JP2781611B2 - Gel substrate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial application field> The present invention relates to an active ingredient such as a fragrance, a deodorant, an insect repellent, a repellent, an attractant, an insecticide, a bactericide, a fumigant, etc. And leave it indoors or in the other air,
The present invention relates to a gel base material used for a gel composition in which a volatilizable active ingredient gradually volatilizes into the atmosphere and exhibits desired effects such as aroma and deodorization.

<Conventional Technology> Various gel compositions containing volatile substances as active ingredients in various gel base materials have been used as fragrances, deodorants, insect repellents, repellents, attractants and the like.

Conventionally, such a gel composition usually uses a water-soluble polymer such as polyvinyl alcohol or an oil-soluble polymer such as sodium stearate or carrageenan as a gel base material,
It is produced by heating and dissolving the active ingredient and the gel base material once and then cooling and solidifying a mixture obtained by uniformly mixing the active ingredient and the gel base material.

For example, Japanese Patent Application Laid-Open No. 56-89261 discloses a method using sodium stearate as a gel base material.
Nos. 152464 and 62-152465 disclose those using carrageenan as a gel base material.

On the other hand, JP-A-57-166168 discloses a method using an isocyanate compound as a gel base material.

<Problems to be Solved by the Invention> However, when carrageenan or the like is used as a gel base as disclosed in JP-A-62-152464 and JP-A-62-152465, the active ingredients are dissolved and mixed. In this case, heating is required, and there is a problem that the volatile active ingredient is volatilized by heating or deteriorated by heat. In addition, those having a base material such as polyvinyl alcohol have a problem that the solvent of the active ingredient is limited to a water-soluble solvent in addition to the above-mentioned problems.

Further, as shown in JP-A-56-89261, those using sodium stearate or the like also need to be heated and dissolved once, and there is a problem that the volatile active ingredient is volatilized and deteriorated, and The gel composition using this does not become completely transparent and has an aesthetic problem.

In addition, those using an isocyanate compound as a gel base material are excellent in that they do not require heating, but are highly toxic and difficult to handle, and the composition is unstable due to water absorption, so that it is used. There are problems such as limitations on possible solvents (solvents having active hydrogen cannot be used).

The object of the present invention is to solve the above-mentioned problems, it does not require heating at the time of production, has good preservability of the active ingredient before curing, and has excellent properties such as low toxicity, odorlessness, transparency, and air permeability. A gel substrate is provided.

Further, in the present invention, preferably, the gel base material can be suitably cured even when the gel base material has a large volume, that is, a so-called thick material, and provides a gel base material having excellent transparency and gas permeability. I do.

Further, the present invention provides a gel base material having good compatibility with a terpene-based fragrance in particular.

A further object of the present invention is to provide a gel composition using such a gel base material and holding a desired active ingredient.

<Means for Solving the Problems> In order to solve the above problems, the present invention relates to a gel base material containing a polymerized monomer and / or oligomer polymerizable by light energy and / or peroxide. A radical polymerizable compound wherein the monomer and / or oligomer has an ethylenically unsaturated bond
100 parts by weight, containing 0.1 to 10 parts by weight of a polymerization initiator, wherein 100 parts by weight of the radical polymerizable compound has a molecular weight of 5
A gel base material comprising 30 to 100 parts by weight of urethane (meth) acrylate having a polybutylene glycol skeleton of 00 to 5000.

 Hereinafter, the present invention will be described in detail.

The gel base material of the present invention contains a monomer and / or an oligomer that can be polymerized by light energy and / or a peroxide, and the monomer and / or the oligomer has an ethylenically unsaturated bond in a weight of 100% by weight. And 0.1 to 10 parts by weight of a polymerization initiator, and in 100 parts by weight of the radically polymerizable compound, urethane (meth) having a polybutylene glycol having a molecular weight of 500 to 5,000, a polyisocyanate and a hydroxyl group It contains 30 to 100 parts by weight of acrylate.

