol was added dropwise over 30 minutes. Then, the temperature was raised to 120 ° C, and at this temperature, 4
Reacted for hours. Infrared absorption spectrum (IR) confirmed that an ether group had been formed. Toluene 200
Parts were added, and the mixture was washed twice with 300 parts of 0.1% hydrochloric acid water and then 300 parts of saturated saline. This was dried over anhydrous magnesium sulfate, and toluene was distilled off. The brown liquid obtained was recrystallized from xylene, filtered and dried to obtain the desired product. This is designated as reactive ultraviolet absorber-1. It was confirmed by instrumental analysis to have this structure. When the purity was measured by HPLC,
It was 98.8%. The maximum absorption wavelength was 340 nm as measured by a spectrophotometer.

<Synthesis Example 2> of 2- (5-chloro-benzotriazol-2-yl) -5- [2- (2-hydroxy-ethoxy) -ethoxy] -phenol (reactive UV absorber-2) In the same manner as in Synthesis Example 1, instead of 2- (2 ', 4'-dihydroxyphenyl) -2H-benzotriazole, 5'-chloro-2- (2', 4'-dihydroxyphenyl) -2H-benzo was used. It was synthesized by using (2-chloroethoxy) ethanol instead of triazole and 4-chloro-1-butanol. This is designated as reactive ultraviolet absorber-2. It was confirmed by instrumental analysis to have this structure. When the purity was measured by HPLC,
It was 99.2%. Further, the maximum absorption wavelength was 351 nm as measured by a spectrophotometer.

<Synthesis Example 3> 2-benzotriazole-
Synthesis of 2-yl-5- (2-hydroxy-3-phenoxy-propoxy) -phenol (reactive UV absorber-3) Using the same reaction apparatus as in Example 1, toluene 200 was used.
Part, 2- (2 ', 4'-dihydroxyphenyl) -2H
-Benzotriazole 45.4 parts benzotriazole,
Charge 30 parts of glycidyl phenyl ether and 2.2 parts of ethyltriphenylphosphonium bromide, and set at 110 ° C.
Was reacted for 2 hours. The liquid became brown and transparent. When the obtained solution was cooled, crystals were precipitated at around 70 ° C., and then further cooled to 10 ° C. for crystallization to obtain a yellowish brown powder. This was filtered, washed with toluene, dried, and recrystallized with a toluene-ethanol mixed solvent. The obtained crystals were filtered, washed with toluene and dried. This is designated as reactive ultraviolet absorber-3. When the purity of this was measured by liquid chromatography, the purity was 98.3.
%Met. It was confirmed by instrumental analysis that it has this structure.

<Synthesis Examples 4 to 9> The compounds shown in Table 1 were obtained in the same manner as in Synthesis Example 3.

[0049]

<Synthesis Example 10> Synthesis of polymer-bound benzotriazole-based UV absorber-1 by dealcoholization condensation of ethylene-co-ethyl acrylate copolymer and UV absorber-1 Cooling tube, temperature in reaction container An ethylene-co-ethyl acrylate copolymer (ethyl acrylate content 25%, MI value 200) was installed with a meter, a water separator and a stirrer.
00 parts, 70.8 parts of reactive ultraviolet absorber-1, 35 parts of xylene, and 0.5 parts of dibutyltin oxide were added and melted at 150 ° C. while flowing nitrogen. Xylene was gradually distilled off and the mixture was heated to 210 ° C. The reaction was carried out at this temperature for 4 hours, then the pressure was reduced and the reaction was carried out for 1 hour. Then, 200 parts of xylene was added, and further 1000 parts of IPA was used for precipitation. This was dried in a vacuum dryer at 40 ° C. for 24 hours to obtain a pale yellow rubbery amorphous resin. This is referred to as a polymer-bound benzotriazole-based ultraviolet absorber-1. This was measured by GPC (gel permeation chromatograph) and found to have a number average molecular weight of 29000 and a weight average molecular weight of 46,000 in terms of polystyrene. Further, as a functional group, 2- (benzotriazolyl) hydroxyphenyl group was added at 30.1% (theoretical value: 31.
84%).

