JPS587457A - Coating resin composition - Google Patents

Abstract

PURPOSE:To prepare the titled composition having excellent corrosion resistance, water resistance, adhesivity and mechanical characteristics, and suitable for forming coating film, by using a polyether polyol resin derived from an epoxy resin and a specific compound, an isocyanate compound and a bituminous material as raw materials. CONSTITUTION:The objective composition is prepared by compounding (A) a polyether polyol redin obtained by reacting (i) a high-molecular epoxy resin having an epoxy equivalent of 1,000-4,000 and prepared by converting an adduct of a dihydric phenol (e.g. bisphenol A) and an alkylene oxide (e.g. ethylene oxide) to glycidyl ether with e.g. epichlorohydrin, and reacting the ether with a dihydric phenol in the presence of a catalyst such as NaOH with (ii) a compound reactive with epoxy group (e.g. phenol), (B) an isocyanate compound (e.g. polyisocyanate), and (C) a bituminous material (e.g. coal tar) or its substitute. The ratio of the hydroxyl group equivalent of the component (A) to the isocyanate group equivalent of the component (B) is 0.4-1.2.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coating resin composition. 41. The present invention relates to a coating resin composition that is suitable for forming coating films and has excellent corrosion resistance, water resistance, other writeability, and mechanical properties.

Conventionally, dihydric phenols, especially 2,2
- A high molecular weight epoxy resin is obtained by further reacting bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A) and epichlorohydrin with dihydric phenol, and further addition of eins. Generally, a polyol resin is obtained and this is blended with a polyisocyanate group-containing compound as a curing agent.

However, although it is known that the mourning polyol based on the above-mentioned high molecular weight epoxy resin has excellent round physical properties, it has insufficient solubility in organic solvents, and the cured product is extremely hard and has poor flexibility. Due to these drawbacks, there were significant restrictions on its use when used as a paint.

An object of the present invention is to provide a coating resin composition which eliminates the above-mentioned drawbacks and has excellent properties. Kll has been reached.

That is, the coating resin composition of the present invention is obtained by reacting a substituted or unsubstituted glycidyl ether of an alkylene oxide adduct of dihydric phenol with dihydric phenol to obtain a high molecular weight epoxy resin, which is further reacted with an epoxy group. characterized by containing a polyether polyol resin obtained by reacting a compound having a group having a property, a compound having more than one incyanate group, and a bituminous substance and/or its substitute. It is something.

Here, dihydric phenol refers to a phenol that has one or more aromatic nuclei in its molecule, and the aromatic nucleus is substituted with two hydroxyl groups, and includes mononuclear dihydric phenol and polynuclear dihydric phenol.
Examples include hydric phenols.

Examples of such mononuclear dihydric phenols include resorcinol, hydrquinone, pyrocatechol, phloroglynol s 1. s-1 hydroxynaphthalene, 2
, 7-hydroxynaphthalene, 2,6-hydroxynaphthalene, and the like.

