JP2002138076A - Compound to generate amine by light irradiation and photosetting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compound that is easily decomposed to generate amine by light irradiation and compatible well with compounds to be cured by amine and can react with these compounds by light irradiation capable of giving cured materials, and a photosetting composition made of the above compound. SOLUTION: This compound to generate an amino group by light irradiation is represented by formula 1 (wherein R1 is an n-valent organic group; each of R2 and R3 is hydrogen, an aromatic group or an aliphatic group; and (n) is a positive integer of 1 or more) containing a carabamoyloxyimino group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound capable of generating an amine upon irradiation with light and a photocurable composition.

[0002]

2. Description of the Related Art As a compound which generates an amine by light irradiation, a cobalt amine complex, o-nitrobenzyl carbamate, oxime ester and the like are known.

However, these compounds which generate an amine upon irradiation with light have a low quantum yield.
l. Chem. Soc. Jpn. , (No. 11), 2
495, (1988), the quantum yield of a cobaltamine complex is about 0.01 for light of 254 nm, and the quantum yield of o-nitrobenzyl carbamate is about 254 nm of light. On the other hand, the quantum yield of the oxime ester was about 366 nm even when the photosensitizer was used in combination.
Is about 0.3 for the light of.

[0004] As a photocurable resin composition in which a compound which generates an amine by light irradiation reacts with a compound which is cured by the amine and cures, for example, an o-nitrobenzyl carbamate compound is prepared by photo-anionic polymerization of an epoxy resin. There is an epoxy resin composition used as an initiator (JP-A-7-70292).

[0005] However, the o-
Nitrobenzyl carbamate compounds have poor photodegradation efficiency to amine compounds, so long-time light irradiation is required and a large amount must be added to epoxy resin to obtain a sufficient curing rate. There was a problem.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a compound which is excellent in photodegradability and which emits an amine upon irradiation with light which has excellent reactivity and compatibility with a compound which is cured by an amine. is there.

[0007]

The compound for generating an amine upon irradiation with light according to the first aspect of the present invention is represented by the following structural formula 1 containing a carbamoyloxyimino group.

[0008]

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In the structural formula 1, R1 is an n-valent organic group, R2 and R3 are each a hydrogen, aromatic or aliphatic group, and n is a positive integer of 1 or more. Claim 2
The compound which generates an amine upon irradiation with light according to the invention of the described invention is
It is represented by the following structural formula 2 containing a carbamoyloxyimino group.

[0010]

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However, in the structural formula 2, R2 and R3
Is hydrogen, an aromatic group or an aliphatic group, and R5 is
At least one member selected from the group consisting of an isocyanate group, a (meth) acryloyl group and a vinyl group;
Is an (m + n) -valent organic group, and n and m are each a positive integer of 1 or more.

The compound for generating an amine upon irradiation with light according to the invention of claim 3 is the compound which generates an amine upon irradiation with light according to claim 1 or 2, wherein R 2 or R 3 of the structural formula 1 or 2 is used. One is a hydrogen or an aliphatic group, and the other is an aromatic group.

The compound for generating an amine upon irradiation with light according to the invention of claim 4 is the same as the compound for generating an amine upon irradiation with light according to any one of claims 1 to 3, except that R1 of the structural formula 1 or 2 Or, R4 is an aromatic group.

The compound for generating an amine upon irradiation with light according to the invention of claim 5 is the same as the compound for generating an amine upon irradiation with light according to any one of claims 1 to 4, except that R2 represented by the structural formula 1 or 2 And R3 are each a group selected from the group consisting of hydrogen, a methyl group, a phenyl group, and a naphthyl group.

The compound for generating an amine upon irradiation with light according to the invention of claim 6 is a polymer or oligomer obtained by copolymerizing a compound having a radical polymerizable group and a monomer having a (meth) acryloyl group and a carbamoyloxyimino group. It is.

[0016] The photocurable composition of the invention according to claim 7 comprises:
A compound comprising a compound which generates an amine by light irradiation according to claim 1 and a compound which is cured by the amine.
The photocurable composition of the invention according to claim 8 is the photocurable composition according to claim 7, which contains a thioxanthone sensitizer.

In the compound of the present invention that generates an amine upon irradiation with light represented by the structural formula 1, R1 is an n-valent organic group, preferably an aliphatic group; an aromatic group; Group or polyester group. R2 and R3 are hydrogen or an organic group such as an aromatic group or an aliphatic group, more preferably hydrogen,
It is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a phenyl group, a naphthyl group or a phenyl group having a substituent introduced therein, and a naphthyl group.

In the structural formula 1, n is an integer of 1 or more, preferably 2 or more. When n is 2 or more, the photodegradability to the amine and the reactivity of the generated amine can be improved.

In the structural formula 1, when the molecular weight of R1 is small, the compatibility with a compound which is cured by an amine decreases,
When the molecular weight is large, the reactivity of the generated amine compound is reduced, so that the molecular weight is preferably 200 to 20,000, more preferably 4 to 4.
It is preferably from 10,000 to 10,000, more preferably from 400 to 5,000.