<Synthesis Example 11> Polymer-bound benzotriazole type ultraviolet absorber by condensation of ethylene-co-ethyl acrylate copolymer and reactive ultraviolet absorber-2
Synthesis of 2 was carried out in the same manner as in Synthesis Example 10 to obtain a polymer-bound benzotriazole type ultraviolet absorber-2. When measured by GPC, the polystyrene equivalent number average molecular weight was 3100.
It was 0 and the weight average molecular weight was 47,500. This had a softening point of 28.2% (theoretical value 29.8%) of 2- (5'-chloro-benzotriazolyl) hydroxyphenoxy group as a functional group.

<Synthesis Example 12> Reactive UV absorber-5
Synthesis of polyester-bonded benzotriazole-based UV absorber-3 of polyester resin using a condenser equipped with a cooling pipe, a thermometer, a water separator and a stirrer, and 110.6 parts of dimethyl terephthalate 1, Four
-Butanediol 16.2 parts, reactive UV absorber-5
90.3 parts and 0.1 part of dibutyltin oxide were charged, and the mixture was heated to 150 ° C. while flowing nitrogen and melted. Then,
When it was further heated to 165 ° C, the distillation of methanol started. The temperature was raised to 230 ° C. over 4 hours, condensation was carried out for 1 hour, and then the pressure was gradually reduced to 5.5 mHg and the polymerization was conducted for 2 hours. Then, it was cooled and taken out. A yellow, relatively brittle, transparent resin was obtained. When the molecular weight of this was measured by GPC, the number average molecular weight was 5700 and the weight average molecular weight was 10030 in terms of polystyrene.
Met. As a result of thermal analysis, Tg was 69 ° C.
This contained 27.4% of 2- (benzotriazolyl) hydroxyphenyl groups. This is referred to as a polymer-bound benzotriazole-based UV absorber-3.

<Synthesis Example 13> Reactive ultraviolet absorber-6
Synthesis of Polymer-Bonded Benzotriazole-Based Ultraviolet Absorber-4 of Polyester Resin Using Polyester A triazole-based UV absorber-4 was obtained. When the molecular weight of this was measured by GPC, the number average molecular weight was 8,000 and the weight average molecular weight was 16,000 in terms of polystyrene. As a result of thermal analysis, Tg was 53 ° C. This is 2-
(Benzotriazolyl) hydroxyphenyl group 2
The content was 5.2%. This is referred to as a polymer-bound benzotriazole-based UV absorber-4.

<Synthesis Example 14> Reactive ultraviolet absorber-5
Synthesis of polymer-bonded UV absorber-5 of polyurethane resin using the same equipment as in Synthesis Example 12, 83.1 parts of isophorone diisocyanate, 50 parts of polytetramethylene glycol (molecular weight 1000), reactive UV absorber 15 parts of -5, 20 parts of 2,2-bis (hydroxymethyl) propionic acid, 0.02 parts of dibutyltin dilaurate and 35 parts of acetone were charged, and the mixture was heated to 80 ° C. and reacted for 4 hours. When the amount of isocyanate reached 5.15%,
With vigorous stirring, 23 parts of isophoronediamine, 9.1 parts of ammonia water (28%) and 417 parts of water were added at once to effect chain extension and neutralization self-emulsification. Then, acetone was distilled off under reduced pressure. The average particle size of the obtained polyurethane dispersion was measured and found to be 80 nm. This is referred to as a polymer-bound benzotriazole-based UV absorber-5. It contained about 5% of 2- (benzotriazolyl) hydroxyphenoxy groups.

<Synthesis Example 15> Reactive UV absorber-8
Synthesis of acrylic resin-based polymer-bound benzotriazole-based UV absorbent-6 using 60 parts of the basic ultraviolet absorber-8 was charged, and further 3 parts of azobisisobutyronitrile was charged, and the mixture was heated to 80 degrees.
The solution became yellow and transparent, and the viscosity gradually increased.
It was polymerized at this temperature for 8 hours and taken out. When the molecular weight was measured by GPC, a number average molecular weight of 10,000 and a weight average molecular weight of 16,000 were obtained. This is referred to as a polymer-bound benzotriazole-based UV absorber-6. This is 2-
(Benzotriazolyl) hydroxyphenyl group 34
% Contained.

<Synthesis Example 16> Reactive ultraviolet absorber-9
Synthesis of acrylic resin polymer-bonded benzotriazole-based UV absorber-7 using the same procedure as in Synthesis Example 15, solvent composition toluene / butyl acetate = 8/2, ethyl methacrylate / butyl methacrylate part / methacrylic acid Obtained in a weight ratio of hydroxyethyl / reactive UV absorber-9 = 20/25/10/45. Number average molecular weight 12,000, weight average molecular weight 2350
0. This is referred to as a polymer-bound benzotriazole-based UV absorber-7. It contained 25% of 2- (benzotriazolyl) hydroxyphenyl groups.

