JP2021178918A - Reactive ultraviolet ray absorber and method for producing the same, and ultraviolet ray/electron beam curable coating agent - Google Patents

Abstract

To provide a reactive ultraviolet ray absorber that can prepare a coating agent able to form a coating film in which properties such as light resistance and weather resistance are maintained for a long period of time.SOLUTION: Provided is a compound represented by the following general formula (1). (R independently to each other indicates an alkylene group of 1 to 10 carbon atoms, a cycloalkylene group of 6 or more carbon atoms, an arylene group, or an alkylarylene group, A independently to each other indicates a hydrogen atom or any organic group having one or more (meth)acryloyloxy groups, B indicates a hydrogen atom or any organic group which may have one or more (meth)acryloyloxy groups.)SELECTED DRAWING: None

Description

The present invention relates to a reactive ultraviolet absorber, a method for producing the same, and an ultraviolet / electron beam curable coating agent.

Conventionally, a large number of ultraviolet absorbers such as benzophenone-based compounds, benzotriazole-based compounds, and triazine-based compounds are commercially available. These ultraviolet absorbers are added to paints, coating agents, inks, plastic materials for molding and the like for the purpose of improving properties such as light resistance and weather resistance. However, since these UV absorbers are non-reactive small molecule compounds, when added to paints, coating agents, etc., they bleed out from the formed coating film or sublimate due to heat during drying or molding. It may happen. Further, when the coating film is exposed to a solvent or a chemical, the ultraviolet absorber may be easily eluted from the coating film, so that it may be difficult to maintain properties such as light resistance and weather resistance.

Therefore, various proposals have been made in order to maintain the characteristics such as light resistance of various articles such as coating films and products. For example, by adding an ultraviolet absorber having a reactive group to a paint or the like and curing the ultraviolet absorber itself as a coating film component, or by using a copolymer having an ultraviolet absorbing group, bleed-out of the ultraviolet absorber can be achieved. It has been proposed to suppress and leave a component that absorbs ultraviolet rays in various articles and products such as a coating film for a long period of time (Patent Documents 1 to 4).

JP-A-2002-226522 Japanese Patent Application Laid-Open No. 2003-253248 Japanese Unexamined Patent Publication No. 2012-167288 Japanese Unexamined Patent Publication No. 2001-19711

However, even the paints and coating agents using the ultraviolet absorbers and the like proposed in Patent Documents 1 to 4 are not always sufficient in terms of characteristics such as light resistance and weather resistance of the formed coating film. I couldn't say it, and there was room for further improvement.

The present invention has been made in view of the problems of the prior art, and the problems thereof are light resistance, weather resistance, scratch resistance, bleed resistance, adhesion to a substrate, and the like. It is an object of the present invention to provide a reactive ultraviolet absorber capable of preparing a coating agent which is excellent in properties and can form a coating film in which these properties are maintained for a long period of time. Further, an object of the present invention is to provide a method for producing the above-mentioned reactive ultraviolet absorber and an ultraviolet / electron beam curable coating agent using the above-mentioned ultraviolet absorber.

That is, according to the present invention, the following reactive ultraviolet absorbers are provided.
[1] A reactive ultraviolet absorber represented by the following general formula (1).

（前記一般式（１）中、Ｒは、相互に独立に、炭素数１〜１０のアルキレン基、炭素数６以上のシクロアルキレン基、アリーレン基、又はアルキルアリーレン基を示し、Ａは、相互に独立に、水素原子又は１以上の（メタ）アクリロイルオキシ基を有する任意の有機基を示し、Ｂは、水素原子又は１以上の（メタ）アクリロイルオキシ基を有してもよい任意の有機基を示す）

(In the above general formula (1), R independently represent an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group, and A indicates each other. Independently, it represents any organic group having a hydrogen atom or one or more (meth) acryloyloxy groups, where B is any organic group which may have a hydrogen atom or one or more (meth) acryloyloxy groups. show)

[2] In the general formula (1), R represents a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylmethylene group, or a butylmethylene group, and A and B are independent of each other. , Hydrogen atom, 3- (meth) acryloyloxy-2-hydroxypropyl group, 3-hydroxy-4- (meth) acryloyloxy-cyclohexylmethyl group, 4- (meth) acryloyloxy-3-hydroxysilokuhexylmethyl group, Alternatively, the reactive ultraviolet absorber according to the above [1], which exhibits a 4'-(meth) acryloyloxybutoxy-2-hydroshikipropyl group (provided that there are less than two hydrogen atoms among A and B).
[3] The reactive ultraviolet absorber according to the above [1] or [2], which has two or more (meth) acryloyloxy groups in one molecule.

Further, according to the present invention, the following method for producing a reactive ultraviolet absorber is provided.
[4] The method for producing a reactive ultraviolet absorber according to any one of the above [1] to [3], wherein the compound (I) represented by the following general formula (I) and 3- (meth) are used. At least one selected from the group consisting of acryloyloxy-1,2-epoxypropane, (meth) acryloyloxy (3,4-epoxycyclohexyl) methane, and (meth) acryloyloxy2- (2-epoxymethoxy) butyl. A method for producing a reactive ultraviolet absorber, which comprises a step of reacting with the compound (II) and reacts the compound (II) with a reaction of more than 2 mol times and 3 mol times or less with 1 mol of the compound (I). ..

（前記一般式（Ｉ）中、Ｒは、相互に独立に、炭素数１〜１０のアルキレン基、炭素数６以上のシクロアルキレン基、アリーレン基、又はアルキルアリーレン基を示す）

(In the general formula (I), R indicates an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group independently of each other).