Examples of polynuclear dihydric phenols include aromatic divalent hydrocarbons having the general formula, and phenylene groups are preferred for the purpose of the present invention. Y' and Y may be the same or different, and may be a methyl group, n-propyl group, n-butyl group, -n
- an alkyl group, preferably with up to 4 carbon atoms, such as hexyl, n-octyl, or a halogen atom, i.e. chlorine, bromine, iodine or fluorine, or a methoxy group, methoxymethyl; Alkoxy groups, such as ethoxyethyl, n-butoxy, amyloxy groups, are preferably alkoxy groups having up to 4 carbon atoms. When a substituent other than a hydroxyl group is present on either or both of the above-mentioned aromatic divalent hydrocarbon groups, these substituents may be the same or different. m and 厘 are integers having values from 0 (zero) to the maximum value corresponding to the number of hydrogen atoms in the aromatic 1lI (mr) that can be substituted by a substituent, and are the same or different values -808- or Alkylene groups such as ethylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 2-ethylhexamethylene group, octamethylene group, nonamethylene group, decamethylene group or alkylidene group such as ethylidene group, propylidene group group, imbutylidene group, imbutylidene group, amylidene group, imbutylidene group, 1-72ndylethylidene group, or cycloaliphatic group, such as 1,4-cyclohexylene group, 1,3-cyclohexylene group, cyclohexylidene group, or halogenated alkylene groups or halogenated alkylidene groups or halogenated cycloaliphatic groups or alkoxy- and aryloxy-substituted alkylidene groups or alkoxy- and aryloxy-substituted substituted alkylene groups or alkoxy- and aryloxy-substituted cycloaliphatic groups, such as methoxymethylene, ethoxyethylene, ethoxyethylene, 2-
Ethoxytrimethylene group, 5-ethoxypentamethylene group, 1,4-(2-methoxyfuclohexane) group, phenoxyethylene group, 2-7 dino'oxytrimethylene group,
1. ! I-(2-phenoxycyclohexane) group or alkylene group such as phenylethylene group, 2-phenyltrimethylene group, 1,7-7enylpentamethylene group, 2-7enyldecamethylene group or aromatic group such as phenylene groups, naphthylene groups or halogenated aromatic groups such as 1.4-(2-chlorophenylene) groups, 1.4-(2-fluorophenylene) groups or alkoxy- and aryloxy-substituted aromatic groups. Group group e.g. 1
,．． 4-(2-methoxyphenylene) group, 1,4-(2
-ethoxyphenylene) group, 1.4- (2-n-propylphenylene) group, 1.4- (2-phenoxyphenylene) group or an alkyl-substituted aromatic group such as 1.4- (2-ethyl phenylene) group, 1$4- (
2-ethylphenylene) group, 1. a-(2-n-propylphenylene) group, 1,4-(2-n-butylphenylene) group, 1,4-(2-n-)'decylphenylene) group, etc. or R can also be a ring fused to said mr group-2, as in the case of the compound represented by the formula, or R can be a polyethoxy group. , polypropoxy group, polythioethoxy group, polybutoxy group, polyphenylethoxy group, or R group may be polydimethylsiloxy group, polydiphenylsiloxy group, polymethylphenylsiloxy group, etc. It can be a group containing a silicon atom, such as a group, or a group separated by an aromatic ring, a tertiary-amino ether bond, a carbonyl group, or a sulfur-containing bond such as sulfur or sulfoxide. Among these polynuclear dihydric phenols, particularly preferred are polynuclear dihydric phenols represented by the general formula (wherein 7 and Y are the above-mentioned has the same meaning as m and 2
has a value of 0 to 4, and Rlt-1 is preferably an alkylene group or alkylidene group having 1 to 3 carbon atoms or a saturated group represented by the formula.

Examples of such dihydric phenols include 2,2-bis(p-hydroxyphenyl)propane, commonly referred to by the trade name bisphenol A, 2,4'-dihydroxydiphenylmethane, bis(2-hydroxyphenyl)methane, bis(4-
-hydroxyphenyl)methane, bis(4-hydroxy-2,6-dimethyl-5-methodiphenyl)methane,
1.1-His(4-hydroxyphenyl)ethane, 1
．． 2-bis(4-hydroxyphenyl)ethane, 1.1
-bis(4-hydroxy-2-chloro7enyl)ethane, 1,1-bis(s,5-dimethyl-4-hydroxyphenyl)ethane, 1. is-bisCs-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-
dichloro-4-hydroxyphenyl)propane, 2,2
-bis(3-phenyl-4-hydroxyphenyl)furopane, 2,2-bix(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(2-isopropyl-4-hydroxyphenyl)furopane, 2 .2-bis(4-hydroxynaphthyl)propane, 2,2-bis(
4-hydroxyphenyl)pentane, 5. s-Bis(hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hebutane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)schiftetrahexylmethane, 1,2-bis( 4-hydroxyphenyl) -1,2-bis(phenyl)furopane, 2.2-
Bis(hydroxyphenyl) alkanes such as bis(4-hydroxyphenyl)-1-phenylpropane, or 4,4#-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 2゜4'-dihydroxybiphenyl Dihydroxybiphenyl or bis(4-hydroxyphenyl)sulfone, 2,4'-'/hydroxydiphenylsulfone, chlor-2,4-dihydroxydiphenylsulfone, 5-chloro-4,4'-dihydroxydiphenylsulfone 51-chlor -4,4'-dihydroxydiphenyl sulfone, etc. (hydroxyphenyl) sulfone or bis(4-hydroxyphenyl) ether, 4.5'-C or 4.2'- or 2.2-
dihydroxy-diphenyl)ether, 4,4-
Dihydro-2,6-dimethyldiphenyl ether, bis(4-hydroxy-s-inbutylphenyl) ether, bis(4-hydroxy-5-inpropylphenyl) ether, bis(4-hydroxy-5-chloro7)
enyl) ether, bis(4-hydroxy-5-fluorophenyl) ether, bis(4-hydroxy-5-bromphenyl) ether, bis(4-hydroxynaphthyl) ether, bis(4-hydroxy-3- chlornaphthyl) ether, bis(2-hydroxybiphenyl) ether, 4,4I-dihydroxy-2,6-simethoxydi7dynyl ether, 4,4I-dihydroxy-2,5
pear (hydroxyphenyl) ethers such as -jetoxydiphenyl ether, and 1,1-his(4-
hydroxyphenyl)-2-phenylethane, 1. ! 5
．． 5-) Limethyl-1-(4-hydroxyphenyl)
Also suitable are -6-hydroxyindan, 2,4-bis(p-hydroxyphenyl)-4-methylpentane.

