JPH06116358A - Unsaturated epoxy ester resin - Google Patents

Abstract

PURPOSE:To obtain the subject resin capable of providing cured products excellent in heat and weather resistances and hardness by thermally reacting a specific epoxy resin with an unsaturated monocarboxylic acid in the presence of a reactional catalyst, etc. CONSTITUTION:The objective resin is obtained by thermally reacting (A) an epoxy resin prepared by epoxidizing a vinyl-containing resin obtained by reacting (i) a compound having one or more vinyl groups and one epoxy group in one molecule (preferably 4-vinylcyclohexene-1-oxide, etc.) with (ii) a polybasic acid anhydride, a polybasic acid, an acid-terminated polymer or a carboxylic acid-containing polymer and (iii) a compound having one or more active hydrogen atoms (e.g. alcohols, an OH-terminated polymer or an OH-containing polymer) with (B) an unsaturated monocarboxylic acid (a part or most of the unsaturated monocarboxylic acid, as necessary, is substituted with a saturated monocarboxylic acid, a polyfunctional carboxylic acid, a saturated polyfunctional carboxylic acid anhydride, etc.) in the presence of a reactional catalyst and, as necessary, a polymerization inhibitor, a solvent or a polymerizable monomer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an unsaturated epoxy ester resin which gives a cured product having excellent weather resistance and heat resistance.

[0002]

2. Description of the Related Art Unsaturated epoxy ester resins have been used in the past for their FRP resin, as a raw material for coating materials for woodworking, metal and plastics, taking advantage of their characteristics such as thermosetting and photocuring.
It is widely used as a resin for printing inks, a resin material for insulating coatings, and a sealant for electronic parts.

[0003]

The epoxy resin which is usually used is an epibis type epoxy resin synthesized from bisphenol A and epichlorohydrin, a novolac epoxy resin synthesized from novolac phenol and epichlorohydrin, and benzene is used in the molecular skeleton. It has a ring. A cured product of an unsaturated epoxy polyester resin obtained by using these epoxy resins has drawbacks such as poor weather resistance and lack of transparency due to the benzene ring.

Aliphatic epoxies, epoxidized vegetable oils and the like are used as other epoxy resins, but the heat resistance,
It has the drawback of lacking toughness.

Under the circumstances, the inventors of the present invention have studied, and as a result, by using the epoxy resin disclosed in Japanese Patent Application No. 04-083739, curing having excellent heat resistance, weather resistance and hardness. It was found that an unsaturated epoxy ester resin giving a product was obtained, and the present invention was completed.

Further, it has been clarified that the characteristics of the epoxy resin can be changed by giving various combinations of (a), (b) and (c) to be used, and a wide range of characteristics can be given.

[0007]

The present invention provides [A] (a)
A compound having one or more vinyl groups and one epoxy group in one molecule, and (b) a polybasic acid anhydride, a polybasic acid, an acid terminal polymer, and a polymer containing a carboxylic acid group. An epoxy resin obtained by further epoxidizing a resin having a vinyl group, which is obtained by reacting at least one selected from the compounds having at least one active hydrogen (c) with (c). B] Unsaturated monocarboxylic acid, or if necessary, part or most of the unsaturated monocarboxylic acid is saturated monocarboxylic acid, polyvalent carboxylic acid, saturated polycarboxylic anhydride, unsaturated polycarboxylic acid Acid, unsaturated polycarboxylic acid anhydride, or saturated alkyd having a terminal carboxyl group, or one or more of them may be substituted to form a reaction catalyst and, if necessary, a polymerization inhibitor, a solvent or a heavy polymer. The present invention relates to an unsaturated epoxy ester resin obtained by heating and reacting in the presence of a compatible monomer.

Next, the present invention will be described in more detail.

