JPH04239514A - Ultraviolet curing type resin composition - Google Patents

Abstract

PURPOSE:To obtain an ultraviolet curing type resin composition capable of providing a gel composition by curing without discoloring even if preserved in high-temperature environment. CONSTITUTION:An ultraviolet curing type resin composition containing (E) 0.3-10 pts.wt. 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide in (I) 100 pts.wt. composition composed of (A) an ethylenically unsaturated bond-containing compound, (B) a photopolymerization initiator, (C) a solvent and (D) a volatile substance.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention contains volatile substances effective as fragrances, deodorants, insect repellents, repellents, attractants, insecticides, fungicides, fumigants, etc. Other related to ultraviolet curable resin compositions used in gel compositions that, when left in the atmosphere, gradually evaporate volatile substances into the atmosphere and exert desired effects such as fragrance and deodorization. .

0002

[Prior Art] Various gel compositions containing volatile substances as active ingredients are used as air fresheners, deodorants, insect repellents, repellents,
It is used as an attractant.

Conventionally, such gel compositions have been prepared by heating, dissolving, and uniformly mixing active ingredients with water-soluble polymers such as polyvinyl alcohol, oil-soluble polymers such as sodium stearate, or polymers such as carrageenan. ,
It was manufactured by cooling and solidifying it.

[0004] However, conventional gel compositions require heating in the manufacturing process, and therefore have the problem that volatile substances, which are active ingredients, are volatilized or deteriorated.

[0005] Therefore, the present inventors have previously proposed a gel composition in which a volatile substance is retained in the cured product of the resin composition, or a resin composition used for producing the gel composition ( JP-A-01-315402, etc.).

The gel composition proposed by the present inventors is different from conventional ones because it is produced without a heating process.
No problems such as volatilization or deterioration of volatile substances, which are active ingredients, occurred. However, this gel composition is particularly
It has become clear that when stored in an environment above ℃, it gradually turns brown.

[0007]

[Problems to be Solved by the Invention] The present invention has been made in view of the above facts, and provides an ultraviolet curable resin composition that, when cured, provides a gel composition that does not change color even when stored in a high-temperature environment. The purpose is to provide.

[0008]

[Means for Solving the Problems] The present invention provides a composition (I) comprising an ethylenically unsaturated bond-containing compound (A), a photopolymerization initiator (B), a solvent (C) and a volatile substance (D). 1
00 parts by weight, 3,4,5,6-dibenzo-1,2
-Oxaphosphane-2-oxide (E) 0.3~
The present invention provides an ultraviolet curable resin composition characterized in that it contains 10 parts by weight.

The present invention will be explained in detail below. The composition (I) used in the present invention is composed of an ethylenically unsaturated bond-containing compound (A), a photopolymerization initiator (B), a solvent (C), and a volatile substance (D).

The ethylenically unsaturated bond-containing compound (A) used in the present invention is a radically polymerizable compound having an ethylenically unsaturated bond in its molecule, which can be polymerized by light energy or a polymerization initiator.

Examples of such ethylenically unsaturated bond-containing compounds (A) include (meth)acrylate compounds (A-1) having an acryloyl group or methacryloyl group at the end of the molecular chain, unsaturated compounds such as fumaric acid, maleic acid, etc. Unsaturated polyester (A
-2), a vinyl compound (A-3) such as styrene, a (meth)acrylamide compound (A-4), or a mixture thereof is preferably used.

More specifically, the (meth)acrylate compound (A-1) is a urethane (meth) having one or more urethane bonds in one molecule and having a (meth)acryloyl group at the end. Acrylate (A-1-a);
Epoxy (meth)acrylate (A-1-b) synthesized from epoxy resin; Polyethylene glycol (meth)acrylate (A-1-b) whose main skeleton is polyethylene glycol (
A-1-c); Polybutadiene (meth)acrylate (A-1-d) having polybutadiene as the main skeleton; Polyester (meth)acrylate having ester bond as the main chain;
(Meth)acrylic oligomers such as polyether (meth)acrylates having an ether bond as the main chain (A-1-e
); Mono(meth) having one (meth)acryloyl group
Examples include acrylate monomer (A-1-f); polyfunctional (meth)acrylate monomer (A-1-g) having two or more (meth)acryloyl groups, and the like.

[0013] Urethane (meth)acrylate (A-1-
A) can be synthesized, for example, from a polyol component, an isocyanate component, and a (meth)acrylate component having a hydroxyl group for introducing a terminal (meth)acryloyl group.