Furthermore, another group of preferable poly-dihydric phenols has the general formula % (where R5 is a methyl or ethyl group, and R2 has 1 to 1 carbon atoms).
9 alkylidene group or other alkylene group, p is 0 to 4), such as 1,4-bis(4-
hydroxybenzyl)benzene, 1,4-bis(4-hydroxybenzyl)tetramethylbenzene, 1,4-bis(4-hydroxybenzyl)tetraethylbenzene,
Examples include 1.4-bis(cyhydroxycumyl)benzene and 1°5-bix(p-hydroxycumyl)benzene.

Other polynuclear dihydric phenols include, for example, initial condensates of phenols and carbonyl compounds (e.g., phenol resin initial condensates, condensation reaction products of phenol and acrolein, condensation reaction products of phenol and glyoxal, phenol and pentanediallyl condensation reaction products, resorcinol and acetone condensation reaction products, xylene-phenol-formalin initial condensates), condensation products of phenols and polychloromethylated aromatic compounds (
Examples include condensation products of phenol and bischloromethylxylene).

The alkylene oxide to be reacted with the dihydric phenol is, for example, an alkylene oxide having 2 to 4 carbon atoms, and preferred examples include ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. Can be mentioned.

Therefore, the production of an alkylene oxide adduct of dihydric phenol is carried out by reacting the dihydric phenol and alkylene oxide in the presence of an alkaline or acidic catalyst. The ratio of 1 to 10 alkylene oxides per 1 hydroxyl group of the dihydric phenol is preferably 1 to 1 to S.

The alkylene oxide adduct of dihydric phenol thus obtained is then subjected to a reaction with one selected from shrimp halogenohydrin, methyl shrimp halogenohydrin, and dihalogenohydrin in the presence of an alkali hydroxide catalyst. , to give a substituted or unsubstituted glycidyl ether compound.

Here, examples of epihalogenohydrin, methylepihalogenohydrin, and dihalogenohydrin include epichlorohydrin, ebibromohydrin, methylepichlorohydrin,
Examples include methylebibromohydrin, dichlorohydrin, dibromohydrin, etc., and it is particularly preferable to use epichlorohydrin, ebibromohydrin, and methylepichlorohydrin.

Here, an alkylene oxide adduct of dihydric phenol, epihalogenohydrin, methyl epihalogenohydrin,
The reaction rate with 91 types selected from dihalogenohydrins is
The latter is preferably 1 to 20 moles per 1 mole of the former, and the epoxy equivalent of the substituted or unsubstituted glycidyl ether compound obtained is preferably 200 to 600.

Furthermore, when the mono-substituted or unsubstituted glycidyl ether compound is reacted with dihydric phenol at a temperature of 80 to 250 DEG C. in the presence of a catalyst, a high molecular weight epoxy resin can be obtained.

The epoxy equivalent of the obtained high molecular weight epoxy resin is 100
0 to 4000 is preferred.

Here, the dihydric phenol mentioned above may be any of the dihydric phenols exemplified as the dihydric phenol that can be used in the production of the alkylene oxide adduct of dihydric phenol.

