JPH04239504A - Photocurable gel substrate - Google Patents

Abstract

PURPOSE:To provide a photocurable gel substrate having excellent active ingredient preservability, odorless property, transparency, air permeability, etc., without requiring to be heated on the production of aqueous gel compositions. CONSTITUTION:A photocurable gel substrate characterized by including 0.1-10 pts.wt. of a photopolymerization initiator and 100 pts.wt. of polymerizable monomers comprising 90-5 pts.wt. of (A-1) a compound having a quaternary ammonium group and an ethylenic unsaturated bond in the molecule and/or (A-2) a compound having a sulfonic acid group and an ethylenic unsaturated bond in the molecule and 10-95 pts.wt. of (B) a water-soluble ethylenic unsaturated bond-containing compound having an ethylenic unsaturated bond and a hydrophilic group excluding the quaternary ammonium group and the sulfonic acid group in the molecule, containing >=10 pts.wt. of (B-1) a multifunctional water-soluble ethylenic unsaturated bond-containing compound having two or more ethylenic unsaturated bonds in the molecule.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention uses fragrances as active ingredients.
The present invention relates to a photocurable gel base material used in producing an aqueous gel composition containing substances such as deodorizing substances, insect repellents, and enzymes.

0002

[Prior Art] Various gel compositions containing volatile substances as active ingredients using various gelling agents are used as air fresheners, deodorants, insect repellents, repellents, attractants, etc. There is. Among such gel compositions, aqueous gel compositions use water-absorbing polymers such as polyvinyl alcohol and natural products such as carrageenan and agar as gelling agents, and the active ingredient and gelling agent are heated once to dissolve them. It was manufactured by uniformly mixing the mixture and cooling and solidifying it. For example, JP-A-62-1
No. 52464 and No. 62-152465,
It has been disclosed that carrageenan is used as a gel base material.

0003

[Problem to be solved by the invention] However, in JP-A-62
When carrageenan or the like is used as a gelling agent, as disclosed in JP-A-152464 and JP-A-62-152465, it is necessary to heat the gelling agent when dissolving and mixing the gelling agent in an aqueous solution containing the active ingredient. Therefore, there were problems such as volatile active ingredients being volatilized by heating or being changed by heat.

[0004] In addition to the above-mentioned problems, gel compositions using water-absorbing polymers such as polyvinyl alcohol also have an aesthetic problem in that the gel composition is difficult to become transparent.

[0005] The present invention solves the above-mentioned problems, and makes it possible to eliminate the need for heating during the production of an aqueous gel composition, and to improve the preservability, odorlessness, transparency, and air permeability of the active ingredients. The purpose of the present invention is to provide a photocurable gel base material that provides an aqueous gel composition with excellent properties.

[0006]

[Means for Solving the Problems] The present inventors have completed the present invention by researching a gel base material that provides an aqueous gel composition by polymerizing a polymerizable compound that is a component of the gel base material.

That is, the present invention provides a compound (A) having a quaternary ammonium group and an ethylenically unsaturated bond in one molecule.
-1) and/or 90 to 5 parts by weight of a compound (A-2) having a sulfonic acid group and an ethylenically unsaturated bond in one molecule, and a compound having two or more ethylenically unsaturated bonds in one molecule. Functional water-soluble ethylenically unsaturated bond-containing compound (
B-1) A water-soluble ethylenically unsaturated bond-containing compound (B) having a hydrophilic group other than a quaternary ammonium group and a sulfonic acid group and an ethylenically unsaturated bond in one molecule containing 10 parts by weight or more (B) 10~ Polymerizable compound 1 consisting of 95 parts by weight
The present invention provides a photocurable gel base material characterized in that it contains 0.1 to 10 parts by weight of a photopolymerization initiator per 0.00 parts by weight.

The present invention will be explained in detail below. A compound (A-1) having a quaternary ammonium group and an ethylenically unsaturated bond in one molecule means a compound (A-1) containing a quaternary ammonium group for making the compound (A-1) hydrophilic, −
1) is a compound that also has an ethylenically unsaturated bond to make it polymerizable, specifically, for example, N,N-dimethylacrylamide, N,N-dimethylaminoethylacrylamide, N,N-dimethylaminopropyl More specifically, compounds obtained by quaternizing a tertiary amine compound having an ethylenically unsaturated bond such as acrylamide using an alkyl chloride, 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, etc. is 4-(p-vinylbenzyl)-3-carbamoylpyridinium chloride, 4-vinylphenylethyltriethylammonium bromide, acrylamide-
Examples include 3-methylbutyldimethylamine ammonium chloride, vinylpyridinium chloride, vinylbenzyltrimethylammonium chloride, and the like.