First, (a) in the component [A] used in the present invention
A compound having one epoxy group and one or more vinyl groups in one molecule has the general formula (IV) << i is an integer of 1 to 5, R ¹ and R ⁴ are hydrogen atoms or an alkyl group having 1 to 50 carbon atoms or a substituted phenyl group,
R ² and R ³ are each a hydrogen atom or an alkyl group having 1 to 50 carbon atoms, and R ² and R ³ may be wrapped around a ring.

Examples of the compound represented by the general formula (IV) are the following compounds. 4-vinylcyclohexene-1-oxide, 5-vinylbicyclo [2.
2.1] hept-2-ene-2-oxide, limonene monoxide, trivinylcyclohexane monoxide,
Compounds represented by the general formula (I) such as divinylbenzene monoxide, butadiene monoxide and 1,2-epoxy-9-decene; compounds represented by the general formula (II) such as allyl glycidyl ether; Examples include compounds such as glycidyl styryl ether.

Further, the following compounds can also be used.

[0012]

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4] These may be used alone or in combination of two or more.

If necessary, ethylene oxide,
Monoepoxides such as propylene oxide, cyclohexene oxide, styrene oxide, and α-olefin epoxide, and diepoxides such as vinylcyclohexene dioxide and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate are contained in the above molecule. You may use together with the compound which has one epoxy group and one or more vinyl groups.

Further, the polybasic acid anhydride or polybasic acid (b) used in the present invention includes aromatic polybasic acid and its acid anhydride, and aliphatic polybasic acid and its acid anhydride. Examples of aromatic polybasic acids and acid anhydrides thereof include:
Examples include phthalic anhydride, isophthalic acid, terephthalic acid and trimellitic anhydride. Examples of the aliphatic polybasic acid and its acid anhydride include tetrahydrophthalic acid, 4-methylhexahydrophthalic acid, hexahydrophthalic acid, adipic acid, maleic acid, and their acid anhydrides, fumaric acid and sebacic acid. , Dodecane diacid, and their acid anhydrides.

The acid-terminated polymer used in the present invention is an acid-terminated polymer obtained by reacting a polybasic acid with polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polycyclohexene glycol, polyvinyl cyclohexene glycol or the like. Examples include ethers, acid-terminated polyesters, acid-terminated polybutadienes and acid-terminated polycaprolactones.

Further, an acrylic copolymer having a carboxylic acid group can be used instead of the acid terminal polymer, and it contains a polybasic acid anhydride, a polybasic acid, an acid terminal polymer, and a carboxylic acid group. These polymers may be used alone or in combination of two or more.

Next, as the compound (c) having active hydrogen used in the present invention, alcohols, phenols, carboxylic acids, amines, thiols, hydroxyl group-terminated polymers, and hydroxyl groups can be used. The polymer etc. which are contained are mentioned.

The alcohols are monovalent, divalent, trivalent or higher, and include, for example, methanol, ethanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, Examples thereof include butanediol, hexanediol, glycerin, butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerol, triglycerol and the like. In addition, neopentyl glycol, neopentyl glycol ester of hydroxyhyvalic acid, dipentaerythritol,
1,4-cyclohexanedimethanol, trimethylpentanediol, 1,3,5-tris (2-hydroxyethyl) cyanuric acid, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, etc. Can also be used.

Examples of the phenols are phenol, cresol, catechol, pyrogallol, hydroquinone,
Hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, ethylene oxide adduct of bisphenol A, propione oxide adduct of bisphenol A, phenol Resin and cresol-novolak resin.

Examples of the hydroxyl group-terminated polymer used in the present invention include polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polycyclohexene glycol and polyvinyl cyclohexene glycol, hydroxyl group terminated polyesters, hydroxyl group terminated polybutadiene, Examples include hydroxyl-terminated polycaprolactone and polycarbonate diol.

Further, an acrylic copolymer having a hydroxyl group can be used instead of the hydroxyl-terminated polymer.

The carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecane diacid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid. Acid, terephthalic acid, etc.