As R2 and R3, one of R2 and R3 is hydrogen or an aliphatic group, and the other is
It is preferably an aromatic group, more preferably selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, a naphthyl group, or a phenyl group having a substituent introduced therein, and a naphthyl group. And more preferably a combination of hydrogen and a phenyl group, a combination of hydrogen and a naphthyl group, a combination of a methyl group and a phenyl group, or a combination of a methyl group and a naphthyl group, and particularly preferably a phenyl group. is there.

[0021] When light in compounds of structure 1 is irradiated, amines having R1 (-NH _{2) n} or R1 (-NH-NH _{2) n} structure is produced. In the compound of the present invention which generates an amine upon irradiation with light, which contains a carbamoyloxyimino group represented by Structural Formula 2, R2 and R3
Is omitted because it is the same as the description of Structural Formula 1.

In the structural formula 2, R4 is an (m + n) organic group, preferably an aliphatic group, an aromatic group, a polyurethane group, a polyether group, or a polyester group, and more preferably an aromatic group. is there.

In the structural formula 2, when the molecular weight of R4 is small, the compatibility with a compound which is cured by an amine decreases,
When the molecular weight is large, the reactivity of the generated amine compound is reduced, so that the molecular weight is preferably 200 to 20,000, more preferably 4 to 4.
It is preferably from 10,000 to 10,000, more preferably from 400 to 5,000.

In the structural formula 2, n and m are each a positive integer of 1 or more, and n is preferably 2 or more. In the structural formula 2, R5 is at least one member selected from the group consisting of an isocyanate group, a (meth) acryloyl group, and a vinyl group.

[0025] When light in the compounds of structure 2 is _{illuminated, (R5-) m R4 (-NH} 2) n or (R5-) _m R
4 (-NH-NH ₂₎ amine is generated having a structure of _n. As the compound that generates an amine by light irradiation represented by Structural Formula 1 or 2 of the present invention, a compound formed of an isocyanate compound in which an isocyanate group is bonded to an aromatic hydrocarbon and an oxime compound is preferable. The resulting compound alone has particularly excellent photodegradability without a photosensitizer.

The method of obtaining a compound which generates an amine by light irradiation represented by the structural formula 1 or 2 of the present invention is not particularly limited. For example, a urethane prepolymer (a low molecular weight isocyanate compound) Oxime compound) and an oxime compound are charged so that the number of moles of isocyanate groups of the isocyanate compound and the number of moles of hydroxyl groups of the oxime are equimolar.
It is obtained by adding and reacting a catalyst such as a secondary amine.

When R1 in the structural formula 1 is a (meth) acryloyl group or a vinyl group, for example, an isocyanate group such as 2-methacryloyloxyethyl isocyanate or dimethyl methisopropenylbenzyl isocyanate is combined with an acroyl group or a vinyl group. A method of reacting a compound having an oxime with an oxime, a method of reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group, and a (meth) acrylate having a carboxyl group, and then reacting the remaining isocyanate group with the oxime. Can be

The above (meth) acrylate having a hydroxyl group is not particularly limited.
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methacryloyloxyethyl acid phosphate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2- (meth) acryloyloxyethyl-2- Hydroxyethyl phthalic acid epoxy ester, etc., having a carboxyl group (meth)
As the acrylate, for example, (meth) acrylic acid,
2- (meth) acryloyloxyethyl succinic acid, 2-
(Meth) acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid and the like can be mentioned.

When R5 in Structural Formula 2 is an isocyanate group, in the production of a compound which generates an amine by light irradiation represented by Structural Formula 2, (mol number of isocyanate group) / (mol number of hydroxyl group of oxime) When it exceeds 1, the value of m in the obtained structural formula 2 exceeds 1 to be the main constituent. When such a product is used as a compound that generates an amine by light irradiation, the amine generated by the light irradiation reacts with the remaining isocyanate group, so that the product itself can be self-cured.
In particular, it is more preferable that R4 is an aromatic hydrocarbon group because self-curing can easily occur.

When (isocyanate group)> (hydroxyl group of oxime), the isocyanate group is more cured than the amino group of the amine generated by light irradiation, so that the isocyanate group is cured by moisture such as moisture. It becomes possible.

Thus, two-step curing can be caused by the reaction between the amine and the isocyanate group generated by light irradiation and the subsequent moisture curing by the isocyanate group. The compound which is cured by the amine in the present invention,
Although not particularly limited, a urethane prepolymer having an isocyanate group as a reactive group, an epoxy resin having an epoxy group, an epoxy group-containing oligomer, an addition polymer of an epoxy group-containing oligomer, an epoxy-modified polycondensation polymer, and an epoxy Examples include a group-containing monomer, an acrylic compound having a (meth) acryloyl group, a vinyl compound having a vinyl group, and other compounds having a radical polymerizable double bond.