<Synthesis Example 17> Reactive UV absorber-8
Synthesis of acrylic resin-based polymer-bonded benzotriazole-based UV absorber-8 using: Using the same apparatus as in Synthesis Example 12, water 150 parts, polyethylene glycol nonylphenyl ether sodium monosulfonate 3 parts, sodium persulfate 0.3 part was charged and heated to 80 ° C. Then, in a separate container, 20 parts of ethyl methacrylate, 30 parts of butyl acrylate, 5 parts of hydroxyethyl methacrylate, and 45 parts of reactive ultraviolet absorber-8 were added.
Part of the mixture was stirred and dissolved, and the monomer mixture was added dropwise over 2 hours. The mixture was aged at that temperature for 6 hours to obtain a latex type polymer-bonded benzotriazole-based ultraviolet absorber. This is a polymer-bound benzotriazole-based UV absorber-8
And It contained 25% of 2- (benzotriazolyl) hydroxyphenyl groups. It was 185 nm when the average particle size was measured with the particle size distribution analyzer.

<Application Example 1> Application to paints Carboxyl group-containing thermosetting acrylic resin (acid value in varnish: 10, solid content: 50%, solvent: Solvesso 100)
/ N-butanol (85:15) mixed solvent) 140 parts,
Methoxymethyl melamine resin (solid content: 60%, solvent:
Methanol / isopropanol / isobutanol: 5
0:35:15) 50 parts, Solvesso 100 / n-butanol (85:15) mixed solvent 40 parts, reactive UV absorber-3 6.5 parts were mixed and dissolved to prepare a surface coating resin solution for steel plate. did. It was applied to a rustproofed and undercoated steel sheet, dried and then cured at 140 ° C. for 30 minutes. The weather resistance test of the coating film was performed with a sunshine type weatherometer. It showed a high gloss retention for a long period of time and showed an excellent effect. Instead of Reactive UV Absorber-3,
Similar effects were obtained when the reactive UV absorbers 5, 6, and 7 and the polymer-bound benzotriazole-based UV absorber-7 were used. This is because the hydroxyl group of the UV absorber reacts with the melamine-based cross-linking agent in the paint, and the polymer-bound benzotriazole-based UV absorber has a high molecular weight, which suppresses volatilization and bleeding due to heat drying from the coating film. It is considered that the long-term performance was demonstrated by this.

<Application Example 2> Application to water-based paint Methyl methacrylate-ethyl acrylate-acrylic acid (64: 32: 4) copolymer latex (solid content 40
%) 33 parts, titanium oxide white pigment 22 parts, mica 3 parts,
Talc 7 parts, 3% hydroxyethyl cellulose aqueous solution 1
0 parts, 1 part of pigment dispersant, 1 part of propylene glycol monomethyl ether, 2 parts of ethylene glycol, 0.5 part of silicone defoaming agent, 0.5 part of preservative, 0 parts of polymer-bound benzotriazole-based UV absorber-8 An outdoor white emulsion paint having a formulation of 5 parts and 15 parts of water was prepared.
White paint was applied to various outdoor structures. A weather resistance test was carried out with a weather ohmmeter. As a result, even after 600 hours, there was no surface crack or yellowing and the performance was maintained for a long time.

<Application Example 3> Application to gravure ink Carboxyl group-containing vinyl chloride-vinyl acetate copolymer 2
0 part, 0.5 part of reactive ultraviolet absorber-3, butyl acetate-methyl isobutyl ketone-xylene mixed solvent (4 parts
3:20:20) dissolved in 70 parts, blue to 9 parts copper phthalocyanine blue pigment, red to 10 parts dimethylquinacridone pigment, yellow to 11 parts yellow polyazo pigment,
In addition, for the black color, 8 parts of carbon black pigment was added and charged in a ball mill and dispersed for 16 hours. To 97 parts thereof, 3 parts of silica was added and mixed, and further 2.7 parts of a 75% solution of hexamethylene diisocyanate-based polyisocyanate having a biuret bond was added and mixed to obtain blue, red, yellow and black ink compositions, respectively. did. A pattern was printed on the surface of the semi-rigid vinyl chloride film by a gravure printing method. Dry the colored ink at room temperature, then 30-4
After aging in a constant temperature room of 0 ° C., a vinyl chloride sheet having a four-color printed pattern was obtained. It showed excellent weather resistance. Similar effects were obtained when reactive UV absorbers-4, 5, 6, 7 and polymer-bound benzotriazole-based UV absorber-7 were used instead of reactive UV absorber-3.

