JPH11209585A - Polyol resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyol resin composition capable of being dissolved in highly safe solvents having high boiling points and low irritation, such as terpentine oil or mineral spirit, and having excellent curability, corrosion resistance, solvent resistance, flexibility and high anticorrosive property. SOLUTION: This polyol resin composition is obtained by adding (B) an active hydrogen-containing compound to (A) a polyepoxy compound containing a phenol novolak epoxy resin whose nuclei may be substituted by >=4C aliphatic or alicyclic hydrocarbon groups and which is crosslinked with a polyisocyanate compound. Therein, a phosphoric acid compound and/or a polyhydroxybenzoic acid are added as a part of the active hydrogen-containing compound B, or an active hydrogen-containing compound except the phosphoric acid compound and/or the polyhydroxybenzoic acid is addition-reacted to the polyepoxy compound A, and subsequently the phosphoric acid compound and/or the polyhydroxybenzoic acid are compounded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyol resin composition, and more particularly to a polyol resin composition which is soluble in highly safe, high boiling and low irritant solvents such as terpenes and mineral spirits, and has excellent weather resistance and corrosion resistance. The present invention relates to a polyol resin composition capable of providing a coating film having good curability and adhesion to various substrates.

[0002]

2. Description of the Related Art A polyol resin obtained by adding an active hydrogen-containing compound such as a secondary amine or a phenol compound to an epoxy resin is cured by using a polyisocyanate or the like as a curing agent. , To form a coating with excellent adhesiveness to various substrates, heat resistance, chemical resistance, electrical properties, mechanical properties, etc.
Widely used as an adhesive and the like.

[0003] When used in these applications, conventionally, a solvent type dissolved in various low-boiling solvents such as benzene, toluene, xylene, methyl ethyl ketone, and ethyl acetate has generally been used. Due to problems such as harm to the human body and adverse effects on the global environment, the use of low-boiling solvents has been restricted, and the use of low-boiling solvents (high-solidification) or high-boiling and low-irritants such as terpenes and mineral spirits has been reduced. Switching to a neutral solvent has been strongly demanded.

However, conventional polyol resins are:
Because of its poor solubility in terpenes and mineral spirits, terpenes with a high boiling point and low irritation could not be used when used as a solvent type. For this reason, it has been strongly desired to find an epoxy resin that is soluble in terpenes and has excellent adhesiveness to various substrates, corrosion resistance, heat resistance, chemical resistance, electrical properties, mechanical properties, and the like.

JP-A-58-7557 and JP-A-59-56460 disclose an addition product of a diglycidyl ether of an alkylene oxide adduct of a dihydric phenol with an active hydrogen-containing compound or a dihydric phenol. It has been proposed to use an addition product of a high-molecular-weight epoxy resin obtained by chain-extending a diglycidyl ether of an alkylene oxide adduct with a divalent carboxylic acid and an active hydrogen-containing compound. Although it has been improved to some extent in terms of water resistance and low-temperature curability, it has problems in workability, such as high viscosity, the necessity of diluting with a large amount of organic solvent, and the use of paint varnish base. Poor wettability to materials and poor adhesion, especially in recent years, in terms of corrosion resistance and durability, it has been widely used. Galvanized steel sheet came, poor adhesion to non-ferrous metal substrates such as aluminum, were not practically satisfactory.

Japanese Patent Application Laid-Open No. 8-208805 proposes a polyol resin composition obtained by adding an active hydrogen-containing compound to an epoxy resin having a terpene phenol structure skeleton. However, a film having such properties as to satisfy satisfactory coating film properties has not yet been obtained.

For this reason, there has been a strong demand for finding a polyol resin composition which does not need to be diluted with an organic solvent which is harmful to the human body and which has particularly excellent adhesion to non-ferrous metals.

[0008] Accordingly, an object of the present invention is to dissolve in highly safe solvents having a high boiling point and low irritation, such as terpenes and mineral spirits, and have curability, corrosion resistance, solvent resistance, flexibility and high corrosion resistance. An object of the present invention is to provide a polyol resin composition having excellent properties.

[0009]

The present inventors have conducted intensive studies and as a result, have found that a novolak epoxy resin whose nucleus has been substituted with a long-chain aliphatic or alicyclic hydrocarbon group has a phosphate compound and / or polyphosphate. It has been found that a specific polyol resin composition obtained by adding or containing hydroxybenzoic acid can achieve the above object.

The present invention has been made based on the above findings, and is a phenol novolak epoxy resin which is nuclear-substituted by an aliphatic or alicyclic hydrocarbon group having 4 or more carbon atoms and may be crosslinked by a polyisocyanate compound. In a polyol resin composition obtained by adding an active hydrogen-containing compound (B) to a polyepoxy compound (A) containing the compound (A), a phosphoric acid compound and / or a polyhydroxy compound are used as a part of the active hydrogen-containing compound (B). After containing benzoic acid or adding a phosphoric acid compound and / or an active hydrogen-containing compound other than polyhydroxybenzoic acid to the polyepoxy compound (A), the phosphoric acid compound and / or polyhydroxybenzoic acid are added to the polyepoxy compound (A). It is intended to provide a polyol resin composition characterized by being blended.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the polyol resin composition of the present invention will be described in detail.

The polyepoxy compound (A) used in the present invention is a phenol novolak epoxy resin which is nuclear-substituted by an aliphatic or alicyclic hydrocarbon group having 4 or more carbon atoms and may be crosslinked by a polyisocyanate compound. (Hereinafter referred to as “nuclear-substituted phenol novolak epoxy resin”).

The above-mentioned core-substituted phenol novolak epoxy resin is specifically exemplified by p-tert-butylphenol, p-tert-amylphenol, hexylphenol,
It is a novolak epoxy resin derived from a nucleus-substituted phenol such as octylphenol, nonylphenol, dodecylphenol, octadecylphenol or terpenephenol, or a mixture thereof.