[0009] The compound (A-2) having a sulfonic acid group and an ethylenically unsaturated bond in one molecule means a sulfonic acid group and an ethylenically unsaturated bond to make the compound (A-2) hydrophilic. It is a compound that also has an ethylenically unsaturated bond to make the compound (A-2) polymerizable, and specifically, t-butylacrylamide sulfonic acid, p-vinylbenzenesulfonic acid, 4-sulfenyl acrylate, Vinylsulfonic acid, 2-sulfoethyl methacrylate, 2-sulfoethyl acrylate, 2-acrylamidopropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid,
2-acrylamido-2-methylpropanesulfonic acid,
Examples include 2-(meth)acrylamido-2-(4-chlorophenyl)propanesulfonic acid and 2-(meth)acrylamido-2-(2-pyridyl)propanesulfonic acid.

[0010] A water-soluble ethylenically unsaturated bond-containing compound (B) having a hydrophilic group other than a quaternary ammonium group and a sulfonic acid group and an ethylenically unsaturated bond in one molecule refers to the compound (B). It is a compound that has both a hydrophilic group such as a hydroxyl group, a carboxyl group, a polyethylene oxide skeleton, a pyrrolidone ring, etc. to make the compound (B) water-soluble, and an ethylenically unsaturated bond to make the compound (B) polymerizable.

Specifically, bis(acrylamido)acetic acid, polypropylene glycol di(meth)acrylate,
Polyethylene glycol di(meth)acrylate and polyfunctional water-soluble ethylenically unsaturated bond-containing compounds having two or more ethylenically unsaturated bonds in one molecule represented by the following formulas (a) and (b) (B-1 ), or acrylamide-N-glycolic acid, (meth)acrylamide,
Acryloylmorpholine, diacetone acrylamide,
N,N-dimethylacrylamide, N-vinylcaprolactam, N-vinyloxazolidone, N-vinylsuccinimide, N-vinylphthalimide, (meth)acrylic acid, N-vinylimidazole, N-methylolacrylamide, (meth)acrylic acid-2 -hydroxypropyl, (meth)acrylic acid-2,3-hydroxypropyl,
Maleic acid, itaconic acid, crotonic acid, dimethylaminoethyl (meth)acrylate, mono(2-(meth)acryloyloxyethyl) acid phosphate, (meth)acryloyloxyethyl phthalic acid, caprolactone-modified acrylic monomer and the following formula ( c), (d) and (
The compound represented by e) is exemplified.

0012

[Chemical formula 1]

The photocurable gel base material of the present invention contains the above-mentioned compound as a polymerizable compound, and the content ratio thereof is as follows.

That is, when the total amount of the polymerizable compound is 100 parts by weight, the compound (A-1) and/or the compound (A-2) accounts for 90 to 5 parts by weight, and the remainder (
10 to 95 parts by weight) is the compound (B), and
10 to 95 parts by weight in 100 parts by weight of the polymerizable compound is the compound (B-1).

[0015] If the amount of the compound (A-1) and/or the compound (A-2) exceeds 90 parts by weight, it will not become gel-like even if the components in the gel base material are photopolymerized by the method described below. ,
On the other hand, if it is less than 5 parts by weight, the aqueous gel composition produced using the gel base material will become cloudy.

[0016] Also, in 100 parts by weight of the polymerizable compound, the above compound (A-1) and/or the above compound (A-2)
10 to 95 parts by weight of the remaining portion (remainder) is the compound (B
), but as the compound (B), the compound (B-
1) is always contained in an amount of 10 to 95 parts by weight per 100 parts by weight of the polymerizable compound.

In other words, the compound (B) is a polyfunctional water-soluble ethylenically unsaturated bond-containing compound (B-1
), or the compound (B-1) and a water-soluble ethylenically unsaturated compound having a hydrophilic group other than a quaternary ammonium group and a sulfonic acid group and only one ethylenically unsaturated bond in one molecule. In the latter case, the compound (B) is used in such a way that the compound (B-1) accounts for 10 parts by weight or more in 100 parts by weight of the polymerizable compound. .

The compound (B-1) is polymerizable compound 10
If the amount is less than 10 parts by weight, even if the components in the gel base material are photopolymerized by the method described below, they will not become gel-like.

The photocurable gel base material of the present invention contains a photopolymerization initiator in addition to the above polymerizable compound.

The photopolymerization initiators used in the present invention include radical photopolymerization initiators, cationic photopolymerization initiators, etc.
Among these, water-soluble ones are preferably used.

As the water-soluble photopolymerization initiator, 4-(2-hydroxyethoxy), which is a radical photopolymerization initiator, is used.
Phenyl-(2-hydroxy-2-propyl)ketone (
For example, Darocure 2959) manufactured by Merck & Co., Ltd. is exemplified.