The urethane prepolymer is obtained by reacting a polyhydroxy compound with a polyisocyanate compound. Examples of the polyhydroxy compound include polyether polyol, polyester polyol,
And polymer polyols.

The epoxy resin is not particularly limited, but examples thereof include epoxy resins of bisphenol A type, bisphenol F type, phenol novolak type, cresol novolak type, glycidyl ether type, glycidylamine type and the like. Can be.

The epoxy group-containing oligomer is not particularly limited. For example, bisphenol A
Type epoxy oligomer (for example, “Epicoat 1001”, “Epicoat 1002” manufactured by Yuka Shell Epoxy Co., Ltd.)
Etc.).

The epoxy-modified polycondensation polymer is not particularly restricted but includes, for example, glycidylated polyester, glycidylated polyurethane and glycidylated polyacrylic polymer. As the acrylic polymer containing an epoxy group, for example, a method of reacting an acrylic polymer containing a hydroxyl group with epichlorohydrin, or a glycidyl (meth) acrylate and a monomer having a vinyl group copolymerizable therewith are used. Glycidylated polyacrylic polymers obtained by a method of copolymerizing can be exemplified.

The acrylic compound having a (meth) acryloyl group is not particularly limited. Examples thereof include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate,
(Meth) acrylic acid n-propyl ester, (meth) acrylic acid isopropyl ester, (meth) acrylic acid n
-Butyl ester, sec-butyl (meth) acrylate, t-butyl (meth) acrylate,
Pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate,
N-octyl (meth) acrylate, n-isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isononyl (meth) acrylate, (meth) ) Lauryl acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, hydroxyethyl (meth) acrylate, n-butoxyethyl (meth) acrylate Esters, phenoxyethyl (meth) acrylate,
(Meth) acrylic acid tetrahydrofurfuryl ester,
(Benzyl) (meth) acrylate, tribromophenyl (meth) acrylate, 2,3-dichloropropyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, ε- (poly) caprolactone acrylate, etc. (Meth) acrylic esters; urethane acrylates obtained by reacting a compound having an isocyanate group with a (meth) acrylic monomer having active hydrogen; a compound having an epoxy group and a (meth) acrylic compound having an acrylic acid or a hydroxyl group Epoxy ester compounds obtained by reaction with a monomer or the like;
Polyester acrylates; alkylene glycol mono (meth) acrylates obtained by reaction of alkylene glycol such as ethylene glycol and propylene glycol with (meth) acrylic acid; ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1 Alkylene glycol di (meth) acrylates such as 1,6-hexanediol dimethacrylate and 1,9-nonanediol dimethacrylate; polyalkylene glycol mono (meth) acrylates; alkylene glycol di (meth) acrylates; diethylene glycol monomethacrylate Dialkylene glycol mono (meth) acrylates; dialkylene glycol di (meth) acrylates; polyalkylene glycol di (meth) a Relates: glycerin mono (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, di Polyol (meth) acrylates such as pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate; (meth) acrylamides; (meth) acrylonitrile; acrylic acid N, N
-Dimethylaminoethyl ester, acrylic acid N, N-
Amino alkyl esters such as diethylaminoethyl ester and Nt-butylaminoethyl acrylate; silicone acrylates; polybutadiene acrylates; 2-hydroxy-3-acryloyloxypropyl methacrylate, ethylene oxide adduct of bisphenol A Examples thereof include dimethacrylate, trimethylolpropane PO-modified trimethacrylate, and trimethylolpropane EO-modified trimethacrylate.

Examples of the vinyl compound having a vinyl group include, but are not particularly limited to, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl ketone, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, N-vinyl pyrrolidone, vinyl Pyridine, vinyl carbazole, styrene, vinyl toluene,
Examples thereof include divinylbenzene, α-methylstyrene, chlorostyrene, t-butylstyrene and the like.

Other compounds having a radical polymerizable double bond are not particularly restricted but include, for example, butadiene, isoprene, fumaric acid and its dialkyl esters, maleic acid and its monoalkyl esters, dialkyl esters, itacone Examples include acids and their monoalkyl esters, dialkyl esters, phthalic acid and their monoalkyl esters, dialkyl esters, and the like.

The compound that generates an amine upon irradiation with light may be a polymer or oligomer obtained by copolymerizing a compound having a radical polymerizable group and a monomer having a (meth) acryloyl group and a carbamoyloxyimino group.

