JPH0374469A - Gel base material - Google Patents

Abstract

PURPOSE:To provide a gel base material excellent in low toxicity, non- odorousness, transparency, etc., useful as a deodorant, aromatic etc., with volatile effective ingredients retained therein, comprising a polymer prepared by polymerization of a monomer and/or oligomer curable at normal temperature. CONSTITUTION:The objective gel base material can be obtained by polymerization at <=80 (pref. 10-60) deg.C of a monomer and/or oligomer component polymerizable with light energy and/or a peroxide, comprising (A) 100 pts.wt. of a radically polymerizable compound having ethylenic unsaturated bond, (pref. containing 30-100 pts.wt. of an urethane (meth)acrylate with a polybutylene glycol pref. 500-5000 in molecular weight as skeleton and (B) 0.1-10 pts.wt. of B1: a photopolymerization initiator (e.g. 2,2-dimethoxy-2-phenylacetone) and/or B2: a peroxide (e.g. benzoyl peroxide).

Description

[Detailed Description of the Invention] <Industrial Application Field> The gel base material of the present invention can contain active ingredients such as fragrances, deodorants, insect repellents, repellents, attractants, insecticides, fungicides, fumigants, etc. Gel bases used in gel compositions that are retained and left in the atmosphere indoors or elsewhere, the volatile active ingredients gradually evaporate into the atmosphere and exert the desired effects such as fragrance and deodorization. Regarding materials.

<Prior Art> Various gel compositions containing volatile substances as active ingredients in various gel base materials are used as fragrances, deodorants, insect repellents, repellents, attractants, and the like.

Conventionally, such gel compositions usually use water-soluble polymers such as polyvinyl alcohol, oil-soluble polymers such as sodium stearate, carrageenan, etc. as gel base materials, and the active ingredient and gel base material are heated once to dissolve them. It is produced by cooling and solidifying a homogeneous mixture.

For example, JP-A-58-89261 uses sodium stearate as a gel base, and JP-A-82-152484 and JP-A-62-152485 use carrageenan as a gel base. It is disclosed that it was used as

On the other hand, Japanese Patent Application Laid-open No. 57-166168 also discloses a gel base material using an isocyanate compound.

<Problem to be solved by the invention> However, Japanese Patent Application Laid-open Nos. 152484/1984 and 62-
When carrageenan or the like is heated in a gel base as disclosed in Japanese Patent No. 152465, heating is required to dissolve and mix the active ingredients, and the volatile active ingredients may volatilize or change in quality due to heat. There are problems such as In addition to the above-mentioned problems, those based on polyvinyl alcohol or the like have the problem that the solvent for the active ingredient is limited to a water-soluble solvent.

Furthermore, as shown in Japanese Patent Application Laid-open No. 56-89261, methods using sodium stearate etc. require heating and dissolution, which causes problems such as volatilization of volatile active ingredients and deterioration of quality. Furthermore, gel compositions using this composition do not become completely transparent, which poses aesthetic problems.

The gel base material is an isocyanate compound.
Although it is superior in that it does not require heating, it is highly toxic and difficult to handle, and its composition is unstable due to its water absorption, and there are restrictions on the solvents that can be used (solvents with active hydrogen are There are problems such as unusable.

The purpose of the present invention is to solve the above problems, do not require heating during production, have good shelf life of active ingredients before curing, have low toxicity,
Provides a gel base material with excellent properties such as odorlessness, transparency, and breathability.

Furthermore, the present invention preferably provides a gel base material that can be suitably cured even when the gel base material has a large volume, that is, a so-called original product, and has excellent transparency and air permeability. do.

The present invention also provides a gel base material that is particularly compatible with terpene fragrances.

A further object of the present invention is to use such a gel base material,
The present invention provides a gel composition that retains a desired active ingredient.

<Means for solving nfi> In order to solve the above l1mM, the present invention provides a gel base material containing polymerized monomers and/or oligomers that can be polymerized by light energy and/or peroxide. , Radical polymerizable compound 1 in which the monomer and oligomer have an ethylenically unsaturated bond
00 parts 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)acrylate having a skeleton of polybutylene glycol having a molecular weight of 500 to 5000 is added. A gel base material containing 30 to 100 parts by weight is provided.

