JPH08208805A - Polyol resin composition - Google Patents

Abstract

PURPOSE: To obtain a polyol resin composition soluble in a highly safe, high boiling point and low irritative solvent, terpene, capable of forming coating films excellent in corrosion resistance, water resistance, etc., and good in adhesion to various substrates, and useful for coatings, etc., by using an epoxy resin having a terpene phenol structure skeleton in the structure. CONSTITUTION: This resin is obtained by addition-reacting (B) an active hydrogen-containing compound having an active hydrogen reactive with an epoxy group to (A) an epoxy resin having an epoxy equivalent of 200-10000 and having a terpene phenol structure skeleton obtained by adding a (alkyl) phenol compound to a cyclic terpene compound. The component A is preferably the addition reaction product of (i) a polyglycidyl ether consisting of either of a mono(poly)nuclear polyhydric phenol polyglycidyl ether and an aliphatic polyglycidyl ether, concretely, an alkylidenebisphenol polyglycidyl ether of the formula (R1 , R2 are H, alkyl; m is 0-2), to (ii) a terpene phenol compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a highly safe high boiling point
A polyol resin composition which is soluble in a terpene (terpene hydrocarbon oil) which is a mild solvent and which can give a coating film having excellent corrosion resistance, curability and adhesion to various substrates. Is.

[0002]

2. Description of the Related Art A polyol resin obtained by adding an active hydrogen compound such as a secondary amine to an epoxy resin is used as a curing agent with polyisocyanate to provide anticorrosion properties and a base group. It is known to form a film with excellent adhesiveness to materials, and in particular, it is obtained from a high-molecular-weight epoxy resin in which a polyhydric phenol is subjected to an addition reaction with a low-molecular-weight epoxy resin to extend the chain Polyol resins are widely used as paints, adhesives, etc. because they have excellent adhesiveness to various base materials, heat resistance, chemical resistance, electrical properties, mechanical properties, and the like.

When used for these purposes, conventionally, a solvent type solvent dissolved in various low boiling point solvents has been generally used, but there is a risk of fire, harmfulness to human body, adverse effect on global environment, etc. Therefore, the use of low boiling point solvents has come to be restricted, and there has been a strong demand for reduction of solvent (high solidification) or switching to a high boiling point and low stimulant solvent such as terpen.

However, the conventional polyol resins have insufficient solubility in organic solvents or various concomitant agents, making it difficult to form a high solid and having a high viscosity of the solution, resulting in poor workability. . Further, since a cured product using a conventional polyol resin is poor in flexibility, its use is greatly restricted when it is used as a paint.

JP-A-58-7557 and JP-A-59-56460 disclose addition products of diglycidyl ethers of alkylene oxide adducts of dihydric phenols with active hydrogen-containing compounds or dihydric phenols. It has been proposed to use an addition product of a high molecular weight epoxy resin in which a diglycidyl ether of an alkylene oxide adduct is chain-extended with a divalent carboxylic acid and an active hydrogen-containing compound, but these polyol resin compositions are anticorrosive. Although it has been improved to some extent in terms of water resistance and low-temperature curability, it is not practically satisfactory because its solubility in a high boiling point, mild solvent such as terpen is insufficient.

Therefore, an object of the present invention is to provide a polyol resin composition which is soluble in turpentine and is excellent in corrosion resistance, water resistance, heat resistance, chemical resistance, electrical characteristics, mechanical characteristics and adhesion to various substrates. To provide.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an epoxy resin having a terpene phenol structure skeleton in its structure is used as an epoxy resin as a raw material used for producing a polyol resin. It was found that the above-mentioned objects can be achieved by using them.

The present invention was made based on the above findings, and has an epoxy equivalent of 200 to 1 having a terpene phenol structural skeleton obtained by adding a phenol or an alkylphenol compound to a (A) cyclic terpene compound.
The present invention provides a polyol resin composition obtained by adding (B) an active hydrogen-containing compound having one active hydrogen having reactivity with an epoxy group to an epoxy resin of 0000.

The polyol resin composition of the present invention will be described in detail below.