Further, compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid and oxycaproic acid, can also be mentioned.

The amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine,
Examples include octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine and ethanolamine.

As the thiols, methyl mercaptan,
Mercapto such as ethyl mercaptan, propyl mercaptan, phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol ester of mercaptopropionic acid, for example, ethylene glycol dimercaptopropionic acid ester, trimethylolpropane trimercaptopropionic acid, pentaerythritol pentamercaptopropionic acid Etc.

Further, as the compound having active hydrogen, polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, Styrene-maleic acid copolymer resin, alkyd resin, polyester polyol resin,
Examples include polyester carboxylic acid resins, polycaprolactone polyol resins, polypropylene polyols, polytetramethylene glycol, and the like.

The compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples thereof include allyl alcohol, acrylic acid, methacrylic acid,
There are 2-hydroxyethyl methacrylate, 3-cyclohexenemethanol, tetrahydrophthalic acid and the like.

Any compound can be used as long as it is a compound having these active hydrogens, and two or more kinds thereof may be mixed.

The epoxy resin used in the present invention includes the compound (a) having at least one vinyl group and one epoxy group in the above molecule, a polybasic acid anhydride, a polybasic acid, and an acid terminal polymer. , And a resin having a vinyl group obtained by reacting at least one selected from the polymer (b) containing a carboxylic acid group and at least one selected from the compound (c) having active hydrogen. Further, it is obtained by epoxidizing with an epoxidizing agent.

The starting materials (a), (b), and (c) are charged in proportions of 1 to 99 parts by weight of (a), preferably 30 to 80 parts, and 99 to 1 parts by weight of (b). Parts, preferably 20 to 70 parts, and 0 to 99 parts by weight of (c), preferably 0 to 30 parts. The component (c) may not be used depending on the case. When the component (c) is not used,
It is necessary to control the molecular weight while detecting the dehydration amount by controlling the reaction time, the degree of reduced pressure, the reaction temperature, and the like.

When the amount of component (a) used is relatively small, the epoxy group content in the target epoxy resin is small. The molar ratio of component (a) / component (b) is 0.
It is 4 to 5.0, preferably 0.5 to 3.0.

When the ratio of the component (a) is high, the ratio of terminal hydroxyl groups increases, and when the terminal hydroxyl group and the terminal carboxyl group are present, all terminals become hydroxyl groups as the dehydration reaction proceeds.

On the contrary, when the ratio of the component (b) is increased, the ratio of the terminal to be the carboxyl group is increased, and in the case where the hydroxyl group end and the carboxyl group end are present, all the terminals become the carboxyl group as the dehydration reaction proceeds. Become. However,
When the ratio of the component (a) increases, a part of the component (a) remains unreacted and remains. Further, if the ratio of the component (b) becomes unnecessarily large, the component (b) remains without reacting.

In the reaction for synthesizing the resin having a vinyl group, a catalyst for promoting the ring-opening reaction of the epoxy group by the carboxyl group and, if necessary, a catalyst for promoting the (dehydration) esterification reaction may be used in combination. Good. .

As the catalyst for promoting the ring-opening reaction of an epoxy group with a carboxyl group which can be used in the present invention, a tertiary amine such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine, tri-n-octylamine, or tetramethylammonium chloride is used. , Quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide, alkylureas such as tetramethylurea, and alkylguanidines such as tetramethylguanidine.

The catalyst for promoting the ring-opening reaction that can be used in the present invention may be used alone or in combination of two or more kinds. This catalyst is 0.1 to 5.0 relative to the epoxy compound.
%, Preferably 0.5 to 3.0% by weight. This ring-opening reaction is carried out at 50 to 200 ° C., preferably 1
Perform at 00-180 ° C.

Examples of the catalyst for promoting the (dehydration) esterification reaction that can be used in the present invention include Sn compounds such as tin octylate and dibutyltin laurate, and Ti compounds such as tetrabutyl titanate.