Here, the compound having a radical polymerizable group is not particularly limited, and examples thereof include (meth) acrylic acid; (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, and (meth) acrylic acid ethyl ester. N-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic acid Pentyl, hexyl (meth) acrylate, cyclohexyl methacrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Decyl (meth) acrylate, (meth) acryl Acid nononyl ester, hydroxyethyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, glycidyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, n-butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, (meth) Tribromophenyl acrylate, 2,3-dichloropropyl (meth) acrylate, ε
-(Meth) acrylic acid alkyl esters represented by (poly) caprolactone acrylate, tetrahydrofuranyl acrylate, etc .; styrene-based monomers represented by α-methylstyrene, vinyltoluene, chlorostyrene, t-butylstyrene, styrene, etc. A vinyl ether monomer represented by methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc .; fumaric acid;
Maleic acid; itaconic acid; phthalic acid; monoalkyl esters of fumaric acid, dialkyl esters of fumaric acid; monoalkyl esters of maleic acid, dialkyl esters of maleic acid; monoalkyl esters of itaconic acid, dialkyl esters of itaconic acid; Monoalkyl esters of phthalic acid, dialkyl esters of phthalic acid; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, t-butylaminoethyl acrylate; (meth) Acrylonitrile; butadiene; isoprene; vinyl chloride; vinylidene chloride; vinyl acetate;
N-vinylpyrrolidone; vinylpyridine; (meth) acrylamide; vinylcarbazole, etc .; divinylbenzene; urethane acrylate obtained by reaction of a compound having an isocyanate group with a (meth) acrylic monomer having active hydrogen; a compound having an epoxy group Epoxy ester compound obtained by, for example, reacting with acrylic acid or a (meth) acrylic monomer having a hydrogen group;
Polyester acrylates; alkylene glycol mono (meth) acrylates, dialkylene glycol mono (meth) acrylates, polyalkylene glycol (meth) acrylates, alkylene obtained by the reaction of alkylene glycol with ethylene glycol or propylene glycol and acrylic acid Glycol di (meth) acrylates, polyalkylene glycol di (meth) acrylates; glycerin mono (meth) acrylates, glycerin di (meth) acrylates, glycerin tri (meth) acrylates; trimethylolalkane tri (meth) acrylate Acrylamides;
Silicon acrylate; polybutadiene acrylate, and the like.

Examples of the monomer having a (meth) acryloyl group and a carbamoyloxyimino group include, for example, R5
Is a (meth) acryloyl group and a compound represented by Structural Formula 2.

A compound having the above radical polymerizable group,
Copolymerization of a monomer having a (meth) acryloyl group and a carbamoyloxyimino group can be performed by a known method. As described above, if a compound having a radically polymerizable group and a compound having a (meth) acryloyl group and a carbamoyloxyimino group are copolymerized to form a polymer, the compound having a radically polymerizable group to be copolymerized can be appropriately converted to a polymer. The selection makes it easier to control the compatibility with the compound which is cured by the amine, and can introduce a plurality of carbamoyloxyimino groups into one molecule of the polymer, so that the curing speed by light irradiation can be increased.

The radical polymerization initiator is not particularly limited, but those capable of initiating radical polymerization by light irradiation are preferable. For example, as a direct cleavage type, arylalkyl ketone, oxime ketone, acylphosphine oxide, arylalkyl ketone S-phenyl thiobenzoate, titanocene, hydrogen abstraction type, aromatic ketone, thioxanthone, benzyl and quinone derivative, 3-ketocoumarin; complex radical polymerization initiator, organic peroxide / electron donating dye, bisimidazole , Onium salts / electron donating dyes, N-phenylglycine / electron withdrawing dyes, N-phenylglycine / diphenyliodonium salts / sensitizers.

The compound capable of generating an amine upon irradiation with light according to the present invention can improve photodegradability by being used in combination with a photosensitizer. The photosensitizer mentioned here includes a triplet excitation energy transfer photosensitizer and an electron transfer photosensitizer.

For example, acetophenones, benzophenone, Michler's ketone, benzyl, benzoin, benzoin ether, benzyl dimethyl ketal, benzoyl benzoate, α-acyloxime ester, tetramethylthiuram monosulfide, thioxanthone, aliphatic amine, and aromatic groups Amines, such as piperidine, in which nitrogen is part of a ring system, allylthiourea, O-
Tolylthiourea, sodium diethyldithiophosphate, soluble salt of aromatic sulfinic acid, N, N-disubstituted-
p-aminobenzonitrile compound, tri-n-butylphosphine, N-nitrosohydroxylamine derivative, oxazolidine compound, tetrahydro-1,3-oxazine compound, condensate of formaldehyde or acetaldehyde with diamine, anthracene (or a derivative thereof) , Xanthine, N-phenylglycine, phthalocyanine, naphthocyanine, thiocyanine, and other cyanine dyes such as porphyrin (or derivatives thereof).

In particular, the compound of the present invention that generates an amine upon irradiation with light can have extremely excellent photodegradability when used in combination with a thioxanthone sensitizer. Here, the thioxanthone-based sensitizer is thioxanthone or a compound having a substituent introduced therein, and examples of the compound having a substituent introduced therein include 2,4-diethylthioxanthone and 2-chlorothioxanthone. , 2, 4
-Diisopropylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone and the like.

Particularly, the effect of improving the photodegradability of the compound represented by the structural formula 2 in which R4 is an aliphatic hydrocarbon and R5 is an isocyanate group by using a thioxanthone photosensitizer is remarkable.

The photosensitizer is preferably used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the compound which generates an amine upon irradiation with light. More preferably, the amount is 1 part by weight to 50 parts by weight. If the amount is less than 1 part by weight, a sufficient sensitizing effect may not be obtained.