Further, according to the present invention, the following ultraviolet / electron beam curable coating agents are provided.
[5] An ultraviolet / electron beam curable coating agent containing 0.1 to 50% by mass of the reactive ultraviolet absorber according to any one of the above [1] to [3].
[6] The ultraviolet / electron beam curable coating agent according to the above [5], which is used outdoors.
[7] The ultraviolet / electron beam curable coating agent according to the above [5] or [6], which further contains an organic pigment.

According to the present invention, it is possible to form a coating film having excellent properties such as light resistance, weather resistance, scratch resistance, bleed resistance, and adhesion to a substrate, and maintaining these properties for a long period of time. It is possible to provide a reactive ultraviolet absorber for which a coating agent can be prepared. Further, according to the present invention, it is possible to provide a method for producing the above-mentioned reactive ultraviolet absorber and an ultraviolet / electron beam curable coating agent using the above-mentioned ultraviolet absorber.

<Reactive UV absorber>
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. The reactive ultraviolet absorber of the present invention is a compound represented by the following general formula (1). Hereinafter, the details of the reactive ultraviolet absorber of the present invention will be described.

（前記一般式（１）中、Ｒは、相互に独立に、炭素数１〜１０のアルキレン基、炭素数６以上のシクロアルキレン基、アリーレン基、又はアルキルアリーレン基を示し、Ａは、相互に独立に、水素原子又は１以上の（メタ）アクリロイルオキシ基を有する任意の有機基を示し、Ｂは、水素原子又は１以上の（メタ）アクリロイルオキシ基を有してもよい任意の有機基を示す）

(In the above general formula (1), R independently represent an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group, and A indicates each other. Independently, it represents any organic group having a hydrogen atom or one or more (meth) acryloyloxy groups, where B is any organic group which may have a hydrogen atom or one or more (meth) acryloyloxy groups. show)

Since the ultraviolet absorbing group of the conventional ultraviolet absorber is a large molecular chain having a structure grafted on the polymer chain, the formed coating film tends to be soft. Further, when the bond between the polymer chain and the ultraviolet absorbing group is broken, a single molecule generated from the ultraviolet absorbing group may easily bleed out. On the other hand, the reactive ultraviolet absorber of the present invention is a 2,4,6-tris (2-hydroxyphenyl) -1,3,5-triazine group (hereinafter, "triphenyltriazine group") which is an ultraviolet absorbing group. It also has a structure in which a plurality of reactive groups are bonded to a triphenyltriazine group. Therefore, even if one of the bonds derived from the plurality of reactive groups is cleaved, the remaining bonds are retained, so that bleeding is effectively suppressed. In addition, since triphenyltriazine is incorporated in the main skeleton, the rigidity of the aromatic ring can be utilized to improve the physical characteristics of the coating film. Therefore, if a coating agent containing the reactive ultraviolet absorber of the present invention is used, a coating film having excellent durability can be formed.

Further, in the reactive ultraviolet absorber of the present invention, a plurality of organic groups including a reactive group are grafted from a triphenyltriazine group which is an ultraviolet absorbing group. Therefore, since these a plurality of organic groups are easily dissolved and compatible with the solvent or monomer used in the coating agent, the amount of the reactive ultraviolet absorber to be blended in the coating agent can be increased.

It is considered that when the triphenyltriazine group, which is an ultraviolet absorbing group, is exposed to ultraviolet rays, the hydrogen atom is delocalized between the hydroxyl group and the nitrogen atom of the triazine ring, and the thermal energy is diffused to absorb the ultraviolet rays. The maximum absorption wavelength of the triphenyltriazine group is usually in the range of 300 to 360 nm.

In the general formula (1), R independently represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group. Specific examples of R include alkylene groups such as methylene, ethylene, propylene, methylethylene, butylene, isobutylene, hexylene, octylene, 2-ethylhexylene and decylene; cyclohexylene, methylcyclohexylene, trimethylcyclohexylene and cyclohexyldimethylene. Cycloalkylene group such as; arylene group such as phenylene and naphthylene; alkylarylene group such as methylphenylene; and the like. Among them, R in the general formula (1) is methylene (-CH _2- ), methylmethylene (-CH (CH ₃ )-), dimethylmethylene (-C (CH ₃ ) _2- ), ethylmethylene (-). CH (CH ₂ CH ₃ )-) and butylmethylene (-CH (CH ₂ CH ₂ CH ₂ CH ₃ )-) are preferable.

In the general formula (1), A represents any organic group having a hydrogen atom or one or more (meth) acryloyloxy groups independently of each other. Further, B represents any organic group which may have a hydrogen atom or one or more (meth) acryloyloxy groups. That is, the reactive ultraviolet absorber of the present invention preferably has two or more (meth) acryloyloxy groups in one molecule. When the number of (meth) acryloyloxy groups in one molecule is one, the ultraviolet-absorbing group is in a state of being grafted to the polymer chain, so that the thermal stability of the formed coating film is likely to decrease and the thermal stability is likely to decrease. Bleed may occur easily. In the general formula (1), A and B are independent of each other, a hydrogen atom, a 3- (meth) acryloyloxy-2-hydroxypropyl group, and a 3-hydroxy-4- (meth) acryloyloxy-cyclohexylmethyl. Group, 4- (meth) acryloyloxy-3-hydroxysilokuhexylmethyl group, or 4'-(meth) acryloyloxybutoxy-2-hydrosikipropyl group (provided that hydrogen atom is 2 of A and B). Less than one) is preferred.