<Application Example 4> Application to electrophotographic dry developer Fine powder of polyester resin (softening point 105 ° C., glass transition point 53 ° C., number average molecular weight 6000) consisting of propylene oxide adduct of bisphenol A and fumaric acid. 67
30 parts of copper phthalocyanine blue (CI Pigment Blue 15: 3) and 3 parts of polymer-bonded benzotriazole-based UV absorber-5 were added to the above parts, and mixed by stirring.
The pigment was finely dispersed and kneaded in this roll mill, cooled and crushed to obtain a crushed product of a high-concentration colored composition containing a blue pigment at 30%. When this was placed on a slide glass, heated and melted, and observed under a microscope, all the pigment particles were finely dispersed, and coarse particles were not observed. Then,
11 parts of the high-concentration coloring composition containing the blue pigment, 3 parts of the chromium complex salt negative charge control agent, and 86 parts of the polyester resin used above were kneaded by a conventional method, and after cooling and coarse crushing,
The powder was finely pulverized with a jet mill and pulverized to obtain a fine powder of 5 to 20 μm. Colloidal silica was added as a fluidizing agent, mixed with magnetic iron powder as a carrier, and copied as a cyan electrophotographic dry developer with a full-color electrophotographic copying machine to obtain a clear cyan image. Similarly, a magenta electrophotographic dry developer using dimethylquinacridone pigment (CI Pigment Red 122) and phthalimidocadimethylquinacridone as magenta color,
As a yellow color, a polycondensation yellow pigment (C.I. pigment 1
28) was used to obtain a yellow electrophotographic dry developer, and as black, carbon black (CI Pigment Black 7) and phthalimidomethylated copper phthalocyanine blue were used to obtain a black electrophotographic dry developer. Using these four colors as an electrophotographic dry developer, a full-color electrophotographic copying machine was used for copying to obtain a clear color image. The thus obtained four-color electrophotographic dry developer was copied by a full-color electrophotographic copying machine, and the obtained image was subjected to a weather resistance test with a carbon arc type fade meter to obtain a clear image. Was the result of being retained for a long time. Similar performance was obtained when -6 was used instead of the polymer-bound benzotriazole type ultraviolet absorber -5.

<Application Example 5> Application to UV ink A UV curable ink was prepared as follows. Polyurethane polyester diol (terephthalic acid-sebacic acid-ethylene glycol-neopentyl glycol co-condensation polyester diol, average molecular weight: 2,000) 66.7
Part, hydroxypropyl methacrylate 19.2 parts,
70 parts of a UV-curable urethane coating agent obtained by reacting 22.2 parts of isophorone disisocyanate,
Trimethylolpropane triacrylate 15 parts, neopentyl glycol diacrylate 5 parts, oligoester acrylate monomer 5 parts, 2-hydroxy-2-methylpropylphenone 3 parts, 2,2-diethoxyacetophenone 2 parts, isopropanol 45 parts, toluene 45
Parts, ethyl acetate 60 parts, reactive UV absorber-80.3
The parts were mixed with stirring. Then 3g / on the polycarbonate plate
m ² , spray painted, high pressure mercury lamp 160w / cm × 3
Book, cured at 50 m / min. For comparison, a commercially available ultraviolet absorber was added instead of the example, or a commercially available ultraviolet absorber was not added, and they were applied and cured in the same manner. The coated polycarbonate plate thus obtained is exposed to UV light at 83 ° C for a predetermined time at 200 ° C.
Compared with a coated plate that was not irradiated with the degree of yellowing of a polycarbonate plate after being irradiated for 400 hours or 600 hours, it was found that after 200 hours, those without addition of an ultraviolet absorber turned yellow. The product and the reactive ultraviolet absorber of the present invention are not discolored. However, after 400 hours, the commercially available product also turned yellow, while the one incorporating the reactive ultraviolet absorber of the present invention did not change color. At 600 hours, both the commercial product and the blank to which the ultraviolet absorber was not added showed the same yellowing, but the reactive ultraviolet absorber of the present invention hardly changed the color. As a result, the blank turns yellow, while the ones to which the examples and the commercially available ultraviolet absorbers are added are effective at the initial stage. However, over time, the effects of the commercially available ultraviolet absorbers are not maintained, but the effects of the examples are sustained. This is because the reactive ultraviolet absorber of the present invention contains an unsaturated bond and is retained in the coating film by curing in the coating film, and the effect is sustained, while the commercially available ultraviolet absorber gradually bleeds. hand,
By disappearing from the coating film surface by the flow of air,
It is considered that the effect is not sustained.

