JPH04353515A - Room temperature-curable epoxy resin composition containing perfume - Google Patents

Abstract

PURPOSE:To provide the subject epoxy resin composition containing a specific urethane-modified epoxy resin, an active organic curing agent and a perfume, not requiring a heating process on the production of cured products, having no problem of toxicity and capable of producing thick molded products. CONSTITUTION:The objective epoxy resin composition having excellent active component storage stability, giving cured products having good elasticity, and containing (A) an urethane-modified epoxy resin obtained by reacting an epoxy and hydroxyl groups-having compound such as ethylene glycol monoglycidyl ether with an urethane bond-containing compound having one or more isocyanate groups at the molecular ends, (B) an active organic resin such as polymethylene diamine or metaphenylene diamine, and (C) a perfume such as citronellol or geraniol. The content of the component C is preferably 2-95 pts.wt. per 100 pts.wt. of the component A.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition containing a fragrance as an active ingredient and curing at room temperature.

0002

BACKGROUND OF THE INVENTION Various gel compositions containing fragrances as active ingredients and using various gelling agents are used as fragrances and the like. Among such gel compositions, aqueous gel compositions use water-absorbing polymers such as polyvinyl alcohol, natural polymers such as carrageenan and agar, or metal soaps such as sodium stearate as gelling agents.
It was manufactured by heating and dissolving the active ingredient and gelling agent, and then cooling and solidifying the uniform mixture. For example, JP-A-62-152464, JP-A-62-152465
JP-A-56-89261 discloses a method using carrageenan as a gelling agent, and JP-A-56-89261 discloses a method using sodium stearate as a gelling agent. On the other hand, as a method that does not require a heating step, there is a technique in which a composition containing a volatile substance and an isocyanate compound is prepared, and the isocyanate compound in the composition is cured at room temperature to obtain a gel composition. Japanese Patent Application Publication No. 5
7-166168, and a technique using photopolymerization is disclosed in JP-A-63-66931.

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 Japanese Patent Application Laid-Open No. 152464 and Japanese Patent No. 62-152465, or sodium stearate etc. as disclosed in Japanese Patent Application Laid-open No. 56-89261. When used as a gelling agent, heating must be performed when dissolving and mixing the gelling agent in an aqueous solution containing the active ingredient, which may cause volatile active ingredients to evaporate or deteriorate. There were problems such as

On the other hand, when an isocyanate compound is used as disclosed in JP-A-57-166168, heating is not necessary, but isocyanate compounds are highly toxic and therefore difficult to handle. Moreover, there was a problem that the composition after curing had strong water absorption and was unstable. Further, with the method using photopolymerization, such as the method disclosed in JP-A No. 63-66931, there was a problem in that thick products could not be manufactured.

The present invention solves the above-mentioned problems, that is, it does not require heating during its production, there is no problem of toxicity, and it is possible to produce thick products. The purpose of the present invention is to provide a room-temperature-curable epoxy resin composition containing a fragrance, which is a cured product having the following properties, and which also has the feature that almost the entire amount of the fragrance can be utilized.

[0006]

[Means to solve the problem]

That is, the present invention provides a urethane-modified epoxy resin (A) obtained by reacting a compound having an epoxy group and a hydroxyl group with a urethane bond-containing compound having an isocyanate group at the terminal, an active organic curing agent (B
) and a fragrance (C).

The present invention will be explained in detail below. The urethane-modified epoxy resin (A) used in the present invention comprises a compound (x) having an epoxy group and a hydroxyl group, and a urethane bond-containing compound (y) having an isocyanate group at the terminal.
) is obtained by reacting with

[0009] Here, the urethane bond-containing compound (y) having an isocyanate group at the end is obtained by reacting a polyhydroxyl compound (y1) and a polyisocyanate compound (y2). The urethane bond-containing compound (y) is not particularly limited as long as it is as described above.

The compound (x) having an epoxy group and a hydroxyl group is a compound having 1 to 3 epoxy groups and 1 to 2 hydroxyl groups in the molecule, such as glycidol, ethylene glycol monoglycidyl ether, , glycidyl ethers of polyhydric alcohols such as glycerin diglycidyl ether, and commercially available epoxy resins having hydroxyl groups. These compounds (x) may be used alone or in combination of two or more.

The urethane bond-containing compound (y) having an isocyanate group at the end is a polyhydroxyl compound (y
1) and a polyisocyanate compound (y2).

Examples of the polyhydroxyl compound (y1) include various polyether polyols or polyester polyols used in the production of general urethane compounds.