The nucleus-substituted phenols may be a mixture containing a small amount (less than 50% by weight, preferably less than 30% by weight) of phenol, cresol, ethylphenol, propylphenol and the like.

These nuclear-substituted phenol novolak epoxy resins are obtained, for example, by condensing a nuclear-substituted phenol and a ketone (including an aldehyde) as exemplified above in the presence of a catalyst to give the resulting phenol novolak resin. It can be easily obtained by reacting epihalohydrin.

The ketones used herein include, for example, formaldehyde, paraformaldehyde, acetaldehyde, acetone, benzaldehyde and the like, and preferably formaldehyde and paraformaldehyde.

Examples of the catalyst that can be used for the reaction between the above-mentioned nuclear-substituted phenols and ketones include:
Acidic catalysts such as formic acid, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, phosphoric acid, salicylic acid, p-toluenesulfonic acid, benzoic acid and oxalic acid; basic catalysts such as dimethylamine, diethylamine, triethylamine and ammonia; sodium hydroxide, water Metal salt catalysts such as potassium oxide, lead acetate, sodium carbonate and the like can be mentioned.

The reaction conditions of the epoxidation step using epihalohydrin are as follows: epihalohydrin is 1.4 to 2 per equivalent of hydroxyl group of the nucleus-substituted phenol novolak resin.
The reaction is carried out at 50 to 120 ° C in the presence of a base, using 0 equivalent.

As the base used herein, for example,
Potassium hydroxide, sodium hydroxide, barium hydroxide,
Examples thereof include magnesium oxide, sodium carbonate and potassium carbonate, and particularly preferred is sodium hydroxide or potassium hydroxide.

The above-mentioned core-substituted phenol novolak epoxy resin has an average number of aromatic nuclei of 2 to 8, preferably 2
By using one having an epoxy equivalent of 200 to 1,000, preferably 250 to 800, excellent properties such as curability and physical properties of a coating film can be obtained.

The terpene phenol is obtained by adding an alkylphenol compound such as phenol or orthocresol to a cyclic terpene compound. For example, the terpene phenol is represented by the following formulas (1) to (6). Compounds as shown are mentioned.

[0022]

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The polyepoxy compound (A) may be used in combination with the above-mentioned core-substituted phenol novolak epoxy resin according to the present invention, and may be used in combination with another polyepoxy compound. , For example, hydroquinone, resorcinol, methylresorcinol,
Polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as pyrocatechol and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A) ), Isopropylidenebis (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 novolak,
Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as orthocresol novolak and resorcinol novolak; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-Polyglycidyl ether of polyhydric alcohol such as ethylene oxide or propylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer Acid, phthalic acid,
Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endmethylenetetrahydrophthalic acid and Glycidyl methacrylate homopolymer or copolymer; N, N-diglycidylaniline,
Epoxy compounds having a glycidylamino group such as bis (4- (N-methyl-N-glycidylamino) phenyl) methane; vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4- Epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6
Epoxidized products of cyclic olefin compounds such as (-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer; and heterocyclic compounds such as triglycidyl isocyanurate. However, when these other polyepoxy compounds are used in a large amount, the effect of the present invention may not be sufficiently exerted. Even when the polyepoxy compounds are used, 50% by weight of the polyepoxy compound (A) is used.
Preferably less than 30% by weight. Therefore, the above-mentioned core-substituted phenol novolak epoxy resin contains 50% in the polyepoxy compound (A).
It is preferred that the content be at least 10% by weight.

It is preferable that the polyepoxy compound (A) is crosslinked with a polyisocyanate compound, because a cured product having more excellent physical properties such as corrosion resistance can be obtained.

Here, the polyepoxy compound (A) should ideally have a structure in which the hydroxyl groups on all the aromatic rings are substituted with glycidyl ether groups, but in fact, the hydroxy groups remain as they are. Or a structure in which halohydrin or epihalohydrin is polyadded, and a considerable amount of alcoholic hydroxyl groups remain therein. In the present invention, the remaining phenolic hydroxyl groups and / or
Alternatively, it is preferable that an alcoholic hydroxyl group generated by the reaction is reacted with an isocyanate group of a polyisocyanate compound to cause crosslinking. In some cases, an oxazolidone structure can be formed by reacting an isocyanate group with an epoxy group using an oxazolidone-forming catalyst.

Examples of the polyisocyanate compound used here include ordinary polyisocyanate compounds and prepolymers obtained from polyols having terminal isocyanate groups and polyisocyanate compounds.

As the above polyisocyanate compound,
Examples thereof include aliphatic, alicyclic, and aromatic divalent isocyanates. Specific examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, phenylene diisocyanate, and xylylene diisocyanate. , Tetramethylxylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate , 1,5-naphthalenediisocyanate, 1,5-tetrahydronaphthalenediisocyanate, isophorone diisocyanate and the like.

The polyols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
Low molecular weight polyols such as 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, hexamethylene glycol, hydrogenated bisphenol A, bis (hydroxyethoxyphenyl) propane Or a polyether polyol such as an ethylene oxide and / or propylene oxide adduct thereof, polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, or polytetramethylene glycol; and the above low molecular weight polyol and / or polyether polyol and succinic acid, glutaric acid, Adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, endmethylene tetrahydrophthalic acid, hexahydrophthalic acid, etc. Polyester polyol which is a condensate with a basic acid or carbonic acid; polyolefin polyol obtained by hydroxylating polyethylene or polypropylene; polybutadiene polyol obtained by hydroxylating 1,2-polybutadiene, 1,4-polybutadiene, polyisoprene; polycarbonate Polyols and the like.

Here, the prepolymer as the polyisocyanate compound has an average molecular weight of 300 to 500.
0, especially 500 to 3000 glycols per mole, diisocyanate 1.2 to 2.5 moles, especially 1.4.
By using a prepolymer obtained by adding ~ 2.2 mol, it is excellent in solubility in low boiling point and low irritating solvents such as terpenes and mineral spirits, and excellent in physical properties such as flexibility and adhesion. It is preferable because a product can be obtained.