<Application Example 6> Application to polypropylene resin-based molded product A masterbatch for coloring a composite material for automobiles was prepared as follows. Propylene block copolymer 95 parts, L
LD polyethylene 5 parts, talc 10 parts, titanium oxide 20
Parts, ultramarine 20 parts, iron oxide 4 parts, yellow iron oxide 3 parts, carbon black 8 parts, polyethylene wax 20 parts, calcium stearate 5 parts, magnesium stearate 5
Parts, polymer-bonded benzotriazole-based UV absorber-1
Mix evenly with 10 parts of high speed mixer and 1 with an extruder.
Extrusion was carried out at 80 ° C. to obtain a pellet-shaped coloring masterbatch. Next, composite material for molded parts for automobiles (resin component is polypropylene / ethylene / propylene rubber / isotactic polypropylene, talc 20%
100 parts), 3 parts of the pigment masterbatch obtained above and 0.1 part of calcium stearate are mixed in a tumbler, and a molding temperature of 220 ° C. and a back pressure of 15 by an injection molding machine.
Molded at kg / cm ² . The obtained test piece showed sufficiently excellent results in physical properties tests such as tensile, bending, Izod impact strength, tensile elongation, bending elastic modulus, etc., and the colorant was uniformly colored, and cracks in the weather resistance accelerated test. It was excellent with no occurrence or discoloration. In place of the polymer-bonded benzotriazole-based UV absorber-1 used above, -2 was used, and the physical properties of the molded product were similarly improved.

<Application Example 7> Application to polyethylene resin film Low density polyethylene (specific gravity 0.918, MFR: 12)
54.6 parts of the polymer-bonded benzotriazole-based UV absorber obtained in Synthesis Example 10 was kneaded with 44.4 parts with a mixing roll (roll surface temperature: 120 ° C.), drawn out as a sheet, and then mixed with a pelletizer to about 3 × 3. A masterbatch containing a polymer-bound benzotriazole-based UV absorber having a size of 2 mm was obtained. This masterbatch contains 16.7% 2- (hydroxyphenyl) -2-benzotriazole groups. Then, 99.4 parts of a low density polyethylene (specific gravity 0.918, MFR: 12) which is the same resin was used, and the polyethylene masterbatch obtained in the above was added to 0.2%.
6 parts (0.1% of 2- (hydroxyphenyl) -2-benzotriazole group) were blended with a mixer to give 30 m /
Films each having a thickness of 50 μ were obtained by an inflation extruder of m. For comparison, 2- (3'-t
-Butyl-5'-methyl-2'-hydroxy-phenyl) -2H-5-chloro-benzotriazole (commercially available product) was added to low density polyethylene to a concentration of 0.1%, kneaded and blown into an inflation extruder. A film having a thickness of 50 μm was obtained. In order to see the ability of the polyethylene film containing the polymer-bound benzotriazole-based UV absorber to prevent UV deterioration, a weather resistance accelerated tester (Sunshine weatherometer, 63 ° C, spray cycle: 1
The weather resistance test is performed at 2 minutes / hour, and the degree of ultraviolet deterioration of the film is determined by the change in the elongation rate of the film (pulling speed: 200 mm
/ Min) and compared with a film of a commercially available ultraviolet absorber. While not added, the breaking strength showed a large deterioration with time, whereas the addition of the ultraviolet absorber component showed little change and the effect was recognized. In particular, it is shown that the film containing the polymer-bound benzotriazole type ultraviolet absorber has a remarkably low residual ratio of the strength at break and is excellent in the long-term sustainability of the effect of preventing ultraviolet deterioration. The strength of the known ultraviolet absorber was lowered, and the result was inferior to that of the polymer-bound benzotriazole type ultraviolet absorber. It is considered that this is because the known functional agent added had a low molecular weight and thus bloomed or volatilized and the content of the active ingredient decreased. Similarly, the polymer-bound benzotriazole-based UV absorber-2 also showed similar effects.