Examples of the epoxy resin having a terpene phenol structural skeleton which is the component (A) used in the present invention include (A-1) mononuclear polyhydric phenol compounds, polynuclear polyhydric phenol compounds and polyhydric alcohols. Polyglycidyl ether compound; glycidyl ester compound such as glycidyl ester of polybasic acid or polymer of glycidyl methacrylate; epoxy compound having glycidyl amino group; epoxidized natural oil and fat; epoxidized cyclic olefin compound; epoxidized conjugated diene polymer; An addition reaction product of an epoxy compound such as a heterocyclic epoxy compound and a phenol compound having a terpene structure skeleton, (A
-2) Addition reaction of a polyglycidyl ether compound of a terpene structure skeleton-containing bisphenol compound obtained by adding 2 moles of phenol or an alkylphenol to a cyclic terpene compound or a polyglycidyl ether compound of the terpene structure skeleton-containing bisphenol compound and a bisphenol compound or dicarboxylic acid Products.

Examples of the polyglycidyl ether compound in the above (A-1) include mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, methylresorcin, pyrocatechol and phloroglucinol; dihydroxynaphthalene, biphenol, methylenebisphenol ( Bisphenol F), methylenebis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl)
Butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac,
Polynuclear polyphenol compounds such as orthocresol novolac and resorcinol novolac; ethylene glycol,
Examples thereof include polyglycidyl ethers of polyhydric alcohols such as propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-ethylene oxide adduct.

Examples of the glycidyl ester compound in the above (A-1) include maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid,
Adipic acid, azelaic acid, sebacic acid, dimer acid,
Trimer acid, phthalic acid, isophthalic acid, terephthalic acid,
Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid and endomethylenetetrahydrophthalic acid, and homopolymers of glycidyl methacrylate Alternatively, a copolymer or the like can be used.

The epoxy compound having a glycidylamino group in the above (A-1) is, for example,
Examples thereof include N, N-diglycidylaniline and bis (4- (N-methyl-N-glycidylamino) phenyl) methane.

The epoxidized natural fats and oils, epoxidized cyclic olefin compounds, epoxidized conjugated diene polymers and heterocyclic epoxy compounds in the above (A-1) include epoxidized soybean oil, epoxidized linseed oil and epoxy. Safflower oil, epoxidized natural oils and fats such as epoxidized tall oil, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy- 6-Methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, epoxidized cyclic olefin compounds such as bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, epoxidized polybutadiene, and epoxy Sheet styrene - epoxidized conjugated diene polymer such as butadiene copolymer, heterocyclic compounds such as triglycidyl isocyanurate and the like.

Among the epoxy resins as the component (A-1), at least one selected from the group consisting of mononuclear polyhydric phenols or polyglycidyl ethers of polynuclear polyhydric phenols and aliphatic polyglycidyl ethers. When using polyglycidyl ether, among others,
When a polyglycidyl ether of alkylidene bisphenol represented by the general formula of the following [Chemical formula 2] (the same as the above-mentioned [Chemical formula 1]) is used, a polyol resin composition having excellent corrosion resistance and adhesion to a substrate is obtained. It is preferable because it is possible.

[0016]

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In the above formula, the alkyl group represented by R ₁ and R ₂ is an alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, heptyl and octyl. Can be given.

The terpene structure skeleton-containing phenol compound used for obtaining the component (A-1) or the terpene structure skeleton-containing bisphenol compound used for obtaining the component (A-2) is It is obtained by adding an alkylphenol compound such as phenol or orthocresol to a cyclic terpene compound, and examples thereof include compounds represented by the following chemical formulas (1) to (5).

[0019]

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The epoxy resin having the terpene phenol structure skeleton, which is the component (A), has the above-mentioned (A-1).
Addition reaction product of the above-mentioned epoxy compound which is a component and a terpene structure skeleton-containing phenol compound [for example, a compound represented by the above chemical formulas (4) and (5)] or a terpene structure skeleton which is the above-mentioned component (A-2) A bisphenol compound-containing [eg, a compound represented by the chemical formula (1) to (3) above] or a polyglycidyl ether thereof or an addition reaction product thereof with a bisphenol compound or a dicarboxylic acid is preferable, and a terpene structure-containing phenol compound is contained. It is preferable that the structural unit derived from is contained in an amount of 5% by weight or more, particularly 10% by weight or more. When the content of the structural unit derived from the terpene structure skeleton-containing phenol compound is less than 5% by weight, the solubility in terpenes may be insufficient.