The polyisocyanate compound is preferably used in an amount of 3 parts by weight in 100 parts by weight of the polyepoxy compound (A).
It is used in an amount not exceeding 0 parts by weight, more preferably 5 to 25 parts by weight. Physical properties may be reduced.

The active hydrogen-containing compound (B) used in the present invention contains, as a part thereof, a phosphoric acid compound and / or polyhydroxybenzoic acid, or contains a phosphorus compound in the polyepoxy compound (A). After adding an active hydrogen-containing compound other than an acid compound and / or polyhydroxybenzoic acid, the phosphoric acid compound and / or polyhydroxybenzoic acid is added.

The phosphoric acid compound used in the present invention includes a phosphoric acid having at least one P-OH bond,
At least one phosphoric acid compound selected from the group consisting of esters and salts thereof, and the phosphoric acid includes, for example, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid,
Phosphorous acid, polyphosphoric acid, phosphonic acid, methanephosphonic acid, benzenephosphonic acid, 1-hydroxyethane-1,
1-diphosphonic acid, phosphinic acid and the like. Examples of the phosphorus acid ester include alkyl, alkenyl or substituted alkyl partial esters of the above acids [alkyl groups include methyl, ethyl, propyl, butyl, hexyl and octyl] , Isooctyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, octadecyl, and the like. Examples of the alkenyl group include allyl, octenyl,
Those having 1 to 30 carbon atoms, such as decenyl and octadecenyl, are preferred. As the substituted alkyl group, a hydroxyalkyl group such as 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-2-phenylethyl, etc. 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 2-hydroxy-3-octoxypropyl, 2-hydroxy-
3-octadecyloxypropyl, 2-hydroxy-3-
Alkoxy or aryloxyhydroxyalkyl groups such as phenoxypropyl, 2-hydroxy-3-toloxypropyl, 2-hydroxy-3-octylphenoxypropyl; 2- (3-methoxy-2-hydroxypropoxy) ethyl, 2- (3 -Butoxy-2-hydroxypropoxy) ethyl, 2- (3-phenoxy-2-hydroxypropoxy) ethyl, 2- (3-toloxy-2-
Preferred are those having a hydroxy group and / or an ether bond such as an alkoxy or aryloxyhydroxyalkoxyalkyl group such as hydroxypropoxy) ethyl, and the like. Examples of the phosphorus acid salt include potassium, lithium and Sodium, calcium, barium, zinc and the like can be mentioned.

The polyhydroxybenzoic acid used in the present invention includes, for example, dihydroxybenzoic acid and gallic acid.

These phosphoric acid compounds and / or polyhydroxybenzoic acids are obtained by reacting one epoxy group of the polyepoxy compound (A) with a P-OH group of the phosphoric acid compound and / or a carboxyl group of the polyhydroxybenzoic acid. Those having added and / or contained 0.01 to 0.5, particularly 0.1 to 0.3 groups of groups are particularly excellent in cured physical properties such as adhesion and corrosion resistance. Is preferred because

In producing the polyol resin composition of the present invention, a known active hydrogen-containing compound other than a phosphoric acid compound and polyhydroxybenzoic acid is usually used in combination. Examples include phenol compounds, secondary amine compounds, compounds having a carboxyl group, and the like.

As the phenol compound, for example,
Monophenol compounds such as phenol, cresol, ethylphenol, propylphenol, p-tert-butylphenol, p-tert-amylphenol, hexylphenol, octylphenol, nonylphenol, dodecylphenol, octadecylphenol or terpenephenol; bisphenol A, bisphenol F, Bisphenol compounds such as bisphenol S; and novolaks of the above mono- and / or bisphenol compounds. Among these phenolic compounds, when a phenolic compound having a structure similar to that of the polyepoxy compound (A) and having a nucleus substituted by an aliphatic or alicyclic hydrocarbon group having 4 or more carbon atoms is used (polyepoxy compound It is preferable to add the phenolic hydroxyl group in an amount of 0.1 or more to one epoxy group in (A)) because of its excellent solubility in a weak solvent such as mineral spirit.

As the secondary amine compound, for example,
Dialkylamine compounds such as dibutylamine and dioctylamine; alkanolamine compounds such as methylethanolamine, butylethanolamine, diethanolamine, diisopropanolamine and dimethylaminopropylethanolamine; morpholine, piperidine,
Heterocyclic amine compounds such as methylpiperazine are exemplified, and alkanolamine compounds are particularly preferable since a polyol resin composition having excellent properties can be obtained.

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, Aliphatic, aromatic or alicyclic monocarboxylic acids such as cyclohexane carboxylic acid, and the like, and particularly excellent properties when a carboxylic acid having an alcoholic hydroxyl group such as 2,2-dimethylolpropionic acid or lactic acid is used. This is preferable because a polyol resin composition having a reduced viscosity can be obtained.

In the polyol resin composition of the present invention, an active hydrogen-containing compound (B) is added to the polyepoxy compound (A), and an active hydrogen of the active hydrogen-containing compound is added to one epoxy group of the polyepoxy compound. It is preferable to add 0.7 to 1 pieces.

As a method of adding the active hydrogen-containing compound (B) to the polyepoxy compound (A), for example, the polyepoxy compound (A) is added to the polyepoxy compound (A) in a required amount or in an excess amount in the presence of a catalyst such as dimethylbenzylamine. Of the active hydrogen-containing compound (B) in a batch or in multiple
A method of heating to 0 ° C. and reacting for 1 to 10 hours is exemplified. The reaction order of the phosphoric acid compound and / or polyhydroxybenzoic acid and the other active hydrogen compound is not limited, and after adding the phosphoric acid compound and / or the polyhydroxybenzoic acid, the other active hydrogen-containing compound is added. A method of adding a phosphate compound and / or polyhydroxybenzoic acid after adding another active hydrogen-containing compound, or a method of adding both simultaneously, may be used. A method of adding a phosphoric acid compound and / or polyhydroxybenzoic acid later is preferable. When adding a phosphoric acid compound and / or polyhydroxybenzoic acid after adding another active hydrogen-containing compound, it is not necessary that all of the phosphoric acid compound and / or polyhydroxybenzoic acid be added, and some of them are added. It may be added, and some may remain unreacted. Further, the phosphoric acid compound and / or the polyhydroxybenzoic acid may be blended without adding to the epoxy group.