The monomer and / or oligomer polymerizable by light energy, photopolymerization initiator and / or peroxide used for the gel base material of the present invention is preferably a radical polymerizable compound having an ethylenically unsaturated bond as described above. It is.

Examples of such radical polymerizable compounds include (meth) acrylate compounds having an acryloyl group or a methacryloyl group at the molecular chain terminal, unsaturated dicarboxylic acids such as fumaric acid and maleic acid, and polyhydric alcohols such as ethylene glycol and propylene glycol. Or a vinyl compound such as styrene or a compound thereof.

The (meth) acrylate compound used in the present invention includes a urethane (meth) acrylate having one or more urethane bonds in one molecule and having a (meth) acryloyl group at a terminal; an epoxy (meth) synthesized from an epoxy resin. ) Acrylate; polybutadiene (meth) acrylate having polybutadiene as a main skeleton; oligoester (meth) acrylate having an ester bond as a main chain; (meth) acrylic oligomers such as polyether (meth) acrylate having an ether bond as a main chain A mono (meth) acrylate monomer having one (meth) acryloyl group; a polyfunctional (meth) acrylate monomer having two or more (meth) acryloyl groups is preferably used.

Urethane (meth) allylate can be synthesized, for example, from a polyol component, an isocyanate component, and a (meth) acrylate component having a hydroxyl group capable of introducing a terminal (meth) acryloyl group.

The polyol component applied to the synthesis of such a urethane (meth) acrylate is a synthetic polymer compound having two or more hydroxyl groups in a molecule, such as a polyether polyol compound, a polyester polyol compound,
Examples thereof include a polyurethane polyol compound and a polyhydroxy polyolefin compound.

Examples of such polyether polyol compounds include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, and polyhexamethylene glycol; or alkylene oxides such as ethylene oxide, propylene oxide, and tetrahydrofuran.
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, 1,3-butanediol, 1,
Examples thereof include polyether polyols obtained by adding to polyhydric alcohols such as 4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2,6-hexanetriol, and pentaerythritol.

Further, as the polyester polyol compound, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, hexahydrophthalic acid, hymic acid, heptic acid, succinic acid, maleic acid, fumaric acid , Adipic acid,
Examples thereof include polyester polyols obtained by a condensation reaction between polybasic acids such as sebacic acid, dodecenylsuccinic acid, trimellitic acid, and pyromellitic acid or anhydrides thereof and the above-mentioned polyhydric alcohols.

Examples of the polyurethane polyol compound include: a polyurethane polyol obtained by an addition reaction of a polyisocyanate compound or a polymer thereof with an excess of a polyhydric alcohol; polyether polyol, polyester polyol, and polyisocyanate described above. The polyurethane polyol obtained by the compound is exemplified.

Further, as the polyhydroxy polyolefin compound, acrylic polyol, polybutadiene polyol,
Examples thereof include polyisoprene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol.

The isocyanate component applied to the synthesis of urethane (meth) acrylate includes ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthylene-1,5-diisocyanate, isophorone Examples thereof include diisocyanate, 1-methyl-2,4-diisocyanatocyclohexine, 1-methyl-2,6-diisocyanatocyclohexane, dicyclohexylmethane diisocyanate and the like.

Further, as the (meth) acrylate component having a hydroxyl group for introducing a terminal (meth) acryloyl group applied to the synthesis of urethane (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
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 and the like.

In order to synthesize urethane (meth) acrylate using the polyol component, isocyanate component and (meth) acrylate component having a hydroxyl group as described above, first, the polyol component is reacted with the polyisocyanate component, and then the hydroxyl group is reacted. A method of reacting a (meth) acrylate component having a hydroxyl group; a method of reacting a polyisocyanate component with a (meth) acrylate component having a hydroxyl group, and then reacting a polyol component; and a method of reacting a polyol component, a polyisocyanate component, and hydrosil. Examples include a synthesis method in which a (meth) acrylate component having a group is reacted simultaneously, and any of the methods is applicable in the present invention.

The reaction temperature at this time is preferably about 30 to 120 ° C.