The present invention will be explained in detail below.

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

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

Such radically polymerizable compounds include compounds having an acryloyl group or methacryloyl group at the end of the molecular chain (
Preferably used are meth)acrylate compounds, unsaturated polyesters made of unsaturated dicarboxylic acids such as fumaric acid and maleic acid, and polyhydric alcohols such as ethylene glycol and propylene glycol, vinyl compounds such as styrene, or mixtures thereof.

The (meth)acrylate compounds used in the present invention include urethane (meth)acrylates having one or more urethane bonds in one molecule and a (meth)acryloyl group at the end; epoxy (meth)acrylates synthesized from epoxy resins; ) Acrylate: Polybutadiene (meth) with polybutadiene as the main skeleton
Acrylate; Oligoester (meth)acrylate whose main chain is an ester bond; (meth)acrylic oligomer such as polyether (meth)acrylate whose main chain is an ether bond; Mono(meth)acrylic oligomer having one (meth)acryloyl group ) Acrylate monomer; A polyfunctional (meth)acrylate monomer having two or more (meth)acryloyl groups is preferably used.

Urethane (meth)acrylate can be synthesized, for example, from a polyol component, an isocyanate component, and a (meth)acrylate component having a hydroxyl group into which a terminal (meth)acryloyl group can be introduced.

The polyol component applied to the synthesis of such urethane (meth)acrylates is a synthetic polymer compound having 1 to 2 or more hydroxyl groups in the molecule, such as polyether polyol compounds, polyester polyol compounds, polyurethane polyols. Examples include polyhydroxypolyolefin compounds and polyhydroxypolyolefin compounds.

Such polyether polyol compounds include polyethylene glycol, polypropylene glycol,
Polyalkylene glycols such as polybutylene glycol, polytetramethylene glycol, polyhexamethylene glycol; or alkylene oxides such as ethylene oxide, propylene oxide, tetrahydrofuran, etc. Obtained by adding to polyhydric alcohols such as methylolpropane, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2゜6-hexanediol, pentaerythritol, etc. Examples include polyether polyols.

In addition, as polyester polyol compounds, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, hexahydrophthalic acid, hemic acid, het acid,
A polyester polyol obtained by the condensation reaction of a polybasic acid such as succinic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, dodecenylsuccinic acid, trimellitic acid, pyromellitic acid, etc. or its anhydride and the above-mentioned polyhydric alcohol. is exemplified.

In addition, polyurethane polyol compounds include polyurethane polyols obtained by addition reaction of polyisocyanate compounds or multimers thereof with an excess of polyhydric alcohol; the above-mentioned polyether polyols, polyester polyols, Examples include polyurethane polyols obtained with isocyanate compounds.

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

In addition, as isocyanate components applied to the synthesis of urethane (meth)acrylate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2
．． 4-Tolylene diisocyanate, 2.8-)-lylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-
Diisocyanate, naphthylene-1,5-diisocyanate, isophorone diisocyanate, 1-methyl-2,
4-Diisocyanatocyclohexane, 1-methyl-2
, 6-diisocyanate cyclohexane, dicyclohexylmethane diisocyanate and the like.

Furthermore, as the (meth)acrylic acid ester component having a hydroxyl group into which a terminal (meth)acryloyl group is introduced, which is applied to the synthesis of urethane (meth)acrylate-I, 2-hydroxyethyl (meth)acrylate, 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 and the like are exemplified.

To synthesize urethane (meth)acrylate using the above polyol component, isocyanate component, and (meth)acrylate component having a hydroxyl group,
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; a polyisocyanate component and a (meth)acrylate component having a hydroxyl group are reacted, and then a polyol component is reacted. Synthesis method for reacting the components; Examples include a synthesis method for simultaneously reacting a polyol component, a polyisocyanate component, and a (meth)acrylate component having a hydroxyl group, and any of these methods can be applied in the present invention.