When the polyol resin composition of the present invention is used for coating or adhesion, other polyol compounds can be used in combination. By using a low-viscosity polyol compound, an organic solvent can be used. It is preferable because a low viscosity and excellent workability can be obtained without using. As such a polyol compound, usually, a polyol compound having an average molecular weight of less than 3,000 is suitably used, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,
2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, hexamethylene glycol, 2-methylpentanediol, 12-hydroxystearyl alcohol, dimer diol, hydrogenated bisphenol A, bis (hydroxyethoxyphenyl) propane , Low molecular weight polyols such as glycerin, trimethylolpropane, and pentaerythritol or ethylene oxide and / or propylene oxide adducts thereof, polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, etc., resorcinol, hydroquinone, bisphenol A, bisphenol F, bisphenol Ethylene oxide and / or propylene oxide adducts of polyhydric phenols such as S, ammonium, Polyether polyols such as ethylene oxide and / or propylene oxide adducts of amines such as diamine, hexamethylene diamine, ethanolamine, and propanolamine; the low-molecular-weight polyol and succinic acid, glutaric acid, adipic acid, sebacic acid, and phthalic acid , Isophthalic acid, terephthalic acid, tetrahydrophthalic acid, endomethylene tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid,
Polybasic acids such as pyromellitic acid, 12-hydroxystearic acid, polyester polyols and polycarbonate polyols which are condensates with hydroxycarboxylic acids or carbonic acids such as castor oil fatty acids, and diethanolamine adducts of the polyepoxy compounds exemplified above. And ordinary polyol compounds.

The amount of these polyol compounds used is not particularly limited, but when used, preferably 50 to 1000 parts by weight, more preferably 100 to 100 parts by weight of the polyol resin composition of the present invention. 100-80
0 parts by weight is used. When used in less than 50 parts by weight, the effect of reducing viscosity is insufficient, and when used in excess of 1000 parts by weight, adhesion to non-ferrous metals, anticorrosion properties, etc. Is undesirably reduced.

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.

The curing agent can be used without any particular limitation as long as it is generally used as a curing agent for a polyol resin. For example, melamine, methylolmelamine, methylmelamine, butylmelamine Melamine compounds such as melamine resin, urea resin, benzoguanamine, guanamine resin, melamine-formaldehyde resin; phenolic resin, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated TDI, hydrogenated MDI, isophorone diisocyanate, isocyanate resin And a polyisocyanate compound such as a urethane prepolymer resin obtained by reacting the above isocyanate compound with a general polyol, and ε-caprolactam, oxime, phenol, alcohol Mask agent modified blocked isocyanate compound and the like in.

The amount of these curing agents varies depending on the purpose, curing temperature, and curing time. Usually, the melamine compound is used in an amount of 100 parts by weight based on the polyol component (the polyol resin composition of the present invention and other polyols). , 1-5
It is used in an amount of 0 part by weight, preferably 5 to 20 parts by weight, and the (block) polyisocyanate compound has an isocyanate equivalent of 0.1 to 1.5, preferably 0.1 to 1.5, based on one hydroxyl equivalent of the polyol component (same as above). Is 0.5 to 1.2
Used in the range. Here, when the curing agent is used less than the above range, curing is insufficient, adhesion, corrosion resistance and the like are inferior, and when the curing agent is used more than the above range, crosslinking is excessively advanced and sufficient flexibility is obtained. It is not preferable because it may not be obtained.

When the polyol resin composition of the present invention is used as a paint or an adhesive, solvents can be used. Examples of these solvents include acetone, toluene, xylene, methyl ethyl ketone, ethyl acetate, propylene glycol and the like. Solvents such as -monoethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, and ethyl acetate can also be used. However, the epoxy resin composition of the present invention can be used in the presence of terpine oil, D-limonene, pinene or the like. Terpene hydrocarbon oils; high-boiling paraffinic solvents such as mineral spirits, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.) (alicyclic mainly containing aliphatic hydrocarbons) , And an aromatic hydrocarbon, wherein the high boiling point is 1
It indicates that the composition contains 90% or more of components at 50 ° C. or higher. ) Is preferable, and the use of these is preferable because danger and harmfulness can be further reduced. Further, these solvents can be optionally used as a mixed solvent of two or more kinds.

The amount of the solvent used depends on the purpose, but is usually 0 to 1000 parts by weight, preferably 10 to 600 parts by weight, per 100 parts by weight of the polyol resin component.

The polyol resin composition of the present invention may further contain, if necessary, other polyol compounds, curing catalysts, plasticizers such as dioctyl phthalate, non-reactive diluents, glass fibers, carbon fibers, cellulose, silica, and the like. Fillers or pigments such as sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely divided silica, titanium dioxide, carbon black, graphite, iron oxide, bituminous substances, thickeners, thixotropic agents And conventional additives such as a flame retardant and an antifoaming agent. Further, adhesive resins such as xylene resin, petroleum resin, rosin and terpene resin can be used in combination.

According to a method for preparing a coating material using the polyol resin composition of the present invention, a desired additive such as a filler is added to the polyol resin composition, glass beads are added thereto, and the mixture is shaken for a predetermined time. There is a method of kneading with a mill or the like. The resulting coating material can be mixed with a curing agent, applied with a predetermined thickness using a bar coater or the like, and dried and cured to form a coating film.