In the general formula (1), as any organic group represented by B (excluding the group having a (meth) acryloyloxy group), a monofunctional epoxy compound or a polyfunctional epoxy compound is reacted with the carboxy group. The groups formed can be mentioned.

Examples of the monofunctional epoxy compound include 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, polyethylene glycol monolauryl ether glycidyl ether, phenyl glycidyl ether, t-butyl phenyl glycidyl ether and the like. By reacting these monofunctional epoxy compounds with a part of the carboxy group in the compound (I) described later, it may be possible to improve the solubility of the obtained reactive ultraviolet absorber in a solvent. Examples of the polyfunctional epoxy compound include hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether. By reacting these polyfunctional epoxy compounds with a part of the carboxy group in the compound (I), an oligomer-type reactive ultraviolet absorber having a relatively high molecular weight can be obtained.

<Manufacturing method of reactive UV absorber>
The reactive ultraviolet absorber of the present invention can be produced, for example, according to the method shown below. That is, the method for producing the reactive ultraviolet absorber of the present invention comprises the compound (I) represented by the following general formula (I), 3- (meth) acryloyloxy-1,2-epoxypropane, and (meth) acryloyl. It comprises a step of reacting with at least one compound (II) selected from the group consisting of oxy (3,4-epoxycyclohexyl) methane and (meth) acryloyloxy2- (2-epoxymethoxy) butyl. Then, in the above step, 1 mol of compound (I) is reacted with compound (II) which is more than 2 mol times and 3 mol times or less. Hereinafter, the details of the method for producing the reactive ultraviolet absorber of the present invention will be described.

（前記一般式（Ｉ）中、Ｒは、相互に独立に、炭素数１〜１０のアルキレン基、炭素数６以上のシクロアルキレン基、アリーレン基、又はアルキルアリーレン基を示す）

(In the general formula (I), R indicates an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group independently of each other).

The compound represented by the general formula (I) can be obtained by etherifying 2,4,6-tris (2,4-dihydroxyphenyl) -1,3,5-triazine. Further, 2,4,6-tris (2,4-dihydroxyphenyl) -1,3,5-triazine can be obtained by subjecting trichlorotriazine and resorcinol to a Friedelcraft reaction in the presence of aluminum chloride or the like.

Of the multiple hydroxyl groups of 2,4,6-tris (2,4-dihydroxyphenyl) -1,3,5-triazine, the hydroxyl group that does not contribute to ultraviolet absorption (hereinafter, also referred to as "hydroxyl group X" for convenience) By reacting a halogenated alkylcarboxylic acid (halocarboxylic acid) in the presence of an alkali such as sodium hydroxide or potassium carbonate, the compound (I) represented by the general formula (I) can be obtained. As the halocarboxylic acid, it is preferable to use a compound that is easily reactive, easily available, and relatively inexpensive. Examples of such halocarboxylic acids include chloroacetic acid, bromoacetic acid, iodoacetic acid, 2-chloropropionic acid, 2-bromopropionic acid, 2-chlorobutyric acid, 2-bromobutyric acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, and 2 -Chloroacetic acid, 2-bromovaleric acid and the like can be mentioned. Next, the target reactive ultraviolet absorber is obtained by reacting the compound (I) represented by the general formula (I) with a compound having a group capable of reacting with a carboxy group and a (meth) acryloyloxy group. Obtainable. The compound represented by the general formula (I) may be produced by a method other than the above-mentioned method, or a commercially available compound may be used.

Examples of the group capable of reacting with the carboxy group in the compound to be reacted with the compound (I) represented by the general formula (I) include a hydroxyl group, an epoxy group, a halogen-substituted alkyl group and the like. Among them, it is preferable to use a compound having an epoxy group, 3- (meth) acryloyloxy-1,2-epoxypropane, (meth) acryloyloxy (3,4-epoxycyclohexyl) methane, and (meth) acryloyloxy. It is further preferred to use at least one compound (II) selected from the group consisting of 2- (2-epoxymethoxy) butyl. When such compound (II) is used, the reaction is mild, no by-products are generated due to desorption, and even if the catalyst remains, there is almost no problem. That is, it is preferable because it can be used as it is without purification after the reaction.

It is preferable to react 1 mol of the compound (I) represented by the general formula (I) with the compound (II) which is more than 2 mol times and 3 mol times or less, and is 2.3 to 2.9 mol times. It is more preferable to react (II), and it is particularly preferable to react the compound (II) of 2.5 to 2.8 mol times or less. When the compound (II) in an amount exceeding 3 mol times is reacted with 1 mol of the compound (I), the compound (II) having an epoxy group remains. Therefore, it becomes necessary to purify the compound (II) in order to remove it, which complicates the process.

When the compound (I) represented by the general formula (I) is reacted with the compound (II), the epoxy group is ring-opened and a hydroxyl group is generated. It is also possible to react the generated hydroxyl group with an acid anhydride to form a half ester to obtain a reactive ultraviolet absorber having alkali developability and high bleed-out resistance. Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, cyclohexendicarboxylic acid anhydride and the like.

An isocyanate compound may be reacted with the generated hydroxyl group. For example, when a monofunctional alkyl monoisocyanate such as octadecyl isocyanate or lauryl monoisocyanate is reacted, the solubility in a solvent can be improved. In addition, 2-isocyanatoethyl (meth) acrylate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate, 2-[(3). , 5-Dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate, 2- [0- (1'-methylpropyridenamino) carboxyamino] ethyl (meth) acrylate and other (meth) acryloyloxy and isocyanate groups. The compound may be reacted.