The polyol component, which is one of the raw materials for the synthesis of urethane (meth)acrylate (A-1-a), is a synthetic polymer compound having two or more hydroxyl groups in the molecule, such as polyether. polyol compound,
Examples include polyester polyol compounds, polyurethane polyol compounds, and polyhydroxypolyolefin compounds.

[0015] As the polyether polyol compound,
polyethylene glycol, polypropylene glycol,
Polyalkylene glycols such as polybutylene glycol, polytetramethylene glycol, and polyhexamethylene glycol, or alkylene oxides such as ethylene oxide, propylene oxide, and tetrahydrofuran, are combined with ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, and trimethylol. Polymers obtained by adding polyhydric alcohols such as propane, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2,6-hexanetriol, and pentaerythritol. Examples include ether polyols.

[0016] Examples of polyester polyol compounds include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, hexahydrophthalic acid, hemic acid, het acid, succinic acid, and maleic acid. , fumaric acid, adipic acid, sebacic acid, dodecenylsuccinic acid, trimellitic acid,
Examples include polyester polyols obtained by a condensation reaction between a polybasic acid such as pyromellitic acid or its anhydride and the above-mentioned polyhydric alcohol.

[0017] Further, as the polyurethane polyol compound, a polyisocyanate compound or a polymer thereof,
Examples of these include polyurethane polyols obtained by an addition reaction with an excess polyhydric alcohol, and polyurethane polyols obtained by reacting the above-mentioned polyether polyols and polyester polyols with a polyisocyanate compound.

Further, examples of the polyhydroxypolyolefin compound include acrylic polyol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol.

In addition, urethane (meth)acrylate (A
The isocyanate component, which is one of the raw materials for synthesis of -1-a), includes ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, , 6-tolylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthylene-1,5-diisocyanate, isophorone diisocyanate, 1-methyl-2, Examples include 4-diisocyanatocyclohexane, 1-methyl-2,6-diisocyanatocyclohexane, and dicyclohexylmethane diisocyanate.

Furthermore, urethane (meth)acrylate (
As a (meth)acrylate component having a hydroxyl group for introducing a terminal (meth)acryloyl group, which is one of the raw materials for synthesis of A-1-a), 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (
meth)acrylate, 4-hydroxybutyl(meth)acrylate, 2-hydroxy-3-chloropropyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, ε-caprolactone-modified hydroxy(meth)acrylate, etc. Illustrated.

[0021] Urethane (meth)acrylate (A
-1-a) is a synthesis method in which a polyol component and a polyisocyanate component are first reacted, and then a (meth)acrylate component having a hydroxyl group is reacted with the polyisocyanate component and a polyisocyanate component having a hydroxyl group. Examples include a synthesis method in which a (meth)acrylate component is reacted and then a polyol component; a synthesis method in which a polyol component, a polyisocyanate component, and a (meth)acrylate component having a hydroxyl group are simultaneously reacted, etc. The ethylenically unsaturated bond-containing compound (A) used in the present invention includes urethane (meth)acrylate (A-1-a) synthesized by any method.
may also be used.

[0022] Also, the reaction temperature at this time is 30 to 120°C.
The temperature is about 60 to 80°C, preferably 60 to 80°C.

[0023] The reaction molar ratio when synthesizing urethane (meth)acrylate (A-1-a) by the above synthesis method is 1 mole of polyol to 1 mole of polyisocyanate.
．． 2 to 5.0 mol, preferably about 0.3 to 5.0 mol of (meth)acrylate having a hydroxyl group, particularly,
Molar ratio of hydroxyl groups to isocyanate groups (OH/
NCO) is preferably 1 or more so that no unreacted isocyanate groups remain in the reaction product.

[0024] The above urethane (meth)acrylate (A
-1-a), hydroquinone, hydroquinone monomethyl ether, tert-
Polymerization inhibitors such as butyl hydroquinone are added to 100% of the total amount.
About 5,000 ppm, or about 100 to 5,000 ppm of the total amount of a urethanization catalyst such as triethylamine, stannous octoate, dibutyltin dilaurate, etc. may be added.

Epoxy (meth)acrylate (A-1-
As for b), bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, and these resins modified with rubber such as NBR, polybutadiene, or urethane resin. Examples include those obtained by reacting glycidyl ether groups of epoxy resin with (meth)acrylic acid.