In order to adjust the content of the structural unit derived from the terpene structure skeleton-containing phenol compound to the above preferable range (5% by weight or more), in the case of the above component (A-1), the epoxy compound For one epoxy group,
The ratio of the phenolic hydroxyl groups of the terpene structure skeleton-containing phenol compound to be preferably 0.05 to 0.8, more preferably 0.1 to 0.7, particularly, the monophenol compound is used as the terpene structure skeleton-containing phenol compound. In this case, it is desirable to react at a ratio of preferably 0.1 to 0.5. In addition, when the addition reaction product of the polyglycidyl ether of the terpene structure skeleton-containing bisphenol compound and the bisphenol compound or the dicarboxylic acid is used among the components (A-2),
The epoxy group of the polyglycidyl ether compound may be reacted with the phenolic hydroxyl group of the bisphenol compound or the carboxyl group of the dicarboxylic acid at a ratio of preferably 0.8 or less, more preferably 0.7 or less. desirable.

The epoxy resin having the terpene phenol structure skeleton, which is the component (A), is as described above.
It can be obtained by reacting an epoxy compound with a phenol compound or a carboxylic acid, and the reaction method can employ a conventional method of adding a phenol compound or a carboxylic acid to an epoxy resin, such as dimethylbenzylamine. In the presence of a basic catalyst, both 60
A method of heating to 200 ° C or the like can be used.

The epoxy resin having the terpene phenol structure skeleton which is the component (A) has an epoxy equivalent of 200 to 10,000, preferably 500 to 400.
When the epoxy equivalent is less than 200, the molecular weight of the obtained polyol resin becomes too small and the mechanical properties of the cured film become insufficient. Has insufficient low temperature curability.

The active hydrogen-containing compound having one active hydrogen having reactivity with an epoxy group, which is the component (B) used in the present invention, includes secondary amine compounds and compounds having a carboxyl group. Especially, a compound having an alcoholic hydroxyl group as a substituent is preferable.

Examples of the secondary amine compound include dialkylamine compounds such as dibutylamine and dioctylamine; alkanolamine compounds such as methylethanolamine, butylethanolamine, diethanolamine, diisopropanolamine and dimethylcyaminopropylethanolamine. Heterocyclic amine compounds such as morpholine, piperidine, 4-methylpiperazine and the like are preferable, and in particular, when an alkanolamine compound is used, a polyol resin composition having excellent properties can be obtained, which is preferable.

Examples of the compound having a carboxyl group include acetic acid, propionic acid, 2,2-dimethylolpropionic acid, lactic acid, butyric acid, octylic acid, lauric acid, benzoic acid, toluic acid, cinnamic acid, phenylacetic acid, Examples thereof include aliphatic, aromatic or alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, and particularly excellent properties when a carboxylic acid having an alcoholic hydroxyl group such as 2,2-dimethylolpropionic acid and lactic acid is used. It is preferable because a polyol resin composition can be obtained.

In the present invention, the reaction ratio of the epoxy resin having the terpene phenol structure skeleton as the component (A) and the active hydrogen-containing compound as the component (B) is one epoxy group of the epoxy resin. On the other hand, the number of active hydrogens in the active hydrogen-containing compound is preferably 0.7.
It is used in a ratio of 0.1 to 1.1, and more preferably 0.9 to 1.0. If the number of active hydrogen is less than 0.7 per one epoxy group, a large amount of unreacted epoxy groups will remain in the polyol resin composition,
On the other hand, if the number exceeds 1.1, the unreacted active hydrogen compound remains, which is not only wasteful but also may adversely affect the characteristics of the coating when a cured coating is formed.

In the present invention, a method of reacting the epoxy resin having the terpene phenol structure skeleton, which is the above-mentioned component (A), with the active hydrogen-containing compound, which is the above-mentioned component (B), includes the epoxy resin containing active hydrogen Conventional methods for adding compounds can be employed. For example, a method of heating both at 60 to 200 ° C. and reacting for 3 to 10 hours in the presence of a catalyst such as dimethylbenzylamine can be used.

The polyol resin composition of the present invention contains a polyol resin obtained by adding the component (B) to the component (A) as a main component.

Further, the polyol resin composition of the present invention comprises
Generally, a curing agent is blended and used for applications such as paints and adhesives.

As the above-mentioned curing agent, any curing agent which is usually used as a curing agent for a polyol resin can be used without particular limitation, and particularly, an average of more than 1 isocyanate in the molecule can be used. It is preferable to use a polyisocyanate compound having a group. Therefore, the polyol resin composition of the present invention is preferably used as a coating resin composition when used together with a polyisocyanate compound.