The polyol resin composition of the present invention can be used, for example, as a paint or adhesive for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc .; Frozen food labels, ream bubble labels, POS labels, adhesive wallpapers, adhesives for floor adhesives; Art paper, coated paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copier, impregnated paper, etc. Sizing agents such as natural fibers, synthetic fibers, glass fibers, carbon fibers, and metal fibers, fiber treatment agents such as anti-fray agents and processing agents; wide-ranging applications such as sealing materials, cement admixtures, and waterproofing materials However, it is particularly preferable to use it as a paint for metal coating.

When the polyol resin composition of the present invention is used as a paint, it can be applied to a substrate by an appropriate method. For example, brush coating, roller coating, spray coating, gravure coating, reverse roll coating, air knife, etc. Coat, bar coat, curtain roll coat,
It can be applied by a method such as dip coating, rod coating, doctor blade coating and the like.

When the polyol resin composition of the present invention is used as a coating material for metal coating, examples of the metal substrate include aluminum, titanium, stainless steel, mild steel, and plated steel. Is acetone,
Various surface treatments such as degreasing with an organic solvent such as alcohol, blast treatment, alkali washing, phosphate treatment, chromate treatment, and fluoride salt treatment can also be performed.

The coated metal sheet obtained here can be used for interior and exterior materials for construction, home appliances such as refrigerators, washing machines, electric stoves, vending machines, office equipment, furniture including food display cases and the like. Can be used for metal products.

[0054]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples.

Production Example 1 (Production of Novolac Epoxy Resin) In a 2 L reactor equipped with a thermometer, a stirrer and a water separator equipped with a cooling pipe, a titanol # 1133 (manufactured by Hitachi Chemical Co., Ltd .; p- 250 g of tributylphenol novolak resin, OH equivalent 158, average number of nuclei 3) 250 g, hitanol # 1501 (manufactured by Hitachi Chemical Co., Ltd .; octylphenol novolak resin, OH equivalent 214, average number of nuclei 3), 250 g, and 1440 g of epichlorohydrin were charged. After stirring to form a homogeneous solution, 268 g of 48% by weight sodium hydroxide was added dropwise at 60 to 110 ° C over 2 hours. During this time, epichlorohydrin was refluxed in the system while water generated in the system was azeotropically removed with epichlorohydrin and removed outside the system by a water separator. After dropping, 100
The mixture was aged at -120 ° C for 2 hours, and the reaction was terminated when the theoretical amount of water flowed out.

150 g of xylene was added to the obtained epichlorohydrin solution of the epoxy compound, washed with a large amount of water to remove generated salt and excess sodium hydroxide, and then neutralized with a 3% by weight phosphoric acid aqueous solution. Next, epichlorohydrin and xylene were distilled off under reduced pressure to obtain an epoxy resin having an epoxy equivalent of 340. To this, 460 g of Swazole # 310 (manufactured by Cosmo Matsuyama Co., Ltd .; a high-boiling paraffin solvent) was added, and a brown liquid epoxy resin (NE) was added.
P-1) 1150 g was obtained. This saponifiable chlorine is 0.3
% By weight, epoxy equivalent was 570, and solid content was 60% by weight.

Production Example 2 (Production of Prepolymer) A 1 L reactor equipped with a thermometer, a stirrer, and a condenser was charged with
Adeka polyether P-700 (manufactured by Asahi Denka Kogyo KK);
Polypropylene glycol, hydroxyl value 155) 362
g, Coronate T-80 (manufactured by Nippon Polyurethane Co .; tolylene diisocyanate), and reacted at 80 to 90 ° C. for 3 hours while paying attention to a temperature rise, and a colorless transparent liquid prepolymer (PP-1, isocyanate content) 7.8% by weight).

Production Example 3 Epoxy resin (NEP-1) 118 was placed in a 2 L reactor equipped with a thermometer, a stirrer, and a water separator equipped with a cooling pipe.
0 g, keeping the inside of the system at 80 to 90 ° C., and paying attention to the temperature rise, and 126.4 g of the prepolymer (PP-1).
(15% by weight of solid content) was added dropwise over 30 minutes.
For 2 hours, and the temperature was further raised to 100 ° C. to react for 1 hour. Finally, 85 g of Swazole # 310 was added to obtain an epoxy resin (NEP-2, solid content 60% by weight, epoxy equivalent 750).

Example 1 NEP-1850 g, YP-90L (manufactured by Yashara Chemical Co., Ltd .; terpene phenol compound, average molecular weight 325, phenolic hydroxyl equivalent) in a flask equipped with a nitrogen inlet tube, a cooling tube, a thermometer and a stirrer. 239) 67 g
And hitanol # 1002 (manufactured by Hitachi Chemical Co., Ltd .;
Octylphenol novolak resin, hydroxyl equivalent 26
0) 333 g and triphenylphosphine 2.5 g were charged and reacted at 130 to 150 ° C. for 4 hours to obtain a high molecular weight brown polyepoxy compound having an epoxy equivalent of 5000.

Thereafter, the inside of the system was cooled to 80 to 90 ° C., and 34 g of diisopropanolamine was added.
After reacting for a long time, most of the epoxy groups in the polyepoxy compound are reacted, and then a mono / di mixture (3-butoxy-2
-Hydroxypropyl) phosphoric acid (P-OH96) 28.
9 g (3% by weight) was added dropwise at 60 to 70 ° C. for 30 minutes, and the mixture was aged at 80 to 90 ° C. for 1 hour, and 280 g of Swazole # 310 was added as a diluting solvent to homogenize the system.
A brown polyol resin composition (solid content 60% by weight, hydroxyl equivalent 96) was obtained.

Example 2 In a flask equipped with a nitrogen introducing tube, a cooling tube, a thermometer, and a stirrer, NEP-2850 g and YP-90L 67 g were placed.
Then, 333 g of titanol # 1002 and 2.5 g of triphenylphosphine were charged and reacted at 130 to 150 ° C. for 4 hours to obtain a high-molecular-weight brown polyepoxy compound having an epoxy equivalent of 5000.