Examples of polyethylene glycol (meth)acrylate (A-1-c) include triethylene glycol (meth)acrylate, tetraethylene glycol (meth)acrylate, and polyethylene glycol #400 (
meth)acrylate, polyethylene glycol #600
(meth)acrylate, polyethylene glycol #10
00 (meth)acrylate and the like.

Polybutadiene (meth)acrylate (A
-1-d) is obtained from, for example, a polybutadiene oligomer having a functional group such as a hydroxyl group or a glycidyl group at the terminal and (meth)acrylic acid. or,
Also preferably used are those obtained by reacting a polybutadiene oligomer having a terminal functional group with a diisocyanate compound to form a prepolymer, and further reacting it with hydroxy (meth)acrylates.

(Meth)acrylic oligomer (A-1-
Examples of e) include polyester (meth)acrylate having an ester bond in its main chain, polyether (meth)acrylate having an ether bond in its main chain, and the like.

[0029] Such polyester (meth)acrylate is obtained from the above-mentioned polyester polyol and (meth)acrylic acid.

[0030] Polyether (meth)acrylate is obtained from the above-mentioned polyether polyol and (meth)acrylic acid.

Mono(meth)acrylate monomer (A-
1-f) includes aryloxyalkyl (meth)acrylates such as 2-phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, and nonylphenol propylene oxide adduct (meth)acrylate; 2-ethylhexyl (meth)acrylate; Alkyl (meth)acrylates such as acrylate, lauryl (meth)acrylate, n-butyl (meth)acrylate;
Hydroxyalkyl (meth)acrylates such as 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate, 4 -methoxybutyl (
Alkoxyalkyl (meth)acrylates such as meth)acrylate; cyclohexyl (meth)acrylate,
Cyclopentyl (meth)acrylate, isobornyl (
Examples include cycloalkyl (meth)acrylates such as meth)acrylate; and cycloalkenyl (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate.

Polyfunctional (meth)acrylate monomer (A
-1-g), polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)
Acrylate, neopentyl glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2-bis[4-(meth)acryloyloxydiethoxyphenyl]propane, hydrogenated dicyclopentadienyl di(meth) Acrylate, bifunctional (meth)acrylate such as di(meth)acrylate represented by the following formula (a);

[Formula (a), R represents a hydrogen atom or a methyl group] Trimethylolpropane tri(meth)
Acrylate, trimethylolpropane propylene oxide adduct tri(meth)acrylate, glycerin propylene oxide adduct tri(meth)acrylate,
Trifunctional (meth)acrylates such as tris[(meth)acryloyloxyethyl]isocyanurate and pentaerythritol tri(meth)acrylate; tetrafunctional or higher functionals such as pentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate Polyfunctional (meth)acrylates and the like are exemplified.

Unsaturated polyester used in the present invention (
A-2) is obtained from an unsaturated dicarboxylic acid and a polyhydric alcohol.

[0034] Examples of the unsaturated dicarboxylic acid include fumaric acid, maleic acid, and itaconic acid.

[0035] Examples of polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, and the like.

[0036] Furthermore, the vinyl compound used in the present invention (
Examples of A-3) include styrene and vinyl acetate.

The (meth)acrylamide compound (A-4) used in the present invention is a compound having a (meth)acrylamide group represented by the following formula (b).

[Formula (b), R represents a hydrogen atom or a methyl group]

Specifically, (meth)acrylamide, N,
N-dimethyl (meth)acrylamide, diacetone (meth)acrylamide, N-tert-butyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylamide, N- Isopropyl (meth)acrylamide, N-n-butoxy (meth)acrylamide,
Examples include N-methylol (meth)acrylamide, N,N-dimethyl (meth)acrylamide, diacetone (meth)acrylamide, and N-(meth)acryloylmorpholine.

The proportion of the ethylenically unsaturated bond-containing compound (A) in the composition (I) used in the present invention is 3 to 5.
0% by weight is preferred. If it is less than 3% by weight, the cured product of the resin composition of the present invention will be difficult to form a gel, and if it exceeds 50% by weight, the gel will become too hard and the volatilization rate of the volatile substance (D) described below will be reduced. Become slow.

The photopolymerization initiator (B) used in the present invention is:
Although the photopolymerization initiators include a radical photopolymerization initiator (B-1) and a cationic photopolymerization initiator (B-2), the radical photopolymerization initiator (B-1) is particularly preferred.