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

The reaction molar ratio when synthesizing urethane (meth)acrylate using the above synthesis method is 1.2 to 5.0 mol of isocyanate and 0.0 mol of (meth)acrylate having a hydroxyl group to 1 mol of polyol. About 3 to 5.0 mol is preferable [B, especially the molar ratio of hydroxyl group to isocyanate group OH/NCO is adjusted to be 1 or more to prevent isocyanate group from remaining in the reaction product. In the synthesis of the above-mentioned urethane (meth)acrylate, if necessary, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, tert-butylhydroquinone, etc. is added in an amount of about 100 to 5000 ppm based on the total amount, and
The total amount of urethanization catalyst such as triethylamine, stannous octoate, dibutyltin dilaurate, etc.
It may be added in an amount of about 0.00 ppm.

Epoxy (meth)acrylates are bisphenol F type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, cyclocyclic epoxy resins, aliphatic epoxy resins, and these resins are combined with rubbers such as NBR, polybutadiene, or urethane resins. Examples include those obtained by reacting (meth)acrylic acid with glycidyl ether groups of modified epoxy resins.

Polybutadiene (meth)acrylate is obtained from (meth)acrylic acid and a polybutadiene oligomer having a functional group such as a hydroxyl group or a glycidyl group at the end.

Alternatively, those obtained by prepolymerizing a terminal functional group and a diisocyanate compound and further reacting with hydroxy (meth)acrylates are also preferably used.

Examples of the (meth)acrylic oligomer 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.

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

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

As mono(meth)acrylate monomers, aryloxyalkyl(meth)acrylates such as 2-phenoxyethyl(meth)acrylate, nonylphenoxyethyl(meth)acrylate, nonylphenol propylene oxide adduct(meth)acrylate; 2-ethylhexyl( meth) acrylate, lauryl (
Alkyl (meth)acrylates such as meth)acrylate and n-butyl (meth)acrylate; 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate hydroxyalkyl (meth)acrylates such as; alkoxyalkyl (meth)acrylates such as 2-ethoxyethyl (meth)acrylate, 4-methoxybutyl (meth)acrylate; cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, isobonyl Examples include cycloalkyl (meth)acrylates such as (meth)acrylate; and cycloalkenyl (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate.

Polyfunctional (meth)acrylate monomers include 1.6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polybrobylene glycol di(meth)acrylate, 2. 2-bis[4-(meth)acryloyloxyjethoxyphenyl]propane, hydrogenated dicyclobentadiethyl di(meth)acrylate, di(meth)acrylate with the following structural formula, (in the above formula, R is a hydrogen atom or methyl Difunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide adduct tri(meth)acrylate, glycerin propylene oxide adduct tri(meth)acrylate Trifunctional (
Meth)acrylate; Examples include polyfunctional (meth)acrylates having four or more functionalities, such as pentaerythritol tetra(meth)acrylate and 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 unsaturated dicarboxylic acids include fumaric acid, maleic acid, itaconic acid, and the like.

In addition, polyhydric alcohols include ethylene glycol,
Examples include propylene glycol and diethylene glycol.

Furthermore, examples of the vinyl compound used in the present invention include styrene, vinyl acetate, and the like.

A mixture of the above materials is also suitably used as the gel base material of the present invention.

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

In particular, in the present invention, urethane (meth)acrylate having a backbone of polybutylene glycol having a molecular weight of 500 to 5,000 is an essential component. Polybutylene glycol shows excellent compatibility with terpene fragrances. If this terpene-based fragrance can be used, the terpene-based fragrance itself can be used in combination with other fragrances as a solvent, thereby expanding the types of fragrances and the scope of their use.

Specifically, the urethane (meth)acrylate having a skeleton of polybutylene glycol having a molecular weight of 500 to 5000 is hydroxypropyl (meth)acrylate (HP
A)/Hexamethylene diisocyanate (MDI)/Polybutylene glycol (PBG)-500/HDI/H
PA, HPA/HDI/PBG-3000/MDI/H
Examples include PA.