Thereafter, the inside of the system was cooled to 80 to 90 ° C., and 34 g of diisopropanolamine was added.
After reacting for a long time, most of the epoxy groups in the polyepoxy compound are reacted, and then a mono / di mixture (3-butoxy-2
-Hydroxypropyl) phosphoric acid (P-OH96) 28.
9 g (3% by weight) was added dropwise at 60 to 70 ° C. for 30 minutes, and the mixture was aged at 80 to 90 ° C. for 1 hour, and 280 g of Swazole # 310 was added as a diluting solvent to homogenize the system.
A brown polyol resin composition (solid content 60% by weight, hydroxyl equivalent 101) was obtained.

Example 3 A high-molecular-weight brown polyepoxy compound having an epoxy equivalent of 5,000 was produced in the same manner as in Example 2, and the system was then treated with 80-80%.
After cooling to 90 ° C., 34 g of diisopropanolamine was added and reacted at 80 to 90 ° C. for 2 hours to largely react the epoxy groups in the polyepoxy compound.
8.9 g (3% by weight) was added dropwise at 60 to 70 ° C. for 30 minutes, and the mixture was aged at 80 to 90 ° C. for one hour. A resin composition (solid content 60% by weight, hydroxyl equivalent 100) was obtained.

Example 4 NEP-2850 g, YP-90LL (manufactured by Yashara Chemical Co., Ltd .; terpene phenol compound, average molecular weight 266, phenolic hydroxyl equivalent) were placed in a flask equipped with a nitrogen inlet tube, a cooling tube, a thermometer, and a stirrer. 170) 60
g and hitanol # 1133 (Hitachi Chemical Industry Co., Ltd.)
Octylphenol novolak resin, hydroxyl equivalent 3
20) 330 g and 2.5 g of triphenylphosphine
And reacted at 130 to 150 ° C. for 4 hours to obtain a high molecular weight brown polyepoxy compound having an epoxy equivalent of 2000.

Thereafter, the inside of the system was cooled to 80 to 90 ° C., and 85 g of diisopropanolamine was added.
After reacting for a long time, most of the epoxy groups in the polyepoxy compound are reacted, and then a mono / di mixture (3-butoxy-2
-Hydroxypropyl) phosphoric acid (P-OH96) 30.
4 g (3% by weight) was added dropwise at 60 to 70 ° C. in 30 minutes, and the mixture was aged at 80 to 90 ° C. for 1 hour. 337 g of Swazole # 310 was added as a diluting solvent to homogenize the system.
A brown polyol resin composition (solid content 60% by weight, hydroxyl equivalent 148) was obtained.

Example 5 NEP-1850 g and YP-90LL 50 were placed in a flask equipped with a nitrogen inlet tube, a cooling tube, a thermometer and a stirrer.
0 g and triphenylphosphine 2.5 g,
After reacting at 130 to 150 ° C. for 4 hours, the epoxy equivalent 2
000 high molecular weight brown polyepoxy compound was obtained.

Thereafter, the inside of the system was cooled to 80 to 90 ° C., and 85 g of diisopropanolamine was added.
The epoxy group of the polyepoxy compound is largely reacted by reacting for a period of time, and then a mono / di mixture (3-butoxy-2-
(Hydroxypropyl) phosphoric acid (P-OH96) 30.4
g (3% by weight) was added dropwise at 60 to 70 ° C. over 30 minutes, and the mixture was aged at 80 to 90 ° C. for 1 hour. (Solid content: 60% by weight, hydroxyl equivalent: 126) was obtained.

Example 6 NEP-2850 g and YP-90LL 50 were placed in a flask equipped with a nitrogen inlet tube, a cooling tube, a thermometer and a stirrer.
0 g and triphenylphosphine 2.5 g,
After reacting at 130 to 150 ° C. for 4 hours, the epoxy equivalent 2
000 high molecular weight brown polyepoxy compound was obtained.

Thereafter, the inside of the system was cooled to 80 to 90 ° C., and 85 g of diisopropanolamine was added.
After reacting for a long time, most of the epoxy groups in the polyepoxy compound are reacted, and then a mono / di mixture (3-butoxy-2
-Hydroxypropyl) phosphoric acid (P-OH96) 30.
4 g (3% by weight) was added dropwise at 60 to 70 ° C. in 30 minutes, and the mixture was aged at 80 to 90 ° C. for 1 hour. 337 g of Swazole # 310 was added as a diluting solvent to homogenize the system.
A brown polyol resin composition (solid content 60% by weight, hydroxyl equivalent 148) was obtained.

Example 7 NEP-2850 g and YP-90L 67 were placed in a flask equipped with a nitrogen inlet tube, a cooling tube, a thermometer and a stirrer.
g, 333 g of Hitanol # 1002 and 2.5 g of triphenylphosphine were charged and reacted at 130 to 150 for 4 hours to obtain a high molecular weight brown polyepoxy compound having an epoxy equivalent of 5000.

Further, 80 g of YP-90LL was added, and 1
The reaction was carried out at 30 to 150 ° C. for 2 hours to make most of the epoxy groups in the polyepoxy compound react.
Cool to 70 ° C. and mix 30.7 g of mono / di mixed (3-butoxy-2-hydroxypropyl) phosphoric acid (P-OH96)
(3% by weight) was added dropwise at 60 to 70 ° C. for 30 minutes, and the mixture was aged at 80 to 90 ° C. for 1 hour. (Solid content 60% by weight, hydroxyl equivalent 87) was obtained.