The catalyst for promoting the (dehydration) esterification reaction used in the present invention may be used alone or in combination of two or more kinds. This catalyst is 0-100 with respect to the reaction system.
It is recommended to use 0 ppm, preferably 50 to 500 ppm. This (dehydration) esterification reaction is 180 to 240 ° C.
Done in.

The epoxy group ring-opening reaction with a carboxyl group and the (dehydration) esterification reaction may be carried out sequentially, but after the raw materials and the catalyst have been charged all at once, the reaction temperature is raised stepwise according to the progress of the reaction. Method is preferred. If necessary, after the component (c) and the catalyst are charged at once,
The components (a) and (b) may be dropped.

Now, the epoxy resin of the present invention is synthesized by allowing an epoxidizing agent to act on the resin having a cyclic olefin or vinyl group thus synthesized.
Examples of the epoxidizing agent that can be used include peracids and hydroperoxides.

Examples of peracids include formic acid, peracetic acid, perbenzoic acid and trifluoroperacetic acid. Of these, peracetic acid is a preferred epoxidizing agent because it is industrially produced in large quantities, is inexpensively available, and has high stability. A catalyst may be used in the epoxidation, if necessary. For example, in the case of peracid, alkali such as sodium carbonate or boric acid such as sulfuric acid can be used as a catalyst.

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature depending on the equipment and the physical properties of the raw materials. The reaction temperature range is determined by the reactivity of the epoxidizing agent used, but when it comes to peracetic acid, which is a preferred epoxidizing agent,
70 ° C is preferred. The reaction is slow at 0 ° C or lower, and the decomposition of peracetic acid occurs at 70 ° C or higher.

The solvent can be used for the purpose of reducing the viscosity of the raw material and stabilizing it by diluting the epoxidizing agent. In the case of peracetic acid, aromatic compounds, ethers, esters and the like can be used.

The charged molar ratio of the epoxidizing agent to the unsaturated bond can be changed according to the purpose such as the amount of the unsaturated bond to be left. When a compound having a large number of epoxy groups is intended, the epoxidizing agent is preferably added in an equimolar amount or more with respect to the unsaturated group. However, it is usually disadvantageous to exceed 2 times the molar amount in view of economical efficiency and side reactions, and in the case of peracetic acid, 1 to 1.5 times the molar amount is preferable.

The composition of interest can be removed from the reaction crude liquid by chemical engineering means such as concentration.

The epoxy resin used in the present invention can be used as a mixture with another epoxy resin as long as the characteristics of the composition are not impaired. Here, the other epoxy resin may be any as long as it is generally used,
Examples include epibis-type epoxies, bisphenol F epoxies, novolac epoxies, cycloaliphatic epoxies and epoxy diluents such as styrene oxide and butylglycidyl ether.

Next, as the unsaturated monocarboxylic acid which is the [B] component of the unsaturated epoxy ester resin of the present invention, acrylic acid, methacrylic acid, crotonic acid and the like are generally used. In addition, a saturated monocarboxylic acid, a saturated polycarboxylic acid, a saturated polycarboxylic acid anhydride, or an unsaturated polycarboxylic acid that partially or most replaces the unsaturated carboxylic acid which is one component in [A] As the unsaturated polycarboxylic acid anhydride, acetic acid, benzoic acid, maleic anhydride, phthalic acid,
Examples thereof include phthalic anhydride, succinic acid, adipic acid, hexahydrophthalic anhydride, pyromellitic dianhydride, and one or more selected from these may be used.

The "part" in the present invention may vary depending on the unsaturated carboxylic acid and the saturated carboxylic acid used, and if 0.1% by weight or more is added, a substitution effect can be expected. The purpose of substitution is to modify the unsaturated epoxy ester for various applications.