Here, if the molecular weight is less than 500, it is too hard and the flexibility as a gel is insufficient, and if it exceeds 5,000, curing becomes slow, which is not preferable. In addition, methane (meth)acrylate having a polybutylene glycol skeleton is the radically polymerizable compound 100! It is preferable to contain 30 to 100 parts by weight in each part. 30! If the amount is less than i part, a transparent gel cannot be obtained.

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

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

The content of such a photopolymerization initiator in the gel base material of the present invention is preferably 0.3 parts by weight per 1001i parts of the above-mentioned radically polymerizable compound having an ethylenically unsaturated bond.
It is about 1 to 10 parts by weight. If the content is less than O,ill parts by weight, there is no effect of addition, and if it exceeds 10 parts by weight, the effect of addition will not improve.

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

The content of such peroxide is preferably 0.1 to 10 parts by weight per 100 parts by weight of the above-mentioned radical polymerizable compound having an ethylenically unsaturated bond. ! It's about the amount of parts. If the content is less than 0.1 parts by weight, there is no effect of addition, and if the content is less than 0.1 parts by weight,
Even if it exceeds parts by weight, the effect of addition will not improve.

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

In addition, when used together, the total content is 0, -1 to 1
0! It is preferable that the amount is about 1 part.

In addition, if necessary, a stabilizer (thermal polymerization inhibitor) such as hydroquinone, tart-butylhydroquinone (TB
H), colorants, sensitizers, curing accelerators, mold release agents, etc. can be used.

The volatile substance used in the present invention is one that gradually evaporates into the atmosphere when left in the atmosphere and exerts the effect as a desired active ingredient such as aroma, deodorization, etc., and is usually used as a fragrance as an air freshener. , deodorants, insect repellents, repellents, attractants, insecticides, fungicides, fumigants, etc. are used.

In the gel composition of the present invention, preferred fragrances include citronellol, geraniol, terpineol, benzyl alcohol, dihydromircenol, dibenzyl ether, benzaldehyde, cyclamenaldehyde, lilyal, benzyl acetate, limonene, benzyl benzoate, and terpineol. Examples include terpene-based, alcohol-based, aldehyde-based, ketone-based, ester-based, and phenol-based natural and synthetic fragrances such as vinyl acetate, and blended fragrances that are mixtures thereof.

Examples of deodorants 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.

In addition, examples of the insect repellent include naphthalene, cypress, p-dichlorobenzene, and the like.

Further, examples of the repellent include neem extract, 1,8-cineole, phthalate ester, and the like.

Examples of attractants include alkenyl alcohols, alkenyl aldehyde pheromones, and furanone derivatives.

Further, in the present invention, a solvent may be added if necessary.

As the solvent, alcohol-based, ketone-based, ester-based, and other solvents that have good compatibility with the volatile substance and the curable resin can be used as appropriate.

Some of these solvents are also used as fragrances.

Examples of solvents include diethyl phthalate, dipropylene glycol, ethylcarpitol, hexylene glycol, 3-methyl-3-methoxybutanol, 3-methyl-
Examples include 3-methoxybutyl acetate.

Furthermore, solvents used as fragrances include benzyl alcohol, dibenzyl ether, benzyl acetate-1,
, methyl benzoate, benzyl benzoate, citronellol, dihydromircenol, dihydroterpineol, geraniol, terpineol, benzaldehyde, cyclamen aldehyde, hydroxycitronellal, p-tart-butyl-α-methylhydroxycinnamic aldehyde, geranyl acetate, linalyl acetate , turbinyl acetate, limonene, and the like.

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

In a gel composition using the gel base material of the present invention, the amount of volatile substances used is preferably 2 to 95% by weight, more preferably 3 to 50% by weight of the entire gel composition. If the content of volatile substances is less than 2% by weight, it is difficult to obtain the desired effects such as aroma, deodorization, insect repellency, etc., and if it exceeds 95% by weight, the amount of gel base material is relatively small. This makes it difficult to obtain a suitable gel-like material.