The content of such a photopolymerization initiator in the photocurable gel base material of the present invention is 100% of the above polymerizable compound.
The amount is 0.1 to 10 parts by weight. If the amount is less than 0.1 part by weight, there is no effect of adding the photopolymerization initiator;
Even if it is added in an amount exceeding 0 parts by weight, not only will the addition effect no longer improve, but also unreacted polymerization initiator will remain in the aqueous gel composition produced using the gel base material, causing discoloration. etc. have negative effects.

The photocurable gel base material of the present invention further includes:
Preference is given to using surfactants. As surfactants, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxy Nonionic surfactants such as ethylene castor oil and polyoxyethylene lanolin alcohol, anionic surfactants such as alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, alkyl Examples include cationic surfactants such as ammonium salts and alkylbenzylammonium salts, and amphoteric surfactants such as lecithin.

The essential components of the photocurable gel base material of the present invention are as described above, but the gel base material may also optionally contain stabilizers (thermal polymerization inhibitors) such as hydroquinone,
It may contain a coloring agent, a sensitizer, a curing accelerator, a mold release agent, etc., such as tert-butylhydroquinone (TBH).

The photocurable gel base material of the present invention can be obtained by measuring and mixing the ingredients.

The photocurable gel base material of the present invention is suitable for producing an aqueous gel composition containing substances such as fragrances, deodorants, insect repellents, and enzymes as active ingredients.

The fragrances include citronellol, geraniol, terpineol, benzyl alcohol, dihydromircenol, dibenzyl ether, benzaldehyde, cyclamenaldehyde, α-methylhydrocinnamic aldehyde, benzyl acetate, limonene,
Examples include natural and synthetic fragrances such as benzyl benzoate and terpinyl acetate, alcohol-based, aldehyde-based, ketone-based, ester-based, and phenol-based fragrances, and blended fragrances that are mixtures thereof.

[0028] Deodorizing substances include α,β-unsaturated carboxylic acids and their esters such as fumaric acid, crotonic acid, and citraconic acid, and active methylene compounds such as acetylacetone, ethyl acetoacetate, and malonic acid. Illustrated.

Furthermore, as insect repellent substances, naphthalene,
Exemplary enzymes include ginger, p-dichlorobenzene, and the like, and examples of enzymes include invertase, glucose isomerase, glucose oxidase, and the like.

[0030] The aqueous gel composition is produced, for example, as follows. In other words, in an aqueous solution of fragrances, enzymes, etc.
A gel base material is contained so that the polymerizable compound is 5% by weight or more, and light irradiation is performed to polymerize the polymerizable compound to obtain an aqueous gel composition.

[0031] At this time, the amount of the polymerizable compound in the aqueous solution is
If it is less than % by weight, it will be difficult to form a gel.

[0032]

[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

(Example) A gel base material whose composition is shown in Table A was prepared, and the gel base material was dissolved in water such that the amount of polymerizable compound in the aqueous solution was 5 or 20% by weight. Here, ultraviolet lamps (Matsushita Electric Industrial Co., Ltd. "Black Light Blue Fluorescent Lamp" 20W x 5, ultraviolet output 3.0W x 5
The polymerization reaction was carried out by irradiating ultraviolet rays using UV light (maximum wavelength: 352 nm) to obtain an aqueous gel composition. The obtained aqueous gel composition was visually evaluated and the results are shown in Table A. In Table A, ○ indicates a transparent gel, Δ indicates a semi-transparent gel, × indicates no gelation, and ● indicates a cloudy gel.

As is clear from Table A, a transparent aqueous gel composition can be easily obtained using the photocurable gel base material of the present invention.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Case 2]

[0038]

EFFECTS OF THE INVENTION The present invention provides a photocurable gel base material that provides an aqueous gel composition with excellent preservability of active ingredients, odorlessness, transparency, and air permeability. The photocurable gel base material of the present invention can be cured by irradiation with light such as ultraviolet rays, and therefore a heating step is not required when producing an aqueous gel composition. By using the base material, it becomes possible to produce an aqueous gel composition containing, as active ingredients, fragrances, deodorants, insect repellents, enzymes, etc. that are easily changed by heating.

Claims (1)

[Claims] Claim 1: A compound (A-1) having a quaternary ammonium group and an ethylenically unsaturated bond in one molecule and/or
or 90 to 5 parts by weight of a compound (A-2) having a sulfonic acid group and an ethylenically unsaturated bond in one molecule, and a polyfunctional water-soluble ethylene having two or more ethylenically unsaturated bonds in one molecule. A water-soluble ethylenically unsaturated bond having a hydrophilic group other than a quaternary ammonium group and a sulfonic acid group and an ethylenically unsaturated bond in one molecule containing 10 parts by weight or more of a compound containing a sexually unsaturated bond (B-1) Containing compound (B) 1
A photocurable gel base material comprising 0.1 to 10 parts by weight of a photopolymerization initiator to 100 parts by weight of a polymerizable compound comprising 0 to 95 parts by weight.