When the compound (I) and the compound (II) are reacted, a catalyst is usually used. Examples of the catalyst include boron fluoride ethyl ether complex; amines such as triethylamine and 1,4-diazabicyclo [2.2.2] octane; trialkylphosphorus and triaryllin compounds such as triphenylphosphine; triethylbenzylammonium chloride, tetramethyl. Quaternary ammonium salts such as ammonium chloride; imidazole compounds such as 2-methyl-4-ethylimidazole and 2-methylimidazole; hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; ethyltriphenylphosphonium bromide And the like, quaternary organic phosphorus salts and the like can be mentioned. The amount of the catalyst is preferably 0.001 to 10 mol%, more preferably 0.1 to 5 mol% with respect to the epoxy group.

It is preferable to react the compound (I) with the compound (II) in a solvent capable of dissolving the compound (I) and the catalyst. As the solvent, aromatic hydrocarbons such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate, butyl acetate and amyl acetate; tetrahydrofuran, dioxane, dioxorane, dimethylethylene glycol and the like. Ether-based solvent; Examples thereof include ether ester-based solvents such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. Of these, it is preferable to use an alcohol solvent, a glycol solvent, an amide solvent, or a sulfoxide solvent.

In the presence of a polymerization inhibitor such as methoxyphenol used as needed, compound (I) and compound (II) are reacted while blowing air as needed. The reaction temperature may be, for example, in the range of room temperature to 150 ° C. As described above, since no by-product is produced even if the compound (I) and the compound (II) are reacted, the obtained solution can be used as it is as a solution of the reactive ultraviolet absorber.

<Ultraviolet / electron beam curable coating agent>
The ultraviolet / electron beam curable coating agent of the present invention (hereinafter, also referred to as “UVEB coating agent”) contains the above-mentioned reactive ultraviolet absorber in an amount of 0.1 to 50% by mass, preferably 0.5 to 30% by mass. %, More preferably 1 to 20% by mass. If the content of the reactive ultraviolet absorber is less than 0.1% by mass, the ultraviolet absorbing ability of the formed coating film is lowered. On the other hand, if the content of the reactive ultraviolet absorber is more than 50% by mass, the reactive ultraviolet absorber that could not be completely reacted is likely to remain in the coating film, and the coating film may become brittle. When it is desired to improve the weather resistance (light resistance) of the formed coating film, the content of the reactive ultraviolet absorber in the UVEB coating agent is preferably 0.1 to 10% by mass. Further, when it is desired to improve the weather resistance (light resistance) of the base of the formed coating film, it is preferable that the content of the reactive ultraviolet absorber in the UVEB coating agent is 1 to 50% by mass.

The UVEB coating agent may further contain a conventionally known material as another component. Other components include curing components such as monofunctional monomers, polyfunctional monomers, photocurable oligomers, and photocurable polymers, as well as photopolymerization initiators for photocuring these curing components, viscosity of coating agents, and the like. Examples thereof include an organic solvent for adjusting the coatability.

Examples of the monofunctional monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and hexyl (meth). Acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, adamantylmethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Meta) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, 2-ethoxyethyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, vinyloxyethoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phthalic anhydride and 2-hydroxyethyl (meth) acrylate Additives, radically polymerizable monomers such as acryloylmorpholine and the like can be mentioned.

Examples of the polyfunctional monomer and the photocurable oligomer include neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, poly (n = 2 or more) ethylene glycol di (meth) acrylate, and polypropylene glycol (n = 2 or more). ) Di (meth) acrylate, polybutylene glycol (n = 2 or more) di (meth) acrylate, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (meth) ) Acryloxidiethoxyphenyl) Propane, Trimethylol Propane Diacrylate, Bis (2- (Meta) Acryloxyethyl) -Hydroxyethyl-Isocyanurate, Trimethylol Propanetri (Meta) Acrylate, Tris (2- (Meta) Acrylate) Loxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol 2-Hydroxyethyl (meth) acrylate is reacted with an epoxypoly (meth) acrylate such as epoxydi (meth) acrylate obtained by reacting A-type diepoxy with (meth) acrylic acid, and a trimer of 1,6-hexamethylene diisocyanate. Urethane tri (meth) acrylate, urethane di (meth) acrylate obtained by reacting isophorone diisocyanate with 2-hydroxypropyl (meth) acrylate, and urethane hexa (meth) acrylate obtained by reacting isophorone diisocyanate with pentaerythritol tri (meth) acrylate. ) Acrylate, Urethane di (meth) acrylate obtained by reacting dicyclohexyldiisocyanate with 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl in a urethanization reaction product of dicyclohexyldiisocyanate and poly (n = 6 to 15) tetramethylene glycol. Urethane poly (meth) acrylate such as urethane di (meth) acrylate reacted with (meth) acrylate, polyester (meth) acrylate reacted with succinic acid and (meth) acrylic acid with trimethylol ethane, and trimethylol propane. Polyester poly (meth) acrylate or the like reacted with succinic acid, ethylene glycol, and (meth) acrylic acid ( Meta) Acrylate and the like can be mentioned.

As the photocurable polymer, a plurality of (meth) acryloyloxy groups exhibiting radical polymerizable properties are introduced into the terminals and side chains of polymers such as poly (meth) acrylate, polyurethane, polyester, polyamide, polyimide, and polyepoxy resin. Polymers and the like can be mentioned. Further, an alkali-developable photocurable polymer having a carboxy group or the like can also be used.