[0049]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail by giving specific examples, but the present invention is not limited to only the following examples.

Example 1 0.05 mol of hexamethylene diisocyanate was added to tetrahydrofuran (THF).
Acetophenone oxime 0.1m dissolved in 100ml
was added, and the mixture was dried and stirred at 50 ° C. for 4 hours under a nitrogen atmosphere to cause a reaction. When tetrahydrofuran was volatilized from the reaction solution, a white solid was obtained. The obtained white solid was dissolved in methyl ethyl ketone at 80 ° C. and purified by recrystallization to produce a compound capable of generating an amine by light irradiation (hereinafter, referred to as compound 1).

(Example 2) To 0.05 mol of tolylene diisocyanate was added 0.1 mol of acetophenone oxime dissolved in 100 ml of tetrahydrofuran.
The mixture was dried and stirred at 50 ° C. for 4 hours in a nitrogen atmosphere to cause a reaction. When tetrahydrofuran was volatilized from the reaction solution, a white solid was obtained. The obtained white solid was dissolved in methyl ethyl ketone at 80 ° C. and purified by recrystallization to produce a compound capable of generating an amine by light irradiation (hereinafter, referred to as compound 2).

Example 3 0.05 m of TMP (trimethylolpropane) -modified hexamethylene diisocyanate (“Sumidur HT” manufactured by Sumitomo Bayer Urethane Co., Ltd.)
Then, 0.15 mol of acetophenone oxime dissolved in 100 ml of tetrahydrofuran was added to the mixture, and the mixture was dried and stirred at 50 ° C. for 4 hours under a nitrogen atmosphere to cause a reaction. When tetrahydrofuran was volatilized from the reaction solution, an orange liquid was obtained. Ethyl acetate was added to the obtained orange liquid, and the mixture was shaken. The mixture was allowed to stand still at 5 ° C. overnight to remove the supernatant ethyl acetate layer. A compound capable of generating an amine upon irradiation was produced (hereinafter, referred to as compound 3).

Example 4 0.05 mol of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK)
Was added with 0.05 mol of acetophenone oxime dissolved in 100 ml of tetrahydrofuran, and the mixture was dried and stirred at 50 ° C. for 4 hours under a nitrogen atmosphere to cause a reaction. Tetrahydrofuran was volatilized from the reaction solution to prepare a liquid compound capable of generating an amine by light irradiation (hereinafter, referred to as compound 4).

(Example 5) Polypropylene glycol having an average molecular weight of 700 ("MN-300", manufactured by Mitsui Chemicals, Inc.)
And hexamethylene diisocyanate with (NCO /
(OH) ratio was 1.9 and reacted at 80 ° C. for 5 hours. To 100 parts by weight of the obtained product, 10 parts by weight of acetophenone oxime was added, and the mixture was dried and stirred at 50 ° C. for 4 hours under a nitrogen atmosphere to react, thereby producing a compound capable of generating an amine by light irradiation (hereinafter, referred to as “the compound”). Compound 5).

Example 6 80 parts by weight of ethyl acrylate, 20 parts by weight of the compound 4 obtained in Example 4, and 200 parts by weight of dehydrated ethyl acetate were combined with a thermal radical polymerization initiator (manufactured by NOF Corporation, "Perhexa"). TNH ") to produce a compound capable of generating an amine upon irradiation with light (hereinafter, referred to as compound 6).

Comparative Example 1 100 ml of tetrahydrofuran was added to 0.05 mol of hexamethylene diisocyanate.
0.1 mol of o-nitrobenzyl alcohol dissolved in
Was added, and the mixture was stirred and reacted at 50 ° C. for 4 hours under a nitrogen atmosphere. When tetrahydrofuran was volatilized from the reaction solution, a white solid was obtained. The obtained white solid was purified by washing with methyl ethyl ketone (hereinafter, the obtained product is referred to as compound A).

Comparative Example 2 0.1 mol of o-nitrobenzyl alcohol dissolved in 100 ml of tetrahydrofuran was added to 0.05 mol of tolylene diisocyanate, followed by drying and stirring at 50 ° C. for 4 hours in a nitrogen atmosphere to cause a reaction. When tetrahydrofuran was volatilized from the reaction solution, a white solid was obtained. The obtained white solid was purified by washing with methyl ethyl ketone (hereinafter, the obtained purified product is referred to as compound B).

[Preparation of Compound Cured by Amine] Polyethertriol having a weight average molecular weight of 4,000 comprising trimethylolpropane and propylene oxide (trade name "ADEKA POLYETHER T-4" manufactured by Asahi Denka Kogyo KK)
000 ") and 100 parts by weight of polypropylene oxide (weight average molecular weight: 6,000), and hexamethylene diisocyanate was added so that the (NCO / OH) ratio became 1.9 in equivalent ratio. The mixture was reacted at a temperature of 5 ° C. for 5 hours to obtain a urethane prepolymer (1).