The saturated or unsaturated alkyd having a carboxyl group at the terminal is an alkyd having a terminal carboxyl group obtained by a dehydration condensation reaction between a polyvalent alcohol and a polycarboxylic acid.

The reaction molar ratio of these carboxylic acid and the epoxy compound is possible if the total of the carboxyl groups of the carboxylic acid is 0.1 mol or more per 1 mol of the epoxy group, but it is in the preferable range from the viewpoint of curability and performance. Is 0.2 to 2 mol.

Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone and methoxyhydroquinone.

The polymerizable monomer is methylmethacrylate.
, Hydroxylethyl methacrylate, styrene, vinyltoluene, ethylene glycol diacrylate, trimethylolpropane triacrylate and the like. The amount used is about 10 to 80% by weight based on the starting material.

Solvents include benzene and ethyl alcohol
, Ethyl acetate, toluene, ethyl cellosolve, etc., and are used alone or in combination. The amount used is about 10 to 80% by weight based on the starting material.

The epoxy compound and the carboxylic acid are heated and reacted in the presence of these, and the reaction temperature is generally 50.
It is carried out at ˜130 ° C., preferably 80˜120 ° C.

The unsaturated epoxy ester resin of the present invention obtained as described above gives a cured product having excellent heat resistance and weather resistance and can be used in a very wide range.

The present invention will be described in detail below with reference to examples.

Claims (11)

[Claims] 1. [A] (a) a compound having at least one vinyl group and one epoxy group in one molecule, and (b) a polybasic acid anhydride, a polybasic acid, an acid terminal polymer, And at least one selected from polymers containing a carboxylic acid group,
(C) An epoxy resin obtained by further epoxidizing a resin having a vinyl group obtained by reacting at least one selected from compounds having one or more active hydrogens, and [B] an unsaturated monocarboxylic acid. Or, if necessary, a part or most of the unsaturated monocarboxylic acid is a saturated monocarboxylic acid, a polyvalent carboxylic acid, a saturated polycarboxylic anhydride, an unsaturated polycarboxylic acid, an unsaturated polyhydric anhydride. Substitute with one or more selected from carboxylic acids and saturated alkyds having terminal carboxyl groups, and heat in the presence of a reaction catalyst and, if necessary, a polymerization inhibitor, solvent or polymerizable monomer. Unsaturated epoxy ester resin obtained by reaction. 2. The unsaturated epoxy ester resin according to claim 1, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is 4-vinylcyclohexene-1-oxide. 3. The compound having one or more vinyl groups and one epoxy group in one molecule is 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide. 1 unsaturated epoxy ester resin. 4. The unsaturated epoxy ester resin according to claim 1, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is limonene monoxide. 5. A compound having at least one vinyl group and one epoxy group in one molecule is represented by the following general formula (I): The unsaturated epoxy ester resin according to claim 1, which is a compound represented by << n is an integer of 0 to 30 >>. 6. A compound having one or more vinyl groups and one epoxy group in one molecule is represented by the following general formula (II): The unsaturated epoxy ester resin according to claim 1, which is a compound represented by << n1 and n2 are integers from 0 to 30 >>. 7. A compound having at least one vinyl group and one epoxy group in one molecule is represented by the following general formula (III): The unsaturated epoxy ester resin according to claim 1, which is a compound represented by << Ph is a substituted phenyl group and n is an integer of 0 to 30. 8. A compound having one or more active hydrogens,
The unsaturated epoxy ester resin according to claim 1, which is a polymer containing an alcohol, a hydroxyl group-terminated polymer, and a hydroxyl group. 9. The unsaturated epoxy ester resin according to claim 1, wherein the acid-terminated polymer is an acid-terminated polyester. 10. The unsaturated epoxy ester resin according to claim 8, wherein the hydroxyl-terminated polymer is a hydroxyl-terminated polyester. 11. The unsaturated epoxy ester resin according to claim 8, wherein the hydroxyl group terminated polymer is a hydroxyl group terminated polyether.