Examples of the photopolymerization initiator include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethylketal, 2,2-diethoxyacetophenone, and 1-hydroxycyclohexylphenylketone. , Methylphenylglioxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one and other carbonyl compounds; tetramethylthium monosulfide, tetramethylthiumum disulfide and other sulfur compounds; 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide, bis (2,6-dimethoxybenzoyl) -2,4 , A phosphate compound such as 4-trimethyl-pentylphosphinoxide; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, camphorquinone and the like can be mentioned.

Examples of the organic solvent include hydrocarbon solvents, alcohol solvents, ester solvents, ketone solvents, glycol solvents, glycol ester solvents, amide solvents, carbonate solvents, sulfoxide solvents, ionic liquids and the like. can.

Since the reactive ultraviolet absorber has a good ultraviolet absorbing ability, it is possible to suppress photodegradation of the pigment added to the UVEB coating agent due to ultraviolet rays and prevent the color change of the formed coating layer (coating film). can. That is, it is preferable that the UVEB coating agent further contains an organic pigment. Examples of organic pigments are C.I. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 97, 109, 110, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 175, 180, 181, 185, 191; C.I. I. Pigment Orange 16, 36, 43, 51, 55, 59, 61, 64, 71, 73; C.I. I. Pigment Red 4, 5, 9, 23, 48, 49, 52, 53, 57, 97, 112, 122, 123, 144, 146, 147, 149, 150, 166, 168, 170, 176, 177, 180, 184, 185, 192, 202, 207, 214, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 238, 240, 242, 254, 255, 264, 269, 272; C.I. I. Pigment Violet 19, 23, 29, 30, 37, 40, 50; C.I. I. Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64; C.I. I. Pigment Green 7, 36, 58; C.I. I. Pigment Black 7; C.I. I. Pigment White 6 and the like can be mentioned.

Two or more kinds of organic pigments can be used in combination. As a method of combining (mixing) two or more kinds of organic pigments, there are a method of mixing powder pigments, a method of mixing paste pigments, a method of mixing at the time of pigmentation to obtain a solid solution, and the like.

UVEB coating agents include light stabilizers such as nitroxide compounds, antioxidants such as hindered phenol, dyes, pigment dispersants, fluorescent whitening agents, and leveling agents for improving the physical properties and coatability of coating materials. , Antifoaming agent, Lubricating agent, Thickener, Antistatic agent, Surfactant, Silane coupling agent, Antioxidant, Anti-yellowing agent, Brewing agent, Infrared absorber, Adhesion promoter, Antifouling agent, Repellent It may contain a liquid agent, a curable catalyst, an inorganic filler such as silica, metal fine particles, or the like.

When used as an ink for inkjet, the viscosity of the UVEB coating agent is preferably 50 mPa · s or less in consideration of ejection properties. When used for coating with a flow coat or dip, the viscosity of the UVEB coating agent is preferably 100 mPa · s or less. On the other hand, a highly viscous coating composition (high solid type) having a solid content of more than 80% by mass may be used.

When a UVEB coating agent is used, a coating film having excellent properties such as light resistance, weather resistance, scratch resistance, bleed resistance, and adhesion to a substrate is formed, and these properties are maintained for a long period of time. be able to. The thickness of the coating film to be formed is preferably 0.1 to 50 μm, for example. If the thickness of the coating film is less than 0.1 μm, the coating film may be easily damaged or the ultraviolet absorbing ability may be slightly insufficient. On the other hand, if the thickness of the coating film is more than 50 μm, cracks may easily occur in the coating film. Considering hardness, scratch resistance, long-term stable adhesion, crack suppression, etc., the thickness of the coating film to be formed is preferably 1 to 30 μm.

Examples of the base material forming the coating film include various polymers, wood, fibers, ceramics, glass, metals, composites thereof, and laminates thereof. Further, in order to further enhance the adhesion of the coating film, the surface of the base material may be activated by corona treatment, plasma treatment, chemical treatment or the like.

A coating film can be formed by applying a UVEB coating agent to the surface of a substrate, an article, or the like and then irradiating it with light to cure it. The UVEB coating agent can be applied to the surface of a base material or the like by brush coating, spray coating, dip coating, flow coating, roll coating, curtain coating, spin coating, inkjet or the like.

The applied UVEB coating agent may be heated or heated to remove volatile components to form an uncured film, and then further irradiated with ultraviolet rays or electron beams to cure the film. Ultraviolet rays and electron beams can be irradiated using a light source such as a high-pressure mercury lamp, a metal halide lamp, a xenon arc, a carbon arc, or an LED lamp. The dose of light, for example, preferably adjusted to 100~10,000mJ / cm ^2, and even more preferably from 300~5,000mJ / cm ^2.

The UVEB coating agent is suitable for painting or coating articles for outdoor use exposed to light. Specifically, it is used for building materials, automobiles, agricultural materials, daily necessities, displays, plastic parts such as home appliances, wood parts, glass parts, etc. to prevent deterioration due to light and maintain a good appearance for a long period of time. Can be retained. Further, by using a UVEB coating agent containing a large amount of a reactive ultraviolet absorber, it is possible to form an ultraviolet absorbing layer that protects the inside and the lower layer from light. The UVEB coating agent is useful as a material for forming a coating layer that coats and protects the surface of packaging members such as foods, pharmaceuticals, display parts, industrial reagents, medical materials, etc., which are easily photodegraded.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In addition, "part" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

<Manufacturing of reactive UV absorber>
(Example 1: Reactive UV absorber-1 (M-RUVA-1))
A compound represented by the following formula (2) (2,4,6-tris [4- (1-octyloxycarbonyl) ethyloxy-2-) is placed in a separable flask equipped with a stirrer, a thermometer, and a fractional distillation device. Hydroxyphenyl] -1,3,5-triazine) (hereinafter, also referred to as "triester compound") was added in an amount of 80 parts and 20 parts of a propylene glycol monomethyl ether acetate was added to homogenize the mixture. Then, 100 parts of methanol was added and stirred.