Further, the preferred amount of the monomer or oligomer mentioned above is 3 to 50% of the total gel composition! The amount is %. If it is less than 3% by weight, it will be difficult to form a gel, and if it is more than 50% by weight, the gel will become too hard and the rate of volatilization of volatile substances will be slow.

The gel composition of the present invention is usually obtained by thoroughly mixing the above-mentioned components and then polymerizing the gel base material. The method for polymerizing the gel base material in the present invention is to polymerize various monomers and/or oligomers using light energy or peroxide to form a gel, and any of these methods can be used. Further, in this case, the polymerization temperature is preferably 80°C or lower, preferably 10 to 60°C.

<Example> The present invention will be specifically explained below 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 gellicol skeletons shown in Table 1 below, and photopolymerization initiators were mixed at room temperature without using a solvent to produce various A gel base material was obtained. The amount of each compound (Ii
The amounts (parts) are shown in Table 1.

Take 2 g of this gel base material and 8 g of limonene in a glass bottle with an inner diameter of 20 mm, stir, and then use an ultraviolet lamp ("Black Light Blue Fluorescent Lamp" manufactured by Powder Denki Sangyo Co., Ltd., 20 W x 5, ultraviolet output 3.0 W x 5, maximum wavelength 352 mm). 5cm below
The mixture was irradiated for 60 minutes and checked to see if gelation occurred.

The results are shown in Table 1.

(Comparative Examples 1 to 3) Gel base materials containing no urethane acrylate containing a polybutylene glycol skeleton were obtained and mixed with limonene.

The amounts of each compound and their compatibility during curing were investigated, and the results are shown in Table 1.

Table 1 3) Urethane acrylate (3) R-45ACR polybutadiene urethane elastomer manufactured by Idemitsu Petrochemical Co., Ltd. *4) Urethane acrylate (4) 2HEA
/Hydrogenated MDI/PTMG850/Hydrogenated MDI/2HEA
HEA: 2-hydroxyethylene acrylic 1 note MDI: diphenylmethane diisocyanate PTMG: 5) Urethane 7 acrylate in polytetramethylene glycol (5) 2HEA/Hydrogenated M
DI/PPG100O/Hydrogenated MDI/51 in 2HEA
L-A Chemical name Lauryl acrylate CH2-CHC00C12H2B Kyoeisha Yushi +7) M-233 CHa OCOCH= CH2 ○...Transparent gel Δ...Cloudy gel ×...Uncured 1) Urethane acrylate (1) HPA/HDI
/PBG-500/MDI/HPAHPA: Hydroxypropyl acrylate HDI: Hexamethylene diisocyanate PBG: Polybutylene glycol I2) Urethane acrylate (2) HPA/) (D
I/PBG-3000/HDI/HPAn Ki 16 Kyoeisha Yushi Chuo 8) TMPTA Trimethylolpropane triacrylate structural formula
Kyoeisha Yushi CH20COCH TomiC
H2 CH3CH2-C-CHz 0COCH”CHaCH2
0COCH-CH2 $9) Illumicure 184 Photopolymerization initiator Manufactured by Ciba Geigy As shown above, when a certain amount or more of urethane acrylate with a backbone of polybutylene glycol is used, a transparent gel can be cured even when limonene is used as a fragrance. I can do it.

<Effects of the Invention> As described above, the gel base material of the present invention uses monomers or oligomers that harden at room temperature, so it can be cured in a short time at room temperature, reducing losses due to volatilization of volatile substances and deterioration. There is no. Moreover, this gel base material is low-toxic and odorless, and does not cause any harm to the human body.

Furthermore, by containing urethane acrylate having a polybutylene glycol skeleton, terpene fragrances such as limosone and dipentene can be used, and a transparent cured gel product can be obtained.

Claims (1)

[Claims] (1) A gel base material containing a monomer and/or oligomer polymerized by light energy and/or peroxide, wherein the monomer and/or oligomer is a radical having an ethylenically unsaturated bond. Polymerizable compound 1
00 parts 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)acrylate having a skeleton of polybutylene glycol having a molecular weight of 500 to 5000 is added. A gel base material comprising 30 to 100 parts by weight.