As the above polyisocyanate compound,
For example, phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate,
4,4'-diphenylmethane diisocyanate, 2,
4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, dianisidine diisocyanate, metaxylylene diisocyanate, hexamethylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, etc. are used alone. Alternatively, two or more kinds may be appropriately mixed and used. Further, a high molecular weight polyisocyanate (prepolymer) having an isocyanate group at the terminal such as an adduct of a polyhydric alcohol such as ethylene glycol, polyethylene glycol, polypropylene glycol or trimethylolpropane with the above polyisocyanate compound
Can also be used.

The above-mentioned curing agent is used so that the number of isocyanate groups in the polyisocyanate compound is preferably 0.4 to 1.2, more preferably 0.7 to 1.0 per hydroxyl group of the polyol resin. To be done. When the number of isocyanate groups in the polyisocyanate compound is less than 0.4 per one hydroxyl group of the polyol resin, a large amount of unreacted hydroxyl groups remain, which may result in insufficient mechanical properties of the cured film. Not only is there
Water resistance may be adversely affected. Further, if the number of isocyanate groups in the polyisocyanate compound exceeds 1.2 per hydroxyl group of the polyol resin, not only it is wasteful, but also foaming may occur.

When used as a coating material, the polyol resin composition of the present invention usually contains a solvent for dissolving the polyol resin composition of the present invention and the curing agent. The polyol resin composition of the present invention is soluble in terpene, which is a highly safe and high boiling point / low irritation solvent, that is, turpentine oil, D-limonene, pinene, etc.
Although these have a feature that they can be used as a diluting solvent, other general solvents, for example, commercially available high-boiling point hydrocarbon solvents can also be used. The high boiling hydrocarbon solvent may be aliphatic, alicyclic, aromatic or a mixture thereof, or may be a single composition such as xylene or mesitylene. Further, instead of a part or all of the high boiling hydrocarbon solvent, acetone, toluene, methyl ethyl ketone, ethyl acetate, propylene glycol monoethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, ethyl acetate Etc. can be used, and these solvents can be optionally used as a mixed solvent of two or more kinds.

Further, the polyol resin composition of the present invention may contain other polyol compounds, curing catalysts, monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar, etc., if necessary or not. Reactive diluent (plasticizer),
Glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, fine powder silica, titanium dioxide,
Carbon black, graphite, iron oxide, fillers or pigments such as bituminous substances, thickeners, thixotropic agents, flame retardants, may contain conventional additives such as defoaming agents, further, xylene resin, Adhesive resins such as petroleum resins can also be used in combination.

When the polyol resin composition of the present invention is used as a paint, the method for preparing the paint is a conventional method, in which desired additives such as fillers are added to the polyol resin composition, glass beads are added, and a predetermined amount is added. The method of kneading with a time shaker etc. is mentioned. A coating film can be formed by mixing the obtained coating material with a curing agent, applying it with a predetermined film thickness using a bar coater or the like, and drying and curing it.

[0037]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. In the examples, “parts” means “parts by weight” unless otherwise specified, and the epoxy equivalent is defined as the molecular weight of the epoxy resin per one epoxy group, and the phenolic OH equivalent is per one phenolic hydroxyl group. Is defined by the molecular weight of the phenol compound, the alcoholic OH equivalent is defined by the molecular weight of the polyol resin composition per one alcoholic hydroxyl group in the polyol resin composition, and the hydroxyl value (OHV) is 1 g of the polyol resin composition. It is defined as the number of mg of potassium hydroxide required to neutralize the alcoholic hydroxyl groups in the solution.

First, a production example (preparation examples 1 to 7) of the above-mentioned terpene phenol structure skeleton-containing epoxy resin which is the component (A) and a production example of a terpene phenol structure skeleton-free epoxy resin (comparative production example 1). Show.

Production Example 1 (Production of epoxy resin containing terpene phenol structure skeleton) Adeka Resin EP-4901 (manufactured by Asahi Denka Kogyo KK; Bisphenol F) was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling tube and a nitrogen inlet. Type epoxy resin, epoxy equivalent 175) 144.0 parts, terpene phenol copolymer YP-90LL (Yasuhara Chemical Co., Ltd., average molecular weight 266, phenolic OH equivalent 300) 26.6 parts (phenolic per epoxy group) Hydroxyl group 0.11
) And dimethylbenzylamine 0.17 as catalyst
Was charged and the temperature in the system was raised to 120 ° C., then 2.5
Reaction for time, epoxy equivalent 250, viscosity 133 ps /
An epoxy resin (TEP-1) containing a yellow liquid terpene phenol structure skeleton at 25 ° C. was obtained.