In addition, the reaction molar ratio at the time of synthesizing urethane (meth) acrylate by the above synthesis method is about 1.2 to 5.0 mol of isocyanate and about 0.3 to 5.0 mol of (meth) acrylate having a hydroxyl group per 1 mol of polyol. Preferred, especially the molar ratio of hydroxyl groups to isocyanate groups
It is preferable that OH / NCO be 1 or more so that no isocyanate group remains in the reaction product.

When synthesizing the above urethane (meth) acrylate, if necessary, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, tert-butyl hydroquinone or the like may be used in an amount of about 100 to 5000 ppm, triethylamine, stannous octoate, dibutyltin. A urethanization catalyst such as dilaurate may be added in an amount of about 100 to 5000 ppm based on the total amount.

Epoxy (meth) acrylate is bisphenol A
Type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin and glycidyl ether group of epoxy resin modified with NBR, polybutadiene or other rubber, or urethane resin. Examples thereof include those obtained by reacting (meth) acrylic acid.

The polybutadiene (meth) acrylate is obtained, for example, from a polybutadiene oligomer having a functional group such as a hydroxyl group or a glycidyl group at a terminal and (meth) acrylic acid. Alternatively, those obtained by prepolymerizing from a terminal functional group and a diisocyanate compound and further reacting with a hydroxy (meth) acrylate are also preferably used.

Examples of the (meth) acrylic oligomer include polyester (meth) acrylate having an ester bond as a main chain, and polyether (meth) acrylate having an ether bond as a main chain.

Such a polyester (meth) acrylate is obtained from the polyester polyol and (meth) acrylic acid.

The polyether (meth) acrylate is obtained from the above-mentioned polyether polyol and (meth) acrylic acid.

Mono (meth) acrylate monomers include 2-phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, nonylphenol propylene oxide adduct (meth) acrylate and other aryloxyalkyl (meth) acrylates; 2-ethylhexyl ( Alkyl (meth) acrylates such as meth) acrylate, lauryl (meth) acrylate, and n-butyl (meth) acrylate; 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate; alkoxyalkyl such as 2-ethoxyethyl (meth) acrylate and 4-methoxybutyl (meth) acrylate (Meth) acrylates; cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate and isobonyl (meth) acrylate; cycloalkenyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate And the like.

Polyfunctional (meth) acrylate monomers include 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2- Screw [4- (meta)
[Acryloyloxydiethoxyphenyl] propane, hydrogenated dicyclopentadiethyldi (meth) acrylate, di (meth) acrylate of the following structural formula, (Wherein R represents a hydrogen atom or a methyl group); trifunctional (meth) acrylate; trimethylolpropane tri (meth) acrylate;
Trifunctional (meta) such as trimethylolpropane propylene oxide adduct tri (meth) acrylate, glycerin propylene oxide adduct tri (meth) acrylate, tris [(meth) acryloyloxyethyl] isocyanurate, pentaerythritol tri (meth) acrylate ) Acrylate; pentaerythritol tetra (meth) acrylate,
Examples thereof include tetrafunctional or higher polyfunctional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate.

The unsaturated polyester used in the present invention is obtained from an unsaturated dicarboxylic acid and a polyhydric alcohol.

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

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, and the like.

Examples of the vinyl compound used in the present invention include styrene and vinyl acetate.

As the gel base material of the present invention, a mixture of the above is also suitably used.

The molecular weight of such a compound is, for example, preferably about 1,000 to 5,000 in the case of an oligomer.

Particularly, in the present invention, urethane (meth) acrylate having a skeleton of polybutylene glycol having a molecular weight of 500 to 5,000 is an essential component. Polybutylene glycol exhibits excellent compatibility with terpene-based flavors. When this terpene-based fragrance can be used, the terpene-based fragrance itself can be used in combination with another fragrance as a solvent, so that the types and use ranges of the fragrance can be expanded.