[0013] Polyether polyol is a product obtained by addition polymerizing one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran to a compound having two or more active hydrogens. It is. Here, 2
Examples of compounds having more than one active hydrogen include polyhydric alcohols, amines, alkanolamines, polyhydric phenols, etc. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, Diethylene glycol, glycerin, hexanetriol, trimethylolpropane, pentaerythritol, etc. are used as amines, ethylenediamine, hexamethylenediamine, etc. are used as alkanolamines, ethanolamine, propanolamine, etc. as polyhydric phenols. Examples include resorcinol and bisphenols.

[0014] Polyester polyols are condensates of polyhydric alcohols and polybasic carboxylic acids, condensates of hydroxycarboxylic acids and polyhydric alcohols, polymers of lactones, etc. Examples of polybasic carboxylic acids include adipic acid, glutaric acid, azelaic acid, fumaric acid, maleic acid, phthalic acid, terephthalic acid, dimer acid, Examples include pyromellitic acid.

Furthermore, as condensates of hydroxycarboxylic acids and polyhydric alcohols, castor oil, reaction products of castor oil and ethylene glycol, reaction products of castor oil and propylene glycol, etc. are also useful. Furthermore, the lactone polymer refers to a product obtained by ring-opening polymerization of ε-caprolactam, α-methyl-ε-caprolactam, ε-methyl-ε-caprolactam, etc. using a suitable polymerization initiator.

The polyisocyanate compound (y2) is a compound having two or more isocyanate groups in the molecule. In the present invention, various materials used in the production of ordinary polyurethane resins can be used, but for example, 2
, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthylene-1,5-diisocyanate, and hydrogenated compounds thereof, ethylene diisocyanate, propylene Diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1-methyl-2,4-
Diisocyanate cyclohexane, 1-methyl-2,6
-Diisocyanate Examples include cyclohexane, dicyclohexylmethane diisocyanate, triphenylmethane triisocyanate, and the like. These polyisocyanate compounds (y2) may be used alone or in combination of two or more.

The urethane-modified epoxy resin (A) is synthesized from the above-mentioned three types of raw materials, including the polyhydroxyl compound (y1) and polyisocyanate used in the synthesis of the urethane bond-containing compound (y) having an isocyanate group at the terminal. The quantitative ratio with compound (y2) is 1 hydroxyl group in polyhydroxyl compound (y1) per 1 isocyanate group in polyisocyanate compound (y2).
The number is preferably 0.95 to 0.75, more preferably 0.95 to 0.75.

[0018] Furthermore, the urethane bond-containing compound (y)
and a compound (x) having an epoxy group and a hydroxy group
The quantitative ratio in the reaction with urethane bond-containing compound (y)
The number of hydroxyl groups in the compound (x) having an epoxy group and a hydroxyl group is preferably one or more, more preferably 1.0 to 1.2 per isocyanate group in the compound (x).

Note that the above urethane-modified epoxy resin (
During the synthesis of A), a urethanization catalyst such as triethylamine, stannous octoate, dibutyltin dilaurate, etc. may be used as necessary.

In the present invention, any urethane-modified epoxy resin (A) obtained as described above may be used, but preferably an epoxy equivalent of 500 to 1
500 is used. This has an epoxy equivalent of 500
If it is less than that, the cured product will be difficult to exhibit sufficient rubber elasticity,
This is because if it exceeds 1,500, the fluidity itself becomes poor and workability decreases.

[0021] The urethane bond-containing compound (y) containing an isocyanate group at the end obtained in this way, and the above-mentioned compound containing an epoxy group and a hydroxyl group (
Compounds (urethane modified epoxy resins (A)-1 to 6) which are examples of urethane modified epoxy resins (A) obtained by reacting with urethane modified epoxy resins (A) are shown in Table 1 below. ) may be used alone or in combination of two or more.

[0022]

[Table 1]

The active organic curing agent (B) used in the present invention refers to various amine-based curing agents known as curing agents for epoxy resins.

Specifically, aliphatic polyamines such as polymethylene diamine and triethylenetetramine, aromatic polyamines such as metaphenylene diamine and diaminodiphenylmethane, alicyclic polyamines such as menthene diamine and isophorone diamine, polyamide resins, etc. Illustrated.

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

The essential components of the epoxy resin composition of the present invention are as described above, and their content ratios are not particularly limited, but the following ratios are preferred.