<Application Example 8> Application to photographic printing paper Ultramarine pigment powder (CI Pigment Blue 29) 10
0 part, 2.5 parts of powdery azo red pigment (CI Pigment Violet 247) and 100 parts of polyethylene wax (average molecular weight: 2000; density: 0.93),
Knead using a test kneader with a capacity of 1.5 liters,
The obtained kneaded product was ground at room temperature. 6.0 parts of this pulverized product and low density polyethylene (MFR: 3.0; density: 0.9
27) 100 parts using a 30 mm same-direction twin-screw extruder,
A bluing masterbatch was obtained by kneading and granulating at 150 ± 10 ° C. 4.8 parts of this bluing masterbatch and white masterbatch (titanium oxide content 50.0%, low density polyethylene (MFR: 4.5; density: 0.917))
20 parts, 100 parts of the above low-density polyethylene, and 1 part of the polymer-bonded benzotriazole-based UV absorber-1 were thoroughly mixed, and a 30 mm T dilaminator was used at a molding temperature of 320 ° C. to prepare a support substrate for photographic paper. Paper (Basis weight 15
0 g / m ² , using softwood bleached sulfuric acid pulp / hardwood bleached sulfurous acid pulp = 2/8 weight ratio)) surface 20)
A μm coating was formed. A paper coating having a good appearance was obtained. This was subjected to a light resistance test with a carbon arc type fade meter. Irradiation was performed for 50 hours and 100 hours, and discoloration was observed.
As a result, no fading was observed after irradiation for 100 hours.
The MFR in the text is a value measured under the conditions of a load of 2.16 kg and a measurement temperature of 190 ° C. according to JIS K7210. The unit of MFR is (g / 10 min), and the unit of density is (g / cm ³ ).

<Application Example 9> Application to water-based adhesive Polytetramethylene glycol (average molecular weight of about 100)
0) -dimethylolpropionic acid-isophorone diisocyanate-diethylenetriamine (247: 24: 12
4: 5) anionic urethane urea resin neutralized with triethylamine was added to 100 parts of an aqueous dispersion (solid content 40%), and 5 parts of polymer-bound benzotriazole-based UV absorber-5 was added.
Parts, and 3 parts of a carbodiimide-based cross-linking agent (Emafix GT, manufactured by Dainichi Seika Co., Ltd.) were added to prepare an aqueous adhesive composition.
A 20 μm thick corona discharge treated polypropylene (OPP) film having a wetting index of 40 dynes was coated with the above aqueous adhesive composition coater to a solid content of 2.5 μm and immediately after drying. A 60 μm thick polypropylene (CPP) film having a wetting index of 38 dynes was dry laminated at about 60 ° C. using a laminating roll. Laminated film is aged at 40 ℃ for 48 hours,
A test piece having a width of 15 mm was prepared, and the tensile strength was 100 mm / min and the adhesive strength was measured at 25 to 26 ° C. by using a sipper tester. As a result, 168 g / 15 mm was shown. Those without the polymer-bound benzotriazole type ultraviolet absorber-5 showed 184 g / 15 mm. This was irradiated with ultraviolet rays for 100 hours using a carbon arc type fade meter, and then the adhesive strength was measured at 25 to 26 ° C. at a tensile strength of 100 mm / min using a sipper tester in the same manner. The product containing the benzotriazole-based ultraviolet absorber-5 showed 135 g / 15 mm. In the case where the ultraviolet absorber was not added, the amount was significantly reduced to 67 g / 15 mm.

[0067]