The urethane (meth) acrylate having a polybutylene glycol skeleton having a molecular weight of 500 to 5,000 is specifically, hydroxypropyl (meth) acrylate (HPA)
/ Hexamethylene diisocyanate (HDI) / Polybutylene glycol (PBG) -500 / HDI / HPA, HPA / HDI / PBG-3
000 / HDI / HPA and the like.

Here, if the molecular weight is less than 500, it is too hard and the flexibility as a gel is insufficient, and if it is more than 5,000, curing becomes slow, which is not preferable. The urethane (meth) acrylate having a polybutylene glycol skeleton is preferably contained in an amount of 30 to 100 parts by weight based on 100 parts by weight of the radically polymerizable compound. If the amount is less than 30 parts by weight, a transparent gel cannot be obtained.

The gel base material of the present invention preferably contains a radically polymerizable compound having an ethylenically unsaturated bond as described above, and further contains a polymerization initiator such as a photopolymerization initiator.

The photopolymerization initiator applied to the present invention may be one used for ordinary photopolymerization, for example, 2,2-dimethoxy-2-
Phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1,2,
4-diethylthioxanthone, benzoin isobutyl ether, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-
Examples are 4'-isopropyl-2-methylpropiophenone and the like, and there is no particular limitation.

The content of such a photopolymerization initiator in the gel base material of the present invention is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the radical polymerizable compound having an ethylenically unsaturated bond described above.
It is about parts by weight. If the content is less than 0.1 part by weight, there is no effect of addition, and if it exceeds 10 parts by weight, the effect of addition is not improved.

In the present invention, not only the photopolymerization initiator as described above, but also a peroxide may be used as a polymerization initiator, if necessary.

Examples of the peroxide include benzoyl peroxide, methyl acetoacetate peroxide, methyl ethyl ketone peroxide, and acetylacetone peroxide. Further, if necessary, examples of the curing accelerator include cobalt naphthenate and dimethylaniline.

The content of such a peroxide is preferably about 0.1 to 10 parts by weight based on 100 parts by weight of the above-mentioned radically polymerizable compound having an ethylenically unsaturated bond. If the content is less than 0.1 part by weight, there is no effect of addition, and if it exceeds 10 parts by weight, the effect of addition is not improved.

A plurality of photopolymerization initiators and peroxides may be used, respectively, or may be used in combination.

When used in combination, the content is preferably about 0.1 to 10 parts by weight in total.

If necessary, stabilizers (thermal polymerization inhibitors), for example,
Hydroquinone, tert-butyl hydroquinone (TB
H), a colorant, a sensitizer, a curing accelerator, a release agent and the like can be used.

The volatile substance used in the present invention is a substance which, when left in the air, gradually volatilizes in the air and exhibits an effect as a desired active ingredient such as aroma and deodorization, and is generally a fragrance as a fragrance. , Deodorants, insect repellents, repellents, attractants, insecticides, fungicides, fumigants, and the like.

In the gel composition of the present invention, preferably used flavors include citronellol, geraniol, terpineol, benzyl alcohol, dihydromyrcenol, dibenzyl ether, benzaldehyde, cyclamenaldehyde, lilial, benzyl acetate, limonene,
Examples include terpene-based, alcohol-based, aldehyde-based, ketone-based, ester-based, and phenol-based natural and synthetic flavors such as benzyl benzoate and terpinyl acetate, and blended flavors that are mixtures thereof.

Examples of the deodorant include α, β-unsaturated carboxylic acids and esters such as fumaric acid, crotonic acid and citraconic acid, and active methylene compounds such as acetylacetone, ethyl acetoacetate and malonic acid.

Insect repellents include naphthalene, show brain, p-
Examples thereof include dichlorobenzene.

Examples of the repellent include neem extract, 1,8-cineole, phthalate, and the like.

Examples of the attractant include alkenyl alcohols, alkenyl aldehyde-based pheromones, and furanone derivatives.

Further, in the present invention, a solvent can be blended if necessary.

As the solvent, a solvent having good compatibility between the volatile substance and the curable resin, such as an alcohol, a ketone, and an ester, can be used as appropriate.

Some of these solvents are also used as perfumes.