Production Example 2 (Production of epoxy resin containing terpene phenol structure skeleton) Adeka Resin EP-4100 (manufactured by Asahi Denka Kogyo KK; bisphenol) was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling tube and a nitrogen inlet. A-type epoxy resin, epoxy equivalent 190) 190.0 parts, terpene phenol copolymer YP-90LL 60.0 parts (0.20 phenolic hydroxyl groups per epoxy group), dimethylbenzylamine 0.39 parts as a catalyst Was charged, the temperature inside the system was raised to 120 ° C., and the reaction was carried out for 3 hours to obtain an epoxy equivalent of 35
0, a yellow liquid terpene structure skeleton-containing phenol-modified epoxy resin (TEP-2) having a viscosity of 4650 ps / 25 ° C.
I got

Production Example 3 (Production of Epoxy Resin Containing Terpene Phenol Structure Skeleton) In a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet, ADEKA RESIN EP-4100 (190 parts) and terpene phenol copolymer YP were prepared. -90LL 115 parts (phenolic hydroxyl group 0.38 per epoxy group) and dimethylbenzylamine 0.39 part as a catalyst were charged, the temperature in the system was raised to 120 ° C., and then the reaction was carried out for 3.5 hours, An epoxy resin (TEP-3) containing a terpene phenol structure skeleton as a yellow solid having an epoxy equivalent of 500 was obtained.

Production Example 4 (Production of epoxy resin containing terpene phenol structure skeleton) In a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet, ADEKA RESIN EP-4901 (150 parts) and ADEKA RESIN EP-4100, 80 were prepared. Part, a terpene diphenol copolymer YP-90 (Yasuhara Chemical Co., Ltd., average molecular weight 324, phenolic OH) containing a compound represented by the chemical formula (1) and / or (2) as a main component.
An equivalent weight of 162, a melting point of 85 ° C.) 150 parts (0.72 phenolic hydroxyl groups per epoxy group) and 0.34 part of dimethylbenzylamine as a catalyst were charged, and 120
After the temperature inside the system was raised to 0 ° C., the reaction was carried out for 4 hours to obtain a yellow solid terpene phenol structure skeleton-containing epoxy resin (TEP-4) having an epoxy equivalent of 1050.

Production Example 5 (Production of epoxy resin containing terpene phenol structure skeleton) A phenol novolac epoxy resin DEN-4 was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet.
31 (manufactured by Dow Chemical Company, average number of functional groups 2.
2, epoxy equivalent 175) 144 parts, terpene phenol copolymer YP-90LL 75 parts (phenolic hydroxyl group 0.38 per epoxy group) and dimethylbenzylamine 0.36 part as a catalyst were charged, and 120 ° C.
After the temperature of the system was raised to 5.5 hours, the reaction was performed for 5.5 hours to obtain a yellow solid terpene phenol structure skeleton-containing epoxy resin (TEP-5) having an epoxy equivalent of 480.

Production Example 6 (Production of epoxy resin containing terpene phenol structure skeleton) A reactor equipped with a thermometer, a stirrer and a cooling tube was charged with 162 parts of YP-90, 740 parts of epichlorohydrin and 1.1 parts of tetraethylammonium chloride. Plus 11
The mixture was heated to 7 ° C. and reacted under reflux for 2 hours. Then it is cooled to 60 ° C, a water separator is attached, and 42 parts of N
Add aOH, and under reduced pressure of 40-100 mmHg, 50-
The water generated during the reaction at 70 ° C. was azeotropically removed with epichlorohydrin and the reaction was carried out for 2 hours. Thereafter, the product was treated by a conventional method to obtain 196 parts of an epoxy resin (TEP-6) containing a terpene phenol structure skeleton having an epoxy equivalent of 233.

Production Example 7 (Production of epoxy resin containing terpene phenol structure skeleton) 66 parts of epoxy resin containing terpene phenol structure skeleton (TEP-4) was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet. , 18 parts of bisphenol A (0.57 phenolic hydroxyl groups per epoxy group) and 0.3 part of dimethylbenzylamine as a catalyst were added, and the mixture was reacted at 150 ° C. for 3 hours to obtain an epoxy-containing epoxy resin having an epoxy equivalent of 700. Resin (TEP
-7) was obtained.