A sodium hydroxide aqueous solution prepared by putting 16 parts of sodium hydroxide and 100 parts of water in a separate container was added to a separable flask. After heating to about 80 ° C. to distill off methanol, the mixture was heated to 92 ° C. to allow hydrous methanol to flow out. After transferring the contents to a separating funnel, ethyl acetate was added, and the organic dissolved matter was extracted and removed to obtain an aqueous layer.

800 parts of ion-exchanged water and the obtained aqueous layer were placed in a flask equipped with a dissolver. 46 parts of 3.5% hydrochloric acid was added under stirring, and the precipitate was obtained by filtration. The obtained precipitate was washed with water, dried and pulverized to obtain a yellow powder. The powder obtained by using a nuclear magnetic resonance apparatus (NMR) and an infrared spectrophotometer (IR) is analyzed, and the compound (2,2', 2 "- [1, represented by the following formula (3) is analyzed. It was confirmed that the substance was 3,5-triazine-2,4,6-triyltris [(3-hydroxy-4,1-phenylene) oxy]] trispropionic acid) (hereinafter, also referred to as "tricarboxylic acid").

The purity measured by high performance liquid chromatography (HLPC) using an acetonitrile / water mixed solvent as a developing solvent was 98.8%. The maximum absorption wavelength measured using a spectrophotometer using dimethyl sulfoxide as a solvent was 350 nm. The obtained tricarboxylic acid was soluble in methanol and glycols and insoluble in tetrahydrofuran (THF), methyl ethyl ketone (MEK), and propylene glycol monomethyl ether acetate (PGMAc).

144.8 parts of propylene glycol monomethyl ether was placed in a separable flask equipped with a stirrer, a thermometer, an air introduction tube, and a fractional distillation device and stirred. 50.1 parts (pure content 50 parts, 0.08 mol) of the obtained tricarboxylic acid was added, and the mixture was heated to 50 ° C. and dissolved. After adding 0.1 part of hydroquinone and 1.6 part of triphenylphosphine and blowing air weakly, 29.2 parts of 3-methacryloyloxy-1,2-epoxypropane (GMA) (2 per mol of tricarboxylic acid). .5 mol times) was further added. Was heated to 100 ° C. and reacted for 2 hours, by IR, the disappearance of the absorption of 909cm ^-1 corresponding to the epoxy group, the generation of absorption around 3480cm ^-1 corresponding to hydroxyl groups, and corresponds to the ester group 1,720 cm ^- An increase in absorption of ^{1 was confirmed.} In addition, it was analyzed by gas chromatography (GC), and it was confirmed that the peak of GMA was not detected. Furthermore, the non-volatile content reaching a constant amount at 180 ° C. was 34.7%. Reactive UV absorber-1 (M-) analyzed using NMR and IR and containing the compound represented by the following formula (4) as a main component and the compound represented by the following formula (5) as a sub-component. It was confirmed that RUVA-1) was obtained. The maximum absorption wavelength was 357 nm. When the obtained solution of M-RUVA-1 was added to MEK, THF, and PGMAc, respectively, they dissolved without precipitation.

(Example 2: Reactive UV absorber-2 (M-RUVA-2))
The main component is the compound represented by the above formula (4) in the same manner as in Example 1 above, except that the amount of GMA is 29.2 parts (2.79 mol times with respect to 1 mol of tricarboxylic acid). A reactive ultraviolet absorber-2 (M-RUVA-2) containing the compound represented by the above formula (5) as a sub-ingredient was obtained. The obtained M-RUVA-2 contained a large amount of the compound represented by the above formula (4) as compared with the M-RUVA-1 obtained in Example 1. Analysis by GC confirmed that no peak of GMA was detected. The non-volatile content reaching a constant amount at 180 ° C. was 35.9%. The maximum absorption wavelength was 357 nm.

(Example 3: Reactive UV absorber-3 (M-RUVA-3))
Same as Example 1 above, except that 40.2 parts of methacryloyloxy (3,4-epoxycyclohexyl) methane (ECHMMA) (2.5 mol times with respect to 1 mol of tricarboxylic acid) was used instead of GMA. A reactive ultraviolet absorber-3 (M-RUVA-3) containing the compound represented by the following formula (6) as a main component and the compound represented by the following formula (7) as a sub-component was obtained. .. It was analyzed by GC and it was confirmed that the peak of ECHMMA was not detected. The non-volatile content reaching a constant amount at 180 ° C. was 38.0%. The maximum absorption wavelength was 356 nm.

(Example 4: Reactive UV absorber-4 (M-RUVA-4))
Same as Example 1 above, except that 41.0 parts of acryloyloxy2- (2-epoxymethoxy) butyl (GHBA) (2.56 mol times with respect to 1 mol of tricarboxylic acid) was used instead of GMA. A reactive ultraviolet absorber-4 (M-RUVA-4) containing the compound represented by the following formula (8) as a main component and the compound represented by the following formula (9) as a sub-component was obtained. .. It was analyzed by GC and it was confirmed that the peak of GHBA was not detected. The non-volatile content reaching a constant amount at 180 ° C. was 37.4%. The maximum absorption wavelength was 356 nm.