(Evaluation of solubility) Infrared absorption spectra (NCO, NHC = O, C = O bond) of Compounds 1 to 6 and Compounds A and B were measured using an infrared absorption spectrum measuring apparatus manufactured by PerkinElmer. Hereinafter, changes in the IR spectrum before and after the reaction were observed, and the solubility of the obtained Compounds 1 to 6 and Compounds A and B in tetrahydrofuran, the urethane prepolymer (1) and the epoxy resin (“ The compatibility with Epicoat 828 ") was evaluated. The evaluation results are shown in Table 1.

1 to 4 show Compound 1
It is a figure which shows IR spectrum of No.-4. The solubility and compatibility were evaluated by adding 1 part by weight of each of the test substances (compounds 1 to 6 and compounds A and B) to 100 parts by weight of each of tetrahydrofuran, urethane prepolymer (1) and epoxy resin. The mixture was added, mixed with stirring, and the state of dissolution was observed. The evaluation was made in three stages: Δ: completely dissolved to obtain a transparent mixture, Δ: almost soluble but slightly cloudy, ×: almost insoluble.

[0061]

[Table 1]

From the results of the IR spectrum measurement in Table 1, the peaks attributed to the isocyanate group (NCO) disappeared and the peaks attributed to the urethane bond (NHC = O) appeared, so that compounds 1 to 6 were formed. Can be confirmed.

From Table 1, it can be seen that Compounds 1 and 6 having a carbamoyloxyimino group with respect to Compounds A and B have good solubility in tetrahydrofuran. Further, it was found that by increasing the molecular weight of the R1 group in Structural Formula 1 to a certain extent, the compatibility with the urethane prepolymer (2) and the epoxy resin was improved, which was found by comparing the compounds 1 and 2 with the compounds 5 and 6. Can be understood by

(Evaluation of Photodegradability) As shown in Table 2, the compound formed by dissolving Compound 2 and Compound B in tetrahydrofuran, applying the solution to a potassium bromide plate, and drying was used. 1710 cm
The peak absorbance of the infrared absorption spectrum of the urethane bond (NHC = O) observed near ^-1 was measured (this value was expressed as E
1).

Next, an ultra-high pressure mercury lamp (Oak Seisakusho Co., Ltd., Jetlight-2300) was added to the same sample as the above sample.
After irradiating at 50 mW / cm ² for 1 minute using, the infrared absorption spectrum was similarly measured, and the peak absorbance of a urethane bond (NHC （O) observed around 1710 cm ⁻¹ was measured (this value was E2).

Further, the same sample as that described above was irradiated with 50 mW / cm ² for 4 minutes using an ultra-high pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., Jetlight-2300), and the infrared absorption spectrum was measured in the same manner. The peak absorbance of a urethane bond (NHC = O) observed around 1710 cm ^-1 was measured (this value is referred to as E3).

From the obtained values of E1, E2 and E3,
The percentages of the calculated values of (E1-E2) / E1 and (E1-E3) / E1 were defined as decomposition rates 1 and 2, respectively, and the measurement was performed for each of compound 2 having a carbamoyloxyimino group and compound B having no carbamoyloxyimino group. Was. Table 2 shows the measurement results.
It was shown to.

[0068]

[Table 2]

As is clear from Table 2, it can be understood that the compound 2 having a carbamoyloxyimino group easily generates an amine by light irradiation.

Synthesis Example 1 Preparation of Urethane Prepolymer Polyethertriol having a weight-average molecular weight of 4,000 comprising trimethylolpropane and propylene oxide (trade name: ADEKA POLYETHER T-4 manufactured by Asahi Denka Kogyo KK)
000) and 100 parts by weight of polypropylene oxide (weight average molecular weight 6,000) were mixed with diphenylmethane-4,4'-diisocyanate (manufactured by Nippon Polyurethane Co., trade name: Millionate MT) by NCO
/ OH ratio is 1.9 in equivalent ratio.
For 5 hours to obtain a urethane prepolymer (2).

Synthesis Example 2 Synthesis of Compound B Having Carbamoyloxyimino Group 0.02 mol of hexamethylene diisocyanate and 0.04 mol of acetophenone oxime were dissolved in 50 ml of tetrahydrofuran (THF).
Stirred at 0 ° C. for 5 hours. Then, let stand at room temperature for 5 hours,
The obtained white crystals were collected by filtration. This was dried in a vacuum drying oven to evaporate THF. The compound thus obtained is referred to as Compound 7.

Synthesis Example 3 Synthesis of a polymer in which a compound having a radical polymerizable group and a monomer having an acryloyl group and a carbamoyloxyimino group were copolymerized. 5 mmol of the compound 4 obtained in the above Example 4 and 10
mmol of butyl acrylate was dissolved in 10 ml of THF. Thereafter, 60 mg of 2,2'-azobisisobutyronitrile was added and polymerized at 60 ° C. for 7 hours under a nitrogen atmosphere to obtain a polymer solution. This polymer solution was placed in a vacuum drying oven, and benzene was removed to obtain a polymer. This polymer is referred to as polymer 1.