Comparative Production Example 1 (Production of Terpene Phenol Structural Skeleton-Free Epoxy Resin) In a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet, 190 parts of ADEKA RESIN EP-4100 and 57 parts of bisphenol A ( 0.50 phenolic hydroxyl groups per epoxy group) and 0.39 part of dimethylbenzylamine as a catalyst were added, the temperature in the system was raised to 150 ° C., and the reaction was carried out for 3.5 hours to obtain an epoxy equivalent of 500. An epoxy resin (Comparative EP-1) was obtained.

Next, a polyol resin composition of the present invention (Examples 1 to 11) using the epoxy resin containing the terpene phenol structure skeleton (Production Examples 1 to 7) and a polyol resin composition having no terpene phenol structure skeleton The manufacturing method of the thing (Comparative Examples 1 and 2) is shown.

Example 1 (Production of Polyol Resin Composition) The terpene phenol structure skeleton-containing epoxy resin obtained in Production Example 1 was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet. (TEP-1) 125 parts,
67 parts of diisopropanolamine (1.0 active hydrogen per epoxy group) was charged, the temperature of the system was raised to 120 ° C., and then the reaction was performed for 5.5 hours, and a yellow solid terpene phenol structure skeleton-containing polyol resin Composition (C-
1) was obtained. The OHV of the obtained polyol resin composition was 464.

Example 2 (Production of Polyol Resin Composition) The terpene phenol structure skeleton-containing epoxy resin obtained in Production Example 2 was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet. (TEP-2) 175 copies,
67 parts of diisopropanolamine (1.0 active hydrogen per epoxy group) was charged, the temperature of the system was raised to 120 ° C., and then the reaction was carried out for 5.5 hours, and a yellow solid terpene phenol structure skeleton-containing polyol resin Composition (C-
2) was obtained. The OHV of the obtained polyol resin composition was 390.

Example 3 (Production of polyol resin composition) The terpene phenol structure skeleton-containing epoxy resin obtained in Production Example 3 was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet. (TEP-3) 250 parts,
60 parts of diisopropanolamine (0.95 active hydrogen per epoxy group) was charged, the temperature of the system was raised to 120 ° C., and then the reaction was carried out for 5 hours, and a yellow solid terpene phenol structure skeleton-containing polyol resin composition (C-3)
I got The OHV of the obtained polyol resin composition was 29.
It was 8.

Example 4 (Production of Polyol Resin Composition) The epoxy resin (TEP-4) obtained in Comparative Production Example 4 was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet. ) 450 parts, diisopropanolamine 5
Charge 7 parts (1.0 active hydrogen per epoxy group) and 0.28 part dimethylbenzylamine,
After raising the temperature of the system to ℃, it was reacted for 5 hours to obtain a yellow solid terpene phenol structure skeleton-containing polyol resin composition (C-4). O of the obtained polyol resin composition
HV was 243.

Example 5 (Production of Polyol Resin Composition) The terpene phenol structure skeleton-containing epoxy resin obtained in Production Example 5 was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet. (TEP-5) 192 copies,
53 parts of diisopropanolamine (1.0 active hydrogen per epoxy group) and 0.14 part of dimethylbenzylamine were charged, the temperature in the system was raised to 120 ° C., and the reaction was allowed to proceed for 5 hours to give a yellow solid terpene. A phenol resin skeleton-containing polyol resin composition (C-5) was obtained. The OHV of the obtained polyol resin composition was 324.

Example 6 (Production of Polyol Resin Composition) The terpene phenol structure skeleton-containing epoxy resin obtained in Production Example 6 was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet. (TEP-6) 233 parts,
A polyol resin composition containing a terpene phenol structure skeleton as a yellow solid was prepared by charging 133 parts of diisopropanolamine (1.0 active hydrogen per epoxy group), heating the temperature of the system to 120 ° C., and then reacting for 5 hours. (C-6)
I got The OHV of the obtained polyol resin composition was 46.
It was 6.

Example 7 (Production of Polyol Resin Composition) The terpene phenol structure skeleton-containing epoxy resin obtained in Production Example 7 was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet. (TEP-7) 140 parts,
27 parts of diisopropanolamine (1.0 active hydrogen per epoxy group) was charged, the temperature of the system was raised to 120 ° C., and then the reaction was carried out for 5 hours to obtain a yellow solid terpene phenol structure skeleton-containing polyol resin composition. (C-7) was obtained. The OHV of the obtained polyol resin composition was 249.
Met.