(Example 5: Reactive UV absorber-5 (M-RUVA-5))
The table is represented by the following formula (10) in the same manner as in Example 4 above, except that the amount of GHBA was replaced with 32 parts and 8.4 parts of 2-ethylhexyl monoglycidyl ether (EHG) was further used. Reactive UV absorber-5 (M-RUVA-5) to be obtained was obtained. A part of the 4'-(meth) acryloyloxybutoxy-2-hydroshikipropyl group in the following formula (10) was a hydrogen atom (-H). Analysis by GC confirmed that neither GHBA nor EHG peaks were detected. The non-volatile content reaching a constant amount at 180 ° C. was 37.2%. The maximum absorption wavelength was 356 nm.

(Comparative Example 1: Comparative Reactive UV Absorber-1 (R-RUVA-1))
A compound represented by the following formula (11) (2- [4-[(2-hydroxy-3- (2'-ethyl) hexyl)) is placed in a separable flask equipped with a stirrer, a thermometer, and a fractional distillation device. Oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine)) (hereinafter, also referred to as "monool form") 50 parts, PGMAc 120.8 parts , And 0.1 part of hydroquinone were added and heated to 100 ° C. while blowing air. A mixture of 12.4 parts of 2-isocyanatoethyl methacrylate (MOI) and 12.4 parts of PGMAc was added, and a mixture of 0.05 parts of tin dilaurate and 12.4 parts of PGMAc was further added. The reaction was carried out at 100 ° C. for 5 hours to obtain a comparatively reactive ultraviolet absorber-1 (R-RUVA-1) represented by the following formula (12). Analysis by IR confirmed the disappearance of absorption near ^{2,200 cm-1 corresponding to MOI.} The non-volatile content reaching a constant amount at 180 ° C. was 29.4%. The maximum absorption wavelength was 341 nm. It was confirmed that the obtained R-RUVA-1 was soluble in a solvent such as MEK.

(Comparative Example 2: Comparative Reactive UV Absorber-2 (R-UVA-2))
The following formula (13) is the same as in Comparative Example 1 described above, except that 19.0 parts of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (BEI) is used instead of 2-isocyanatoethyl methacrylate. ) Was obtained as a comparatively reactive ultraviolet absorber-2 (R-RUVA-2). The non-volatile content reaching a constant amount at 180 ° C. was 31.7%. The maximum absorption wavelength was 340 nm.

<Manufacturing of coating agent and formation of coating film>
(Examples 6 to 9, Comparative Examples 3 to 6)
Reactive UV absorber manufactured for 30 parts of urethane acrylate oligomer 1 (trade name "WR-100", manufactured by Dainichiseika Kogyo Co., Ltd.) and 70 parts of urethane acrylate oligomer 2 (trade name "GD785", manufactured by DIC). , Triester form, or monool form (as a solid content) was added. MEK was added and diluted so as to have a solid content of 50% to obtain a coating agent. A coating agent obtained using a No. 6 bar coater was applied to a primer-treated olefin sheet or a transparent PET film (100 μm), dried at 60 ° C. for 1 minute, and then an electron beam (50 kGy, A pressure voltage of 165 kv) was applied to cure the coating agent to form a coating film.

<Evaluation>
(Weather resistance test)
Using an olefin sheet having a coating film formed on its surface, a "super UV test" and a "QUV test" were performed under the conditions shown below.
[Super UV test]
Lamp type: Metal halide lamp Lamp illuminance: 50mW / cm ²
Temperature: 63 ° C
Irradiation time: 20 hours Cycle: Shower 30 seconds, condensation 4 hours cycle for 1,000 hours [QUV test]
Lamp type: UV lamp Lamp illuminance: 0.71 W / m ²
Temperature: 60 ° C
Irradiation time: 4 hours Cycle: 5,000 hours cycle of condensation at 50 ° C for 4 hours

The 60 ° C. gloss retention rate (%) of the coating film after each test was measured. The results are shown in Table 1. In addition, the edge of the coating film was visually observed to evaluate the adhesion. The results are shown in Table 1.

(Scratch resistance)
Steel wool was placed on the surface of the coating film formed on the olefin sheet and reciprocated 10 times under a ^{load of 100 g / cm 2.} The appearance of the coating film after 10 round trips was visually confirmed, and the scratch resistance was evaluated. The results are shown in Table 1.

(Bleed resistance)
After immersing the PET film having the coating film formed on the surface in warm water at 60 ° C. for 1 week, the appearance of the coating film was visually confirmed. In addition, the total light transmittance (absorbance of the maximum absorption wavelength) before and after immersion was measured, and the retention rate (%) of the total light transmittance was calculated. The results are shown in Table 1.

<Preparation and evaluation of UV ink>
(Example 10)
Polyester urethane acrylate (terephthalic acid / sebacic acid / ethylene glycol / neopentyl glycol copolymer (hydroxyl value: 37.4 mgKOH / g), isophorone diisocyanate, and urethane oligomer with hydroxyethyl acrylate, number average molecular weight: 4,500) 50 parts, trimethylolpropane triacrylate 15 parts, phenoxyethyl acrylate 35 parts, reactive ultraviolet absorber-4 (M-RUVA-4) 10 parts (as solid content), 2-hydroxy-2-methylpropylphenone 3 parts , And 2,2-diethoxyacetophenone were mixed and stirred to obtain UV ink.

UV ink obtained by using a number 6 bar coater is ^{applied to a polycarbonate plate so as to be 3 g / m 2,} and then UV (high pressure mercury lamp 160 w / cm × 3, 50 m / min) is applied to the UV ink. Was cured to form a coating film. As comparative examples, (i) a product to which a triester was added instead of M-RUVA-4; and (ii) a product to which M-RUVA-4 was not added; were prepared to form a coating film. bottom.