Examples of the radical photopolymerization initiator (B-1) include 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl] −
2-morpholino-propanone-1,2,4-diethylthioxanthone, benzoin isobutyl ether, 2,
2-diethoxyacetophenone, 2-hydroxy-2-
Examples include methylpropiophenone, 2-hydroxy-4'-isopropyl-2-methylpropiophenone,
There are no particular restrictions.

The cationic photopolymerization initiator (B-2) includes a cation moiety such as aromatic diazonium salt, aromatic iodonium salt, aromatic sulfonium salt, aromatic selenium salt, and SbF6-, AsF6-, PF6- , BF4
Examples include compounds consisting of anion moieties such as -.

The content of the photopolymerization initiator (B) in the composition (I) used in the present invention is preferably from 0.1 to 100 parts by weight of the aforementioned ethylenically unsaturated bond-containing compound (A). The amount is about 10 parts by weight. If the content is less than 0.1 parts by weight, there will be no effect of addition, and if the content exceeds 10 parts by weight, the effect of addition will not improve.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more.

The solvent (C) used in the present invention is compatible with both the ethylenically unsaturated bond-containing compound (A) and the volatile substance (D) described below, and is compatible with water, alcoholic solvents, ketones, etc. There are solvent-based solvents, ester-based solvents, etc.

[0046] Some of these solvents (C) can also be used as fragrances (D-1), which are a type of volatile substances (D) to be described later.

Examples of the solvent (C) include diethyl phthalate, dipropylene glycol, ethyl carbitol,
Examples include hexylene glycol, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate.

Furthermore, examples of the solvent (C) which can also be used as fragrance (D-1) include benzyl alcohol, dibenzyl ether, benzyl acetate, methyl benzoate, benzyl benzoate, citronellol, dihydromircenol, dihydroterpineol, geraniol,
Examples include terpineol, benzaldehyde, cyclamenaldehyde, hydroxycitronellal, p-tert-butyl-α-methylhydroxycinnamic aldehyde, geranyl acetate, linalyl acetate, terpinyl acetate, limonene, dipentene, and the like.

Among these, benzyl benzoate, diethyl phthalate, dipropylene glycol, ethyl carbitol, hexylene glycol, 3-methyl-
3-methoxybutanol and the like are more preferably used.

The proportion of the solvent (C) in the composition (I) used in the present invention is preferably 2 to 95% by weight, and 3 to 50% by weight.
% by weight is more preferred. If it exceeds 95% by weight, the cured product of the resin composition of the present invention will be difficult to form a gel;
If it is less than that, the gel becomes too hard and the volatilization rate of the volatile substance (D) described below becomes slow.

[0051] The volatile substance (D) used in the present invention is a substance that gradually evaporates into the atmosphere when left in the atmosphere and exerts desired effects such as fragrance and deodorization. Fragrance (D-1), deodorant, insect repellent, repellent,
Active ingredients such as attractants, insecticides, fungicides, fumigants, etc.

The fragrance (D-1) includes citronellol, geraniol, terpineol, benzyl alcohol, dihydromircenol, dibenzyl ether, benzaldehyde, cyclamenaldehyde, lilyal, benzyl acetate, limonene, benzyl benzoate, terpinyl acetate, etc. Examples include natural and synthetic fragrances such as terpene-based, alcohol-based, aldehyde-based, ketone-based, ester-based, and phenol-based fragrances, and blended fragrances that are mixtures thereof.

[0053] Also, as the active ingredient (D-2) of the deodorant, α, β such as fumaric acid, crotonic acid, citraconic acid, etc.
Examples include unsaturated carboxylic acids and their esters, and active methylene compounds such as acetylacetone, ethyl acetoacetate, and malonic acid.

[0054] Also, examples of the active ingredient (D-3) of the insect repellent include naphthalene, coriander, p-dichlorobenzene, and the like.

[0055] Examples of the active ingredient (D-4) of the repellent include neem extract, 1,8-cineole, and phthalate ester.

[0056] Examples of the active ingredient (D-5) of the attractant include alkenyl alcohols, alkenyl aldehyde pheromones, and furanone derivatives.

The proportion of the volatile substance (D) in the composition (I) used in the present invention is preferably 2 to 95% by weight,
More preferably 3 to 50% by weight. Volatile substances (D
) is less than 2% by weight, it is difficult to obtain the desired effects such as aromaticity, deodorization, insect repellency, etc., and when it exceeds 95% by weight, the ethylenically unsaturated bond-containing compound is relatively As the amount of (A) decreases, it becomes difficult for the cured product of the resin composition of the present invention to become a suitable gel-like material.