Example 8 In a flask equipped with a nitrogen inlet tube, a cooling tube, a thermometer and a stirrer, 60 g of diethanolamine was added to NEP-2510 g while maintaining the system at 80 to 90 ° C.
The reaction was carried out at 90 ° C. for 2 hours to obtain a polyepoxy compound. The epoxy group was largely reacted, and then a mono / di mixture (3.
-Butoxy-2-hydroxypropyl) phosphoric acid (PO)
H96) 11.3 g (3% by weight) at 60-70 ° C for 30
And aged at 80 to 90 ° C. for 1 hour. 48 g of Swazole # 310 was added as a diluting solvent to make the system uniform, and the brown polyol resin composition (solid content: 60
% By weight, with a hydroxyl equivalent of 160).

Example 9 A flask equipped with a nitrogen inlet tube, a cooling tube, a thermometer and a stirrer was charged with NEP-2850 g and YP-90L 67 g.
And bisphenol A, 55 g, hitanol # 1002
333 g and 2.4 g of triphenylphosphine were charged and reacted at 130 to 150 for 4 hours to obtain a high molecular weight brown polyepoxy compound having an epoxy equivalent of 5000.

Thereafter, the inside of the system was cooled to 80 to 90 ° C., and 34 g of diisopropanolamine was added.
After reacting for a long time, most of the epoxy groups in the polyepoxy compound are reacted, and then a mono / di mixture (3-butoxy-2
-Hydroxypropyl) phosphoric acid (P-OH96) 28.
8 g (3% by weight) was added dropwise at 60 to 70 ° C. in 30 minutes, and the mixture was aged at 80 to 90 ° C. for 1 hour.
A brown polyol resin composition (solid content 60% by weight, hydroxyl equivalent 527) was obtained.

Example 10 In a flask equipped with a nitrogen inlet tube, a cooling tube, a thermometer, and a stirrer, NEP-2750 g and ADEKARESIN EP-
4100 (manufactured by Asahi Denka Kogyo KK; bisphenol A type epoxy resin, epoxy equivalent 190), 80 g, YP-90
L, 80 g of L and 400 g of HITANOL # 1002 (manufactured by Hitachi Chemical Co., Ltd .; octylphenol novolak resin, hydroxyl equivalent: 260) and 2.5 g of triphenylphosphine were reacted at 130 to 150 for 4 hours to obtain a high molecular weight epoxy equivalent of 5000. A brown polyepoxy compound was obtained.

Thereafter, the inside of the system was cooled to 80 to 90 ° C., 25 g of diisopropanolamine was added, and
After reacting for a long time, most of the epoxy groups in the polyepoxy compound are reacted, and then a mono / di mixture (3-butoxy-2
-Hydroxypropyl) phosphoric acid (P-OH96) 29.
5 g (3% by weight) was added dropwise at 60 to 70 ° C. over 30 minutes, and the mixture was aged at 80 to 90 ° C. for 1 hour.
A brown polyol resin composition (solid content 60% by weight, hydroxyl equivalent 575) was obtained.

Comparative Example 1 In a flask equipped with a nitrogen inlet tube, a cooling tube, a thermometer and a stirrer, 850 g of Adekaresin EP-4100, Y
140 g of P-90L and hitanol # 10023
33 g and 2.0 g of triphenylphosphine were charged and reacted at 130 to 150 for 4 hours to obtain a high molecular weight brown polyepoxy compound having an epoxy equivalent of 2000.

Thereafter, the inside of the system was cooled to 80 to 90 ° C., 67 g of diisopropanolamine was added, and the mixture was heated at 80 to 90 ° C. for 2 hours.
After reacting for a long time, most of the epoxy groups in the polyepoxy compound are reacted, and then a mono / di mixture (3-butoxy-2
-Hydroxypropyl) phosphoric acid (P-OH96)
1 g (3% by weight) was added dropwise at 60 to 70 ° C. in 30 minutes, and the mixture was aged at 80 to 90 ° C. for 1 hour to obtain a brown solid polyol resin composition (hydroxyl equivalent 233).

Comparative Example 2 NEP-2850 g, YP-90L 170 were placed in a flask equipped with a nitrogen inlet tube, a cooling tube, a thermometer, and a stirrer.
g and 333 g of HITANOL # 1002 and 1.5 g of triphenylphosphine were charged and reacted at 130 to 150 for 4 hours to obtain a high-molecular-weight brown polyepoxy compound having an epoxy equivalent of 2000.

Thereafter, the system was cooled to 80 to 90 ° C., and 70 g of diisopropanolamine was added.
The reaction was carried out for a time to obtain a yellow solid polyol resin composition (hydroxyl equivalent: 137).

Comparative Example 3 A flask equipped with a nitrogen inlet tube, a cooling tube, a thermometer and a stirrer was charged with 500 g of ADEKARESIN EP-4100, 260 g of bisphenol A and 0.5 g of dimethylbenzylamine, and reacted at 130 to 150 for 4 hours. Thus, a high molecular weight brown polyepoxy compound having an epoxy equivalent of 2000 was obtained.

Thereafter, the inside of the system was cooled to 80 to 90 ° C., 40 g of diethanolamine was added, and the mixture was reacted at 80 to 90 ° C. for 2 hours to largely react epoxy groups in the polyepoxy compound. -Butoxy-2-hydroxypropyl) phosphoric acid (P-OH96) 24.7 g
(3% by weight) was added dropwise at 60 to 70 ° C. over 30 minutes, and then aged at 80 to 90 ° C. for 1 hour to obtain a colorless solid polyol resin composition (hydroxyl equivalent: 286).

Use Example 1 100 g of the polyol resin composition obtained in Examples 1 to 10 and Comparative Examples 1 to 3 was added to Mineral Spirit 900.
g, and its solubility was confirmed by the following evaluation criteria. The results are shown in Table 1 below. : Uniformly dissolved, no insoluble matter was observed △: A trace amount of insoluble matter was observed, but almost uniformly dispersed ×: A large amount of insoluble matter was observed

[0084]

[Table 1]

Use Example 2 Using the polyol resin compositions obtained in the above Examples 1 to 10 and Comparative Examples 1 to 3, kneading for 2 hours with a shaker using glass beads according to the following formulation to prepare a white paint. did.