EFFECT OF THE INVENTION 2- (2 ', 4'-dihydroxyphenyl) -2H-benzotriazole type ultraviolet absorber having an epoxy compound having at least one epoxy group in the molecule or an alcohol having at least one halogen group. Is a reactive UV absorber having a 2- (benzotriazolyl) hydroxyphenoxy residue and an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group in the molecule used by reacting a compound having a hydroxyl group? By using a reactive ultraviolet absorber having an unsaturated bond introduced, the action of energy rays such as ultraviolet rays, electron beams and visible light, the action of heat and radical polymerization initiators and / or the action of ionic polymerization initiators. Reactive ultraviolet light by curing by addition polymerization reaction or addition bonding reaction by The sorbent is retained in the article, and a reactive ultraviolet absorber having excellent long-term performance retention due to non-bleeding, extraction resistance, and heat resistance is obtained, and the reactive ultraviolet absorber and other polymerizable compounds And the addition to the main chain of the polymer molecule obtained by addition-condensation, addition-polymerization, or addition-polymerization with a reactive ultraviolet absorber having an addition-polymerizable group and another monomer having an unsaturated bond, and A polymer-bonded benzotriazole-based UV absorber formed by bonding to a side chain or / and a side chain can also exert the same effect, and exerts an effect of improving performance maintenance of an article.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 246/00 C08F 246/00 4J040 C08G 85/00 C08G 85/00 4J100 C09D 11/00 C09D 11/00 157 / 12 157/12 201/02 201/02 C09J 157/12 C09J 157/12 201/02 201/02 G03C 1/815 G03C 1/815 (72) Inventor Tetsuo Fukuda 1-7-chome, Nihonbashi-Bakurocho, Chuo-ku, Tokyo 6 In Dainichi Seika Kogyo Co., Ltd. (72) Inventor Ryoya Yamashita 1-7-6 Nihonbashi Bakuro-cho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (72) Inoue Nakamura Nihonbashi Bakuro-cho, Chuo-ku, Tokyo 1-Chome 7-6 Dainichi Seika Kogyo Co., Ltd. F term (reference) 2H023 FD00 4C083 AC851 BB46 EE17 4J031 CD09 CD24 4J038 CB002 CC021 CD091 CF031 CG002 CG141 CG161 CG171 CK022 DB001 DB002 DD002 DD181 DF002 DG002 DL002 GA09 JB35 KA12 4J039 AD00 AE00 BC52 EA35 4J040 DC091 DF001 DN012 EC001 ED001 EF001 GA17 HC25 LA07 4J100 AB01P AB02P AB04P AG03P AG04P AJ02P AL03P AL04P AL05P AL08P AL08Q AL09P AL10P AL36P AM02P AM15P AM19P AM21P BA02Q BA03P BA03Q BA12P BA31P BB01Q BC04P BC43P BC43Q BC75Q CA04 DA36

Claims (16)