Example 8 (Production of Polyol Resin Composition) 500 parts of epoxy resin (TEP-3) containing a terpene phenol structure skeleton was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet. , 105 parts of diethanolamine (1.0 active hydrogen per epoxy group)
Was charged, the temperature of the system was raised to 120 ° C., and then the reaction was performed for 5.5 hours to obtain a yellow solid terpene phenol structure skeleton-containing polyol resin composition (C-8). The OHV of the obtained polyol resin composition was 336.

Example 9 (Production of Polyol Resin Composition) 500 parts of an epoxy resin (TEP-3) containing a terpene phenol structure skeleton was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet. , Dibutylamine 12
9 parts (1.0 active hydrogen per epoxy group) was charged, the temperature of the system was raised to 120 ° C., and then the reaction was carried out for 5.5 hours to obtain a yellow solid terpene phenol structure skeleton-containing polyol resin composition ( C-9) was obtained. The OHV of the obtained polyol resin composition was 145.

Example 10 (Production of Polyol Resin Composition) 500 parts of epoxy resin (TEP-3) containing a terpene phenol structure skeleton was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet. , Dimethylolpropionic acid 140 parts (active hydrogen 1.
(0 piece) was charged and the temperature inside the system was raised to 120 ° C.
The reaction was carried out for 5 hours to obtain a yellow solid terpene phenol structure skeleton-containing polyol resin composition (C-10). The OHV of the obtained polyol resin composition was 285.

Example 11 (Production of Polyol Resin Composition) 500 parts of epoxy resin containing terpene phenol structure skeleton (TEP-3) was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet. , 122 parts of benzoic acid (1.0 active hydrogen per epoxy group) were charged, and the temperature of the system was raised to 120 ° C., followed by reaction for 5.5 hours, and a yellow solid terpene phenol structure skeleton-containing polyol resin A composition (C-11) was obtained. The OHV of the obtained polyol resin composition was 126.

Comparative Example 1 (Production of Polyol Resin Composition) The comparative epoxy resin obtained in Comparative Production Example 1 (Comparative EP) was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet. -1) 250 parts, 67 parts of diisopropanolamine (1.0 active hydrogen per epoxy group)
3.5), and after raising the temperature of the system to 120 ° C, 3.5
After reacting for a time, a yellow solid polyol resin composition (C-
12) was obtained. OHV of the obtained polyol resin composition
Was 366.

Comparative Example 2 (Production of Polyol Resin Composition) Adeka Resin EP4100, 190 was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen inlet.
Part, 133 parts of diisopropanolamine (epoxy group 1
(1.0 active hydrogen per unit) was charged, the temperature in the system was raised to 120 ° C., and then the reaction was carried out for 3.5 hours to obtain a yellow solid polyol resin composition (C-13). The OHV of the obtained polyol resin composition was 521.

100 g of each of the polyol resin compositions obtained in Examples 1 to 11 and Comparative Examples 1 and 2 was added to turpentine oil 10
It was dissolved in 0 g and its solubility was observed. The evaluation was performed in the following three stages. The results are shown in [Table 1] below. ⊚: Dissolved uniformly and no insoluble matter was observed. ◯: A small amount of insoluble matter is observed, but it is almost uniformly dissolved. X: A large amount of insoluble matter is recognized.

[0062]

[Table 1]

The above polyol resin compositions C-1 to C-1
3, and glass beads were kneaded with a shaker for 2 hours according to the following formulation to prepare a white paint. Since the polyol resin compositions C-12 and C-13 have insufficient solubility in turpentine oil, xylene was used in the same weight part instead of turpentine oil.

(Compounding) Polyol resin composition 20 parts by weight Titanium dioxide 20 Bentonite 1 Turpentine oil 14.1 Solvesso 100 3.5 (High boiling point hydrocarbon solvent manufactured by Exxon Chemical Co., Ltd.)

To the resulting white paint, a tolylene diisocyanate 1: 3 adduct of trimethylolpropane as a curing agent (Coronate L, N manufactured by Nippon Polyurethane Co., Ltd.) was added.
CO% = 13.3%, solid content 75%) was added so as to be a hydroxyl group of the polyol resin composition / NCO of the curing agent = 1 / 0.7 equivalent ratio to obtain a coating composition.