The ratio of the urethane-modified epoxy resin (A) to the active organic curing agent (B) is as follows: 1.0 of the epoxy group in the urethane-modified epoxy resin (A)
The amount ratio of active hydrogen in B) is preferably 0.5 to 1.0, more preferably 0.8 to 1.0. If the ratio of active hydrogen in the active organic curing agent (B) is less than 0.5 to 1.0 of the epoxy group in the urethane-modified epoxy resin (A), curing may be insufficient. ,1
．． If the quantity ratio exceeds 0, the pot life is too short, which may cause problems in workability.

The fragrance (C) is preferably 2 to 95 parts by weight, more preferably 3 to 50 parts by weight, based on 100 parts by weight of the urethane-modified epoxy resin (A). If it is less than 2 parts by weight, it is difficult to obtain sufficient aromatic properties, and if it exceeds 95 parts by weight, the reactivity between the urethane-modified epoxy resin (A) and the active organic curing agent (B) becomes low. , it becomes difficult to obtain a suitable cured product.

In addition to this, the epoxy resin composition of the present invention may contain commonly used additives such as diluents, plasticizers, anti-aging agents, pigments, fillers, A coloring agent, an antifoaming agent, a curing accelerator, a curing retardant, etc. may be included. Further, volatile substances other than perfumes, such as insect repellents, deodorants, attractants, repellents, etc., may be contained.

The epoxy resin composition of the present invention is a two-component type, and contains a urethane-modified epoxy resin (A) as a main component,
A fragrance (C), a liquid containing additives other than a curing accelerator and a curing retardant as necessary, and an active organic curing agent (B)
It consists of a two-part composition containing as a main component, and optionally additives such as an antifoaming agent and pigments that are not reactive with the active organic curing agent (B), as well as a curing accelerator or a curing retardant.

[0031] When using the epoxy resin composition of the present invention,
Mix the first and second parts in a predetermined ratio, degas if necessary, apply it to the master mold (forming the mold material) or inject it into the mold (molding the casting material), and then store at room temperature for 15 to 24 hours. It is sufficient to allow it to harden for about an hour.

[0032]

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

(Example 1) Urethane-modified epoxy resin (
To 100 parts by weight of (A)-1 in Table 1, 500 g of a raw material containing 3 parts by weight of an active organic curing agent (isophorone diamine) and 15 parts by weight of a rose-based blended fragrance was added at room temperature (20°C).
) for about 10 minutes, and a molded doll was obtained by a casting method. Curing was carried out by standing at room temperature for 18 hours. The obtained molded product has a softness that is pleasant to the touch, and
The scent was emitted continuously for more than three months.

(Example 2) Urethane-modified epoxy resin (
To 100 parts by weight of (A)-2 in Table 1, 300 g of a raw material containing 3 parts by weight of an active organic curing agent (isophorone diamine) and 20 parts by weight of an emerode fragrance was added at room temperature (20°C).
) for about 10 minutes, and a fish-shaped molded product was obtained by casting. Curing was performed by leaving it at room temperature for 15 hours. The obtained molded article continuously emitted aroma for more than 3 months.

[0035]

Effects of the Invention The present invention provides a room-temperature-curable epoxy resin composition that has excellent shelf life for its active ingredients and provides a cured product with elasticity. The room-temperature-curable epoxy resin composition of the present invention does not require a heating step during its production, and can be cured at room temperature. Therefore, the room-temperature-curable epoxy resin composition of the present invention is an aromatic agent containing a fragrance that is easily changed by heating as an active ingredient. Suitable for manufacturing etc. Further, since the cured product of the room temperature curable epoxy resin composition of the present invention has elasticity, a smooth feel can be obtained. Furthermore, in the cured product of the room-temperature-curable epoxy resin composition of the present invention, since the fragrance easily moves inside the cured product, almost the entire amount of the fragrance retained in the cured product can be effectively utilized. In addition, by using the room-temperature-curable epoxy resin composition of the present invention, a thick cured product can be obtained, so that it can be molded into a wider range of desired shapes.

Claims (2)

[Claims] Claim 1: A urethane-modified epoxy resin (A) obtained by reacting a compound having an epoxy group and a hydroxyl group with a urethane bond-containing compound having an isocyanate group at the end, an active organic curing agent (B), and a fragrance. (
A room temperature curable epoxy resin composition characterized by containing C). 2. The content of the fragrance (C) is 2 to 100 parts by weight based on 100 parts by weight of the urethane-modified epoxy resin (A).
The room temperature curable epoxy resin composition according to claim 1, which is 95 parts by weight.