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

Further, as a solvent used also as a fragrance, benzyl alcohol, dibenzyl ether, benzyl acetate, methyl benzoate, benzyl benzoate, citronellol, dihydromyrcenol, dihydroterpineol, geraniol, terpineol, benzaldehyde, cyclamenaldehyde, hydroxycitronellal, p-tert-butyl-α-methylhydroxycinnamic aldehyde, geranyl acetate, linalyl acetate, terpinyl acetate, limonene and the like.

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

In the gel composition using the gel base material of the present invention, the amount of the volatile substance is preferably 2 to 95% by weight, more preferably 3 to 50% by weight of the whole gel composition. If the volatile substance is less than 2% by weight, it is difficult to obtain desired effects due to aromaticity, deodorization, insect repellency, etc., and if it exceeds 95% by weight, the amount of the gel base material is relatively small. Thus, it becomes difficult to obtain a suitable gel.

The preferred amount of the monomer or oligomer is 3 to 50% by weight of the whole gel composition. 3% by weight
If it is less than 50%, it is difficult to form a gel, and if it is more than 50% by weight, the gel becomes too hard, and the volatilization rate of the volatile substance is reduced.

The gel composition of the present invention is usually obtained by sufficiently mixing the above-mentioned components and then polymerizing the gel base material to obtain a gel composition. The method of polymerizing a gel base material in the present invention is a method of polymerizing various monomers and / or oligomers with light energy or peroxide to form a gel, and any of these methods is applicable. Also, in this case,
The polymerization temperature is 80 ° C or lower, preferably 10 to 60 ° C.

<Examples> Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to these.

(Examples 1 to 7) Radical polymerizable compounds such as urethane acrylates containing various polybutylene glycol skeletons shown in Table 1 below, and photopolymerization initiators and the like were mixed at room temperature without using a solvent to obtain various types. A gel substrate was obtained. The amounts (parts by weight) of each compound are shown in Table 1.

2 g of this gel base material and 8 g of limonene are placed in a glass bottle having an inner diameter of 20 mm, and after stirring, an ultraviolet lamp (Matsushita Electric Industrial Co., Ltd. “Black Light Blue Fluorescent Lamp”, 20 W × 5, UV output 3.0
Irradiation was performed at 5 cm under 5 cm (W × 5 lines, maximum wavelength: 352 mm) for 60 minutes to check whether or not gelation occurred.

 Table 1 shows the results.

(Comparative Examples 1 to 3) A gel base material containing no urethane acrylate having a polybutylene glycol skeleton was obtained and mixed with limonene.

The amount of each compound and its compatibility at the time of curing were examined. The results are shown in Table 1.

As described above, when a certain amount or more of urethane acrylate having polybutylene glycol as a skeleton is used, a transparent gel can be cured even with limonene as a fragrance.

<Effects of the Invention> As described above, since the gel base material of the present invention uses a room-temperature-curable monomer or oligomer, it can be cured in a short time at room temperature, and volatilization of volatile substances, loss due to deterioration. There is no. The gel base material has low toxicity and odorless, and does not harm the human body.

Further, by containing a urethane acrylate having a polybutylene glycol skeleton, terpene-based flavors such as limoson and dipentene can be used, and a transparent gel cured product can be obtained.

Continuation of the front page (56) References JP-A-51-139640 (JP, A) JP-A-51-98342 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A01N 25 / 00-25/34 C08F 2/00-2/60 C08L 1/00-101/14 A61L 9/00-9/01

Claims (1)

(57) [Claims] 1. A gel base material comprising a polymerized monomer and / or oligomer polymerizable by light energy and / or peroxide, wherein said monomer and / or oligomer has an ethylenically unsaturated bond. Radical polymerizable compound having 10
0 parts by weight, containing 0.1 to 10 parts by weight of a polymerization initiator, in 100 parts by weight of the radical polymerizable compound, the molecular weight is 500
A gel base material comprising 30 to 100 parts by weight of urethane (meth) acrylate having a polybutylene glycol skeleton of up to 5,000.