A "super UV test" was performed under the conditions shown below using a polycarbonate plate having a coating film formed on the surface.
[Super UV test]
Lamp type: Metal halide lamp Lamp illuminance: 50mW / cm ²
Temperature: 83 ° C
Irradiation time: 200 hours

The degree of yellowing of the coating film before and after the super UV test was visually confirmed and compared. (Ii) The coating film formed with the UV ink of the comparative example to which M-RUVA-4 was not added was yellowed. Further, (i) the coating film formed with the UV ink of the comparative example to which the triester body was added had a slight yellow discoloration and the surface was sticky. On the other hand, the coating film formed with the UV ink of Example 10 was not discolored and the surface was not sticky.

<Manufacturing and evaluation of UV curable coating agent (yellow color)>
(Examples 11 to 14)
Yellow pigments (Pigment Yellow 74 (manufactured by Dainichiseika Kogyo Co., Ltd.), Pigment Yellow 150 (manufactured by Rankses), Pigment Yellow 155 (manufactured by Dainichiseika Kogyo Co., Ltd.), and Pigment Yellow 180 (manufactured by Dainichiseika Kogyo Co., Ltd.)) 20 parts each, 2 parts of acidic synergist represented by the following formula (14), synthetic example 9 described in Japanese Patent No. 5933380, polyethylene glycol monopropylene glycol monomethyl ether monoamine (molecular weight 2000). , A polymer-type dispersant having a number average molecular weight of 17,300, PDI 1.41, and an amine value of 40.0 mgKOH / g obtained by living radical polymerization of macromonomer / dimethylaminoethyl methacrylate / methyl methacrylate, which is a reaction product with MOI. , 100% solid content) and 70 parts of phenoxyethyl acrylate (POE) were placed in a poly bottle. Zirconia beads (0.1 m) were filled and dispersed using a paint conditioner for 3 hours. After removing the zirconia beads, POE was added and diluted to a non-volatile content of 25%. Coarse particles were removed by filtration through a filter (0.5 μm) to prepare a mill base (pigment dispersion) of four types of yellow pigments.

21.6 parts of each pigment dispersion prepared, 2 parts of reactive UV absorber-5 (M-RUVA-5), 51.4 parts of 2- (2-vinyloxyethoxy) ethyl acrylate, trimethylolethylene oxide adduct 20 parts of propanetriacrylate, 3 parts of 2-hydroxy-2-methylpropylphenone, and 2 parts of 2,2-diethoxyacetophenone are mixed and homogenized, and then filtered through a filter (1.0 μm) to give a yellow color. UV curable coating agents (4 types) were obtained. As a comparative example, a yellow-colored ultraviolet curable coating agent (4 types) to which (iii) M-RUVA-5 was not added was prepared.

A UV-curable coating agent obtained using a No. 6 bar coater was applied to each of a primer-treated transparent PET film (100 μm), and then dried at 60 ° C. for 1 minute. The ultraviolet curable coating agent was cured by irradiating with ultraviolet rays for 120 hours using a xenon weather meter to form a coating film. As a result, it was found that the pigment in the UV curable coating agent of the comparative example had faded. Further, among the ultraviolet curable coating agents of Examples, Pigment Yellow 74 was slightly faded, but the other pigments were hardly changed. The viscosities of the coating agents of the examples were as low as around 5.0 mPa · s. Therefore, the coating agent of the example is useful as an inkjet ink.

The reactive ultraviolet absorber of the present invention is, for example, a coating agent for protection or design of automobiles, buildings, outer walls, ships, roads, solar power generators, etc., and a packaging material for packaging foods and pharmaceuticals. It is useful as a material to be blended in the coating agent of.

Claims (7)

A reactive ultraviolet absorber represented by the following general formula (1).

(In the above general formula (1), R independently represent an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group, and A indicates each other. Independently, it represents any organic group having a hydrogen atom or one or more (meth) acryloyloxy groups, where B is any organic group which may have a hydrogen atom or one or more (meth) acryloyloxy groups. show) In the general formula (1), R represents a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylmethylene group, or a butylmethylene group independently of each other.
A and B are independent of each other, hydrogen atom, 3- (meth) acryloyloxy-2-hydroxypropyl group, 3-hydroxy-4- (meth) acryloyloxy-cyclohexylmethyl group, 4- (meth) acryloyloxy. -3-Hydroxysiroquehexylmethyl group or 4'-(meth) acryloyloxybutoxy-2-hydrosikipropyl group (provided that there are less than two hydrogen atoms in A and B). The reactive UV absorber described. The reactive UV absorber according to claim 1 or 2, which has two or more (meth) acryloyloxy groups in one molecule. The method for producing a reactive ultraviolet absorber according to any one of claims 1 to 3.
Compound (I) represented by the following general formula (I), 3- (meth) acryloyloxy-1,2-epoxypropane, (meth) acryloyloxy (3,4-epoxycyclohexyl) methane, and (meth). It comprises a step of reacting with at least one compound (II) selected from the group consisting of acryloyloxy2- (2-epoxymethoxy) butyl.
A method for producing a reactive ultraviolet absorber by reacting 1 mol of the compound (I) with the compound (II) having a reaction value of more than 2 mol times and 3 mol times or less.

(In the general formula (I), R indicates an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group independently of each other). An ultraviolet / electron beam curable coating agent containing 0.1 to 50% by mass of the reactive ultraviolet absorber according to any one of claims 1 to 3. The ultraviolet / electron beam curable coating agent according to claim 5, which is used outdoors. The ultraviolet / electron beam curable coating agent according to claim 5 or 6, further containing an organic pigment.