[Claims] 1. A compound obtained by reacting a 2- (2 ′, 4′-dihydroxyphenyl) -2H-benzotriazole type ultraviolet absorber with an epoxy compound or a compound having an alcoholic hydroxyl group and a halogen group, An ultraviolet absorber characterized by being a reactive ultraviolet absorber having a 2- (benzotriazolyl) hydroxyphenoxy residue, and an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group in the molecule. 2. A 2- (2 ′, 4′-dihydroxyphenyl) -2H-benzotriazole type ultraviolet absorber having an epoxy compound having at least one epoxy group in the molecule or at least one having an alcoholic hydroxyl group. To obtain a reactive ultraviolet absorber having a 2- (benzotriazolyl) hydroxyphenoxy residue and an alcoholic hydroxyl group, or an alcoholic hydroxyl group and an epoxy group in a molecule by reacting a compound containing a halogen group A method for producing an ultraviolet absorber, comprising: 3. A paint or an ink which is cured by an addition polymerization reaction or an addition bond reaction by the action of energy rays such as ultraviolet rays, electron beams or visible light, the action of heat or radical polymerization initiator and / or the action of ionic polymerization initiator. Suitable for applications such as adhesives, coating agents such as coating agents, cosmetics, foods, photographic materials, textile products, plastic molding materials, etc. 2
An ultraviolet absorber characterized by being an addition-polymerizable ultraviolet absorber having a (-benzotriazolyl) hydroxyphenoxy residue and an addition-polymerizable unsaturated group. 4. A 2- (2 ′, 4′-dihydroxyphenyl) -2H-benzotriazole-based UV absorber is reacted with an addition-polymerizable unsaturated compound having an epoxy group or a halogen group, or according to claim 1. A reactive ultraviolet absorber having an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group described above is reacted with an addition-polymerizable unsaturated compound having a reactive group capable of reacting with the 2- (benzotriazole). Zolyl) hydroxyphenoxy-based residue, and an addition-polymerizable ultraviolet absorber having an addition-polymerizable unsaturated group are obtained. 5. An ultraviolet absorber used as an additive for coating materials such as paints, inks, adhesives, coating agents, cosmetics, pharmaceuticals, foods, photographic materials, textile products, plastic molding materials, etc. The absorbent is 2-
A 2- (benzotriazolyl) hydroxyphenoxy-based residue derived from a (2 ′, 4′-dihydroxyphenyl) -2H-benzotriazole-based UV absorber is bound in a polymer molecule having an average molecular weight of 1,000 or more. A polymer-bonded benzotriazole-based ultraviolet absorber characterized in that 6. The average molecular weight of claim 5, 1,000.
The above polymers are polyolefin-based polymers, polyether-based polymers, polyester-based polymers, polyamide-based polymers, polyvinyl-based polymers, poly (meth) acrylic-based polymers, polysilicone-based polymers, polyurethane-based polymers. ,
The polymer-bonded benzotriazole-based ultraviolet absorber according to claim 5, which is at least one polymer selected from the group consisting of polyurea-based polymers, epoxy resin-based resins, and melamine-based resins, or a copolymer thereof. 7. The polymer-bound benzotriazole according to claim 5, wherein the 2- (benzotriazolyl) hydroxyphenoxy-based residue is contained in the main chain of the polymer molecule and / or bonded to the side chain. UV absorber. 8. A polymer molecule containing 2- (benzotriazolyl) hydroxyphenoxy-based residue in an amount of 10 to 90% by weight.
The polymer-bound benzotriazole-based ultraviolet absorber according to claim 5, which is contained in 9. 2- (Benzotriazolyl) in the molecule
Reaction of a reactive ultraviolet absorber having a hydroxyphenoxy residue and a condensable reactive group and / or an addition polymerizable reactive group with a polymer having a group reactive with the reactive group, or synthesis of those polymers By carrying out addition copolymerization reaction or condensation copolymerization reaction with the raw materials,
A method for producing a UV absorber, comprising obtaining a polymer-bound benzotriazole UV absorber containing a 2- (benzotriazolyl) hydroxyphenoxy residue in the molecule. 10. A medium containing the 2- (benzotriazolyl) hydroxyphenoxy-based residue according to claim 1 and a reactive ultraviolet absorber having an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group in a medium. A reactive ultraviolet absorber composition comprising: 11. An addition-polymerizable ultraviolet absorber having a 2- (benzotriazolyl) hydroxyphenoxy-based residue and an addition-polymerizable unsaturated group is treated with an ultraviolet ray, an energy ray such as an electron beam or a visible ray, and heat. Coatings, inks, adhesives, coating agents such as coating agents, cosmetics, foods, photographic materials and fibers that are cured by an addition polymerization reaction or an addition bonding reaction by the action of a radical polymerization initiator and / or the action of an ionic polymerization initiator An addition-polymerizable ultraviolet absorbent composition, which is diluted and contained in a medium such as a product or a plastic molding material. 12. Coating of a polymer-bonded benzotriazole-based UV absorber according to claim 5, which contains a 2- (benzotriazolyl) hydroxyphenoxy-based residue, for coatings, inks, adhesives, coating agents and the like. A polymer-bonded benzotriazole-based UV absorber composition, which is diluted and contained in a medium used for agents, cosmetics, pharmaceuticals, foods, photographic materials, textiles, and plastic molding materials. 13. A reactive ultraviolet absorber or a reactive ultraviolet absorber having a 2- (benzotriazolyl) hydroxyphenoxy residue according to claim 1 and an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group. Coating agents, coating agents such as paints, inks, adhesives, coating agents, cosmetics, foods, photographic materials and textile products,
A method of absorbing ultraviolet rays by using it as an additive for plastic molding materials. 14. An addition-polymerizable ultraviolet absorber containing the 2- (benzotriazolyl) hydroxyphenoxy-based residue according to claim 3 or a medium for the addition-polymerizable ultraviolet absorber according to claim 11. , Inks, adhesives that cure the composition of the above by an addition polymerization reaction or an addition bonding reaction by the action of energy rays such as electron rays and visible light, the action of heat or radical polymerization initiator and / or the action of ionic polymerization initiator A method of UV-absorbing a product by using it as an additive for coating agents such as coating agents, cosmetics, foods, photographic materials and textiles, and plastic molding materials. 15. A polymer-bound benzotriazole-based UV absorber containing the 2- (benzotriazolyl) hydroxyphenoxy-based residue according to claim 5 or the polymer-bound benzotriazole-based UV absorber according to claim 12. Use the UV absorber composition as an additive for paints, inks, adhesives, coatings and other coating agents, cosmetics, pharmaceuticals, foods, photographic materials, textile products, plastic molding materials, etc. how to. 16. An article which has been subjected to an ultraviolet absorption treatment by the ultraviolet absorption treatment method according to claim 4, claim 8, or claim 15.