Next, the obtained coating composition was applied onto a metal plate using a 070 bar coater so as to have a film thickness of 30 to 50 μm, and left standing at 25 ° C. for 7 days to dry and cure. The characteristics of the obtained coating film test piece were evaluated as follows, and the results are shown in [Table 2] below.

The method of evaluating each performance is as follows. Erichsen; using Erichsen tester, φ20mm,
It was conducted under the condition of 8 mm. Alkali resistance test; 2 based on JIS K-5400
Evaluation after 4 hours. Corrosion resistance test: Based on JIS K-5400, the sandblasted plate coating film test piece was subjected to SST for 500 hours. The criteria are as follows. Flat part ○: No rust or blister △: 〃 Somewhat seen ×: 〃 Cross-cut part that is often seen ○: Rust, blister 0.5 mm or less ○ ~ △; 〃 0.5-1 mm △ ； 〃 1-1.5 mm △ to ×; 〃 1.5 to 2 mm ×; 〃 2 mm or more Aluminum adhesion; A coating film test piece was prepared in the same manner except that an aluminum plate specified in JIS H-4000 was used, and the coating film was cross-cut. The tape peeling test was carried out by inserting and the peeling state of the coating film was compared. ○: No peeling △: Partial peeling observed ×: Whole surface peeled

[0068]

[Table 2]

From the results of the above [Table 1] and [Table 2], the following is clear. The polyol resin composition (C-1 to C-11) of the present invention is excellent in terpene solubility and can form a coating film having good corrosion resistance and adhesion to a substrate, and particularly active hydrogen. When a carboxylic acid having an alcoholic hydroxyl group or a secondary amine compound is used as the compound, a coating film having excellent corrosion resistance can be formed.

On the other hand, a polyol resin composition (C-12 and 13) containing no terpene structural skeleton.
Not only has poor solubility in terpenes, but also poor adhesion to the substrate when a coating film is formed.

[0071]

The polyol resin composition of the present invention (Claim 1) is soluble in terpene, which is a highly safe and high boiling point and hypoallergenic solvent, and has corrosion resistance, water resistance, heat resistance and chemical resistance. It has excellent electrical properties and mechanical properties, and can form a coating film with good adhesion to various substrates such as aluminum and zinc plates, and is useful for applications such as paints and adhesives.
The polyol resin composition of the present invention (claims 2 and 3) is obtained by using a specific compound as the component (A), and is further excellent in corrosion resistance, adhesion to a substrate and the like. . Polyol resin composition of the present invention (claims 4 and 5)
Is obtained by using a specific compound as the component (B), and is further excellent in the above characteristics. The polyol resin composition of the present invention (claim 6) is obtained by adding the component (B) to the component (A) in a specific ratio, and is further excellent in the above properties. The polyol resin composition of the present invention (claim 7) is useful as a coating resin composition when blended with a polyisocyanate compound.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Suzuki 7-35 Higashiohisa, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd.

Claims (7)

[Claims] 1. An epoxy resin having a terpene phenol structure skeleton obtained by adding a phenol or an alkylphenol compound to a cyclic terpene compound (A) and having an epoxy equivalent of 200 to 10,000, and a (B) epoxy group A polyol resin composition obtained by adding an active hydrogen-containing compound having one reactive active hydrogen. 2. The epoxy resin having the terpene phenol structural skeleton, which is the component (A), is selected from the group consisting of mononuclear polyhydric phenols or polyglycidyl ethers of polynuclear polyhydric phenols and aliphatic polyglycidyl ethers. The polyol resin composition according to claim 1, which is an addition product of at least one polyglycidyl ether and a terpene phenol compound. 3. The polyol resin composition according to claim 2, wherein the polyglycidyl ether is a polyglycidyl ether of alkylidene bisphenol represented by the general formula shown below. Embedded image 4. The polyol resin composition according to claim 1, wherein the active hydrogen-containing compound which is the component (B) is a carboxylic acid or a secondary amine compound. 5. The polyol resin composition according to claim 4, wherein the carboxylic acid or secondary amine compound is a compound having an alcoholic hydroxyl group. 6. The amount of active hydrogen of the active hydrogen compound of the component (B) is 0.7 to 1. per 1 epoxy group of the epoxy resin having the terpene phenol structure skeleton of the component (A). The polyol resin composition according to any one of claims 1 to 5, which is added in a ratio of one. 7. A coating resin composition containing the polyol resin composition according to claim 1 and a polyisocyanate compound.