Example 7 10 parts by weight of the compound 7 and 1 part by weight of benzophenone were added to 100 parts by weight of the urethane prepolymer (2) obtained as described above. Under dry conditions, stir at 60 ° C. until uniform,
A photoreactive adhesive composition was obtained.

Example 8 5 parts by weight of the compound 4 obtained in the above Example 4 was added to 100 parts by weight of the urethane prepolymer (2) obtained as described above, and urethane acrylate (manufactured by Kyoeisha Chemical Co., Ltd., product no. : AH-600) 5 parts by weight and benzophenone 1 part by weight. Under dry conditions, 6
The mixture was stirred at 0 ° C. until the mixture became uniform to obtain a photoreactive adhesive composition.

Example 9 100 parts by weight of the urethane prepolymer (2) obtained as described above was mixed with the polymer 1
And 10 parts by weight of benzophenone.
Under dry conditions, the mixture was stirred at 60 ° C. until uniform, to obtain a photoreactive adhesive composition.

(Comparative Example 3) Only the urethane prepolymer (2) synthesized as described above was used as a comparative example.

(Evaluation of Examples 7 to 9 and Comparative Example 3) The adhesive strength, heat resistance and gel fraction of the adhesive compositions of Examples and Comparative Examples were measured in the following manner. The results are shown in Table 3 below.

Adhesive force Under an atmosphere of 23 ° C., the obtained one-pack type photoreactive adhesive composition was applied to a polished stainless steel plate (SUS plate) (3c).
m × 10cm × 0.2cm, 45g) 3cm
It was applied at a thickness of × 10 cm and 50 μm. Then, an ultra-high pressure mercury lamp (Oak Manufacturing Co., Ltd., Jetlight-23)
00) for 3 minutes at 40 mW / cm ² ,
A corona-treated PET film was laminated to obtain a test piece.

Next, it was left still at room temperature for 30 minutes, and the 180 ° peeling adhesive force was measured at a pulling speed of 50 mm / min to determine the initial adhesive force. After the test piece was cured at 23 ° C. for 7 days, the tensile peel adhesion was measured at a pulling speed of 50 mm / min, and the adhesive strength after curing was determined.

Heat resistance Under an atmosphere of 23 ° C., the obtained one-component photoreactive adhesive composition was applied to a polished stainless steel plate (SUS plate) for 10 minutes.
It was applied at a thickness of 0 μm. Then, using a high-pressure mercury lamp (Oak Seisakusho Co., Ltd., Jetlight-2300), 4
After irradiation with light at 0 mW / cm ² for 3 minutes, a corona-treated PET film was laminated. Thereafter, the corona-treated PET film was fixed, suspended vertically in an oven at 80 ° C., and the displacement of the SUS plate was measured.

Gel Fraction The obtained one-part photoreactive adhesive composition was placed in an atmosphere of 23 ° C.
100 μm thick PET film released from the mold
It was applied so as to be visible. Then, an ultra-high pressure mercury lamp (O
Using Jetlight-2300 manufactured by Ku Seisakusho Co., Ltd.
40mW / cm ^TwoIrradiate with light for 3 minutes
Dissolved in lofran
The rate (% by weight) was determined.

[0082]

[Table 3]

(Examples 10 to 14, Comparative Examples 4 and 5) Compounds 1 to 3, 5, 6 and 2-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., 100 parts by weight of urethane prepolymer (1)) Example 10: Compound No. DETX-S) was mixed as shown in Table 4 and stirred under dry conditions until uniform.
~ 14 photoreactive adhesive compositions were obtained.

In Comparative Examples 4 and 5, Compounds A and B were used. The obtained photoreactive adhesive composition is applied on a release PET film so as to have a thickness of 50 μm, and an ultra-high pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd.,
50mW / c using “Jetlight 2300”)
Light irradiation was performed for 1 minute at m ² .

The coated film of the photoreactive adhesive composition irradiated with light is sandwiched between two polished stainless steel plates (3 cm × 10 cm × 0.2 cm) in an atmosphere of 23 ° C. and pressed. Stuck together.

(Examples 15 and 16, Comparative Examples 6 and 7) Compound 4 and 2-diethylthioxanthone (trade name: DETX-S, manufactured by Nippon Kayaku Co., Ltd.) based on 100 parts by weight of urethane prepolymer (1) And urethane acrylate (manufactured by Kyoeisha Chemical Co., Ltd., product number: AH600) as shown in Table 5 and stirred under dry conditions until uniform, to obtain a photoreactive adhesive composition. In addition, for compound 4, 2-diethylthioxanthone also functions as a photoradical polymerization initiator.

In Comparative Examples 6 and 7, Compound A
Was used. The obtained photoreactive adhesive composition is used for releasing PE.
A T-film is coated so as to have a thickness of 50 μm, and an ultra-high pressure mercury lamp (Oak Seisakusho,
50mW / c using “Jetlight 2300”)
Light irradiation was performed for 1 minute at m ² .