3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide (E) used in the present invention
is a compound represented by the following formula (c).

[Chemical formula 3]

In the present invention, 3,4,5,6-dibenzo-
1,2-oxaphosphane-2-oxide (E) is added in an amount of 0.3 to 10 parts by weight based on 100 parts by weight of the composition (I).
Use parts by weight. If it is less than 0.3 parts by weight, browning of the cured product of the resin composition of the present invention cannot be prevented, and if it exceeds 10 parts by weight,
It is no longer possible to expect any improvement in effectiveness.

The essential components of the resin composition of the present invention are as described above, but in addition, thermal polymerization inhibitors such as hydroquinone, tert-butylhydroquinone (TBH), etc. , a photosensitizer, a chain transfer agent, a curing accelerator, a mold release agent, a coloring agent, etc. may also be used.

The resin composition of the present invention can be obtained by measuring and mixing the ingredients.

Further, the resin composition of the present invention is cured by irradiation with light such as ultraviolet rays.

[0063]

[Examples] The present invention will be specifically explained below with reference to Examples.

(Example 1) Resin compositions whose compositions are shown in Table 1 were prepared, and they were exposed to ultraviolet light (maximum wavelength 355 nm).
was irradiated to obtain a gel composition (cured resin). These gel compositions were stored in a thermostatic chamber at 60° C., and the presence or absence of discoloration was visually evaluated using those stored at 20° C. as a control. The results are shown in Table 1. As is clear from Table 1, 3, 4,
5,6-dibenzo-1,2-oxaphosphan-2-
Only the gel composition containing oxide did not change color over an extended period of 8 weeks or more.

[0065]

[Table 1]

(Description of components in Table 1) *1 2HEA/1.6HMDI/PP
G-1000/1.6HMDI/
2HEA urethane acrylate, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd. HEA: 2-hydroxyethyl acrylate
1.6HMDI: 1,6-hexamethylene diisocyanate PPG-100
0: Polypropylene with a weight average molecular weight of 1000

Recall *2 Ethylene glycol #400 diacrylate, Kyoeisha Yushi Kagaku Kogyo
*3 Pentaerythritol triacrylate, Kyoeisha Yushi Kagaku Kogyo Co., Ltd.
*4 Diacetone acrylamide, manufactured by Kyowa Hakko Co., Ltd. *5 Radical photopolymerization initiator, 1-hydroxycyclohexylbenzof
Enon, manufactured by Ciba Geigy
*6 3,4,5,6-dibenzo-1,2-oxaphosphan-2-oxide, manufactured by Sanko Kagaku Co., Ltd. *7 Manufactured by Ciba Geigy *8 Manufactured by Ciba Geigy
*9 Manufactured by Ciba Geigy *10
Manufactured by Ciba Geigy *11 Manufactured by Ciba Geigy

(Example 2) Resin compositions whose compositions are shown in Table 2 were prepared, and they were treated with ultraviolet light (maximum wavelength 35
5 nm) to obtain a gel composition (cured resin material). At this time, photocurability was visually judged. These gel compositions were stored in a constant temperature room at 60°C and kept at 20°C.
The presence or absence of discoloration was visually evaluated using the sample stored at ℃ as a control. The results are shown in Table 2. As is clear from Table 2, 3
, 4,5,6-dibenzo-1,2-oxaphosphane-2-oxide in an amount of 0.3 parts by weight or more based on 100 parts by weight of composition (I). No discoloration over long periods of time. However, 3,
4,5,6-dibenzo-1,2-oxaphosphane-
1 of 2-oxide per 100 parts by weight of composition (I)
When the content exceeds 0 parts by weight, the photocurability of the resin composition also became poor.

[0068]

[Table 2]

[0069]

Effects of the Invention The present invention provides a resin composition that, when cured, becomes a gel composition containing a volatile substance as an active ingredient, which does not discolor even when stored in a high-temperature environment. things are provided. According to the present invention, the beauty of the gel composition is not impaired for a long period of time after production, so that fragrances and the like using this gel composition have high commercial value.

Claims (1)

[Claims] [Claim 1] Ethylenically unsaturated bond-containing compound (A
), 3,
4,5,6-dibenzo-1,2-oxaphosphane-
An ultraviolet curable resin composition containing 0.3 to 10 parts by weight of 2-oxide (E).