(Blending) Parts by weight Polyol resin composition 20 Titanium dioxide 60 Talc 120 Bentonite 1 Mineral spirit 200

The resulting white paint was added with TP- as a curing agent.
703 (manufactured by Nippon Polyurethane Co., Ltd .; weak solvent-soluble polyisocyanate, NCO content: 12.4%, solid content: 85)
% By weight) of the polyol resin composition / NCO = 1 / 0.8 equivalent ratio of the curing agent to give a coating composition.

Next, the obtained coating composition was applied on a mild steel plate (SPCC-B) using an applicator to a dry film thickness of 70 μm.
[Except for the rust surface adhesion test].

The method of each performance evaluation is as follows. However, the drying conditions were drying and curing at room temperature for 24 hours. Erichsen; using an Erichsen tester, φ20 mm,
The test was performed under the condition of 8 mm. ；: No abnormality ×: Peeling occurred Solvent resistance: After coating film was applied, it was left at room temperature for 15 hours.
One drop of toluene was dropped on the coating film, and a rubbing test using absorbent cotton was performed up to 100 times, and the number of times until the base material appeared was observed. However, if the base does not appear up to 100 times,
And Low-temperature curability: The presence or absence of tacking when left at 5 ° C. for 15 hours after application of the coating film was evaluated by finger touch, and evaluated in two stages of ××. Corrosion resistance test: A coating film test piece was subjected to SST for 500 hours based on JIS K-5400. The criteria are as follows. Flat surface ○: No rust and blistering △; 〃 Slightly seen ×; 〃 Cross cut part ○: Less than 0.5mm rusted and blistered △; 〃 0.5 to 2mm ×; 超 Over 2mm Rust surface adhesion; After applying the coating composition to a rusted steel plate (three types of Keren steel plates exposed outdoors for one year and removing floating rust with a wire brush), the peel strength of the coating film dried and cured at room temperature for 7 days is measured by the adhesive strength. It was measured using a John tester to evaluate the rust surface adhesion.

The results of the above performance evaluation are shown in the following [Table 2].

[0091]

[Table 2]

As is clear from the above examples, a phenol novolak epoxy resin whose nucleus is substituted by an aliphatic or alicyclic hydrocarbon group having 4 or more carbon atoms and which may be crosslinked with a polyisocyanate compound; When the polyol resin composition of the present invention obtained from a phosphoric acid compound and / or a polyhydroxybenzoic acid such as gallic acid is used as a coating material, it has excellent solubility in mineral spirit, which is a weak solvent, and has excellent physical properties such as corrosion resistance. A coating can be obtained.

On the other hand, the polyol resin compositions (Comparative Examples 1 and 3) obtained from ordinary epoxy resins other than the nucleus-substituted phenol novolak epoxy resin according to the present invention and the phosphoric acid compound have comparatively low solubility in mineral spirits. None, the adhesion to the rust surface, the physical properties such as corrosion resistance are insufficient, and even when the long-chain phenol novolak epoxy resin according to the present invention is used, polyhydroxybenzoic acid such as a phosphate compound or gallic acid is used. When no acid is used (Comparative Example 2), the corrosion resistance is insufficient, and the adhesion to the rust surface is particularly insufficient.

[0094]

Industrial Applicability The polyol resin composition of the present invention is soluble in a highly safe solvent having a high boiling point and low irritation, and has curability, corrosion resistance, solvent resistance, flexibility and high corrosion resistance. It is excellent. Therefore, the polyol resin composition of the present invention is useful for applications such as various paints, adhesives, and sealing materials.

Claims (7)

[Claims] 1. A polyepoxy compound (A) containing a phenol novolak epoxy resin which is nuclear-substituted by an aliphatic or alicyclic hydrocarbon group having 4 or more carbon atoms and which may be crosslinked with a polyisocyanate compound. The polyol resin composition obtained by adding the active hydrogen-containing compound (B), which contains a phosphate compound and / or polyhydroxybenzoic acid as a part of the active hydrogen-containing compound (B), or After adding an active hydrogen-containing compound other than the phosphoric acid compound and / or polyhydroxybenzoic acid to the epoxy compound (A), the phosphoric acid compound and / or
Or a polyol resin composition characterized by blending polyhydroxybenzoic acid. 2. The polyepoxy compound (A) contains a phenol novolak epoxy resin whose nucleus is substituted by an aliphatic or alicyclic hydrocarbon group having 4 or more carbon atoms and which is crosslinked with a polyisocyanate compound. The polyol resin composition according to claim 1, wherein: 3. The active hydrogen-containing compound (B) is added to the polyepoxy compound (A) with respect to one epoxy group of the polyepoxy compound (A). 3. The polyol resin composition according to claim 1, wherein the polyol resin composition is added in an amount of 0.7 to 1. 4. The polyepoxy compound (A) is provided with the phosphoric acid compound and polyhydroxybenzoic acid, and the P-OH group and / or the Or the polyhydroxybenzoic acid is added or contained in an amount of 0.01 to 0.5 carboxyl groups.
4. The polyol resin composition according to any one of 3. 5. The active hydrogen-containing compound (B)
A phenol compound having a nucleus substituted by an aliphatic or alicyclic hydrocarbon group having 4 or more carbon atoms is added to the polyepoxy compound (A) with respect to one epoxy group of the polyepoxy compound (A). The polyol resin composition according to any one of claims 1 to 4, wherein the phenolic hydroxyl group of the compound is added in an amount of 0.1 or more. 6. The polyol resin composition according to claim 1, wherein the polyepoxy compound (A) contains the phenol novolak epoxy resin in an amount of 50% by weight or more. 7. The method according to claim 1, wherein 10 to 600 parts by weight of at least one kind of a high-boiling paraffin liquid solvent or a terpene hydrocarbon oil is used in combination with 100 parts by weight of the polyol resin. The polyol resin composition according to the above.