The light-irradiated coating film of the photoreactive adhesive composition was applied at 23 ° C. to cover the entire surface of a polished stainless steel plate (SUS plate) (3 cm × 10 cm × 0.2 cm). And sandwiched between two sized polished stainless steel plates in a sandwich form, and then bonded together.

To evaluate the performance of the photoreactive adhesive compositions obtained in Examples 10 to 16 and Comparative Examples 4 to 7, the gel fraction, the initial adhesive strength and the adhesive strength after curing were measured. The results are shown in Tables 4 and 5. The initial adhesive strength and the adhesive strength after curing were measured in the following manner.

(Preparation of Test Samples) The coated photoreactive adhesive composition was applied to a polished stainless steel plate (3 cm × 10 cm × 0.2 cm) in an atmosphere of 23 ° C. in an atmosphere of 3 cm × 3 cm. It was applied with a thickness of 50 μm. Then, a high-pressure mercury lamp (Oak Seisakusho, Jetlight 2)
Using 300), irradiation was performed at 50 mW / cm ² for 1 minute, and then sandwiched between a polished stainless steel plate of another size in a sandwich shape and bonded together.

Initial adhesion: A test sample was prepared at room temperature for 30 days.
After standing still for 5 minutes, the shear adhesive strength was measured at a pulling rate of 5 mm / min to determine the initial adhesive strength.

Adhesive Strength after Curing After the test pieces were cured at 23 ° C. for 7 days, the shear adhesive strength was measured at a pulling speed of 50 mm / min to determine the adhesive strength after curing.

[0093]

[Table 4]

[0094]

[Table 5]

In Tables 4 and 5, as is clear from comparison with Comparative Examples 4 to 7, all of the photoreactive adhesive compositions of Examples 10 to 14 were appropriately crosslinked.
It shows a good gel fraction. This good gel fraction shows a high initial adhesive strength, which leads to a remarkably good workability of the photoreactive adhesive composition. It is clearly shown that the difference in performance is manifested by the presence or absence of a compound having a carbamoyloxyimino group that generates an amine upon light irradiation. Further, the curability is improved by polyfunctionalization of the compound having a carbamoyloxyimino group.

Further, the comparison of Example 15 with Example 16 and Comparative Examples 6 and 7 showed that the addition of the compound having a radical polymerizable group showed that the gel fraction was further increased and a high initial adhesive force was obtained. I have.

[0097]

The compound according to the present invention, which generates an amine upon irradiation with light, is excellent in photodegradability, and can be used to produce a highly efficient amine upon irradiation with light and is cured by an amine such as a urethane prepolymer or an epoxy compound. Since it can be rapidly cured, it is used together with a compound that is cured by an amine to constitute a photocurable composition, an adhesive,
It can be suitably used as a photocuring agent such as an adhesive, a paint, a coating material, a resist, a sealing material, and an ink.

[Brief description of the drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of Compound 1 synthesized in Example 1.

FIG. 2 is a view showing an infrared absorption spectrum of Compound 2 synthesized in Example 2.

FIG. 3 shows an infrared absorption spectrum of Compound 3 synthesized in Example 3.

FIG. 4 is a diagram showing an infrared absorption spectrum of Compound 4 synthesized in Example 4.

Claims (8)

[Claims] 1. A compound having a carbamoyloxyimino group and generating an amine by light irradiation represented by the following structural formula 1. Embedded image However, in the structural formula 1, R1 is an n-valent organic group, R2
And R3 are each hydrogen, an aromatic group or an aliphatic group,
n is a positive integer of 1 or more. 2. A compound having a carbamoyloxyimino group and generating an amine by light irradiation represented by the following structural formula 2. Embedded image However, in the structural formula 2, R2 and R3 are each hydrogen, an aromatic group or an aliphatic group, and R5 is at least one or more selected from the group consisting of an isocyanate group, a (meth) acryloyl group, and a vinyl group; R4 is (m + n)
The valence organic group, n and m are each a positive integer of 1 or more. 3. The structural formula 1 or 2, wherein one of R2 and R3 is hydrogen or an aliphatic group, and the other is an aromatic group.
Or a compound which generates an amine upon irradiation with light. 4. The structural formula 1 or 2, wherein R1 or R4 is an aromatic group.
3. The compound which generates an amine upon irradiation with light according to any one of the above items 3. 5. The structural formula 1 or 2, wherein R2 and R3 are each a group selected from the group consisting of hydrogen, methyl, phenyl and naphthyl. 4. The compound which generates an amine by light irradiation according to any one of the above items 4. 6. A compound having a radical polymerizable group,
A compound which generates an amine by light irradiation, which is a polymer or an oligomer obtained by copolymerizing a monomer having a (meth) acryloyl group and a carbamoyloxyimino group. 7. A photocurable composition comprising the compound according to claim 1 which generates an amine upon irradiation with light and a compound which is cured by the amine. 8. The photocurable composition according to claim 7, further comprising a thioxanthone sensitizer.