In addition, the catalysts used for this reaction include caustic soda,
Inorganic alkalis such as caustic potash and soda carbonate, tertiary amines such as triethylamine, triethanolagine, dimethylamine, and pyridine, imidazoles, quaternary ammonium salts such as tetramethylammonium chloride, boron trifluoride, and aluminum chloride. , tin tetrachloride, titanium tetrachloride, etc.0 Furthermore, the reaction ratio of the above-mentioned substituted or unsubstituted glycidyl etherified product and dihydric phenol is such that the epoxy equivalent weight required by the high molecular weight epoxy resin is obtained. arbitrarily determined.

Compounds having groups reactive with high molecular weight epoxy resins include, for example, compounds containing phenol groups, compounds containing amino groups, and compounds containing carboxyl groups.

The compound containing a phenol group used at this time includes, for example, monohydric phenol or dihydric phenol,
Particularly preferred are monohydric phenols, such as phenol, cresol,
Examples include xylenol and t-butylphenol.

Examples of compounds containing amino groups include primary amines and secondary amines, and hydroxylamine containing a hydroxyl group is preferred. Examples of primary amines include methylamine, ethylamine, propylamine, etc.; examples of secondary amines include diptylamine; and examples of hydroxylamine include ethanolamine, glopanolamine, jetanolamine, diisopropylamine, etc. Examples include tool amines and the like.

Examples of the compound having a carboxyl group include monocarboxylic acids and dicarboxylic acids, with monocarboxylic acids being preferred. Examples of monocarboxylic acids include acetic acid, propionic acid, and lactic acid; examples of dicarboxylic acids include maleic acid, adipic acid, succinic acid, phthalic acid, inphthalic acid, and tetrahydroheptalic acid.

The reaction ratio between a high molecular weight epoxy resin and a compound having a group that is reactive with an epoxy group is such that the ratio of the group that is reactive with an epoxy group that the latter has to the epoxy group that the former has is 1. A ratio of 1 to 0.7, particularly 1.0 to 0.9 is preferred.

In addition, when the reaction between a high molecular weight epoxy resin and a compound having a group reactive with an epoxy group is used, for example, a compound having a phenol group or a carboxyl group is used as the compound having a group reactive with an epoxy group. It may be carried out in the presence of a catalyst such as, for example, at a temperature of 80 to 250°C, and if a compound having an amino group is used as the compound having reactivity with an epoxy group, it may be carried out without a catalyst, for example, at a temperature of 80 to 250 °C.
It can be carried out at a temperature of 0 to 150°C.

Compounds having more than one inocyanate group that can be used in the present invention include, for example, toluene diisocyanate, xylylene diisocyanate, crude diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate methyl ester, and toluene of trimethylolpropane. Diisocyanate 5 mol adduct and high molecular weight polyisocyanate obtained from these (
prepolymers), etc.

The blending ratio of the compound having more than one isocyanate group is such that the blending ratio of 7 isocyanate group equivalents of hydroxyl group equivalents in the polyether polyol resin is 0.4 to 1.2, preferably 0.7 to 1.0. A ratio like this is good.

As the bituminous substance used in the composition of the present invention, coal tar, coal tar pitch, various cutback tars, swollen charcoal materials, asphalt, etc. can be used.

There are various alternatives to bituminous substances, such as aromatic oil resins, coumaron resins, petroleum resins, DOP, DBP, which are generally used as diluents, and other high boiling point substances such as petroleum-based and coal-based substances. Neutral oil etc. can be used. The blending ratio of the bituminous substance and/or the substitute for the bituminous substance is generally 0.5 to 2 times the weight of the polyether polyol resin.

Various curing catalysts, fillers, diluents, dehydrating agents, resins, etc. can be added to the composition of the present invention, if necessary.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

The parts in the examples are by weight.

Examples 1 to 6 and Comparative Examples 1 to 6 (1) Production of polyether polyol resin [Production Example 1] 150 parts of a liquid epoxy resin (epoxy equivalent = 410) obtained by adding propylene oxide to bisphenol A and converting it into glycidyl ether. Sodium hydroxide was added as a catalyst to 25 parts of bisphenosim, and the mixture was heated and stirred at 200° C. for 10 hours.

The obtained high molecular weight epoxy resin has an epoxy equivalent of 12
It was 50.

Furthermore, 14 parts of phenol was added, and the mixture was heated and stirred at 200° C. for 6 hours to obtain a polyether polyol resin (f). The hydroxyl equivalent of the scissor polyether polyol resin was 420, and it was arbitrarily dissolved in an aromatic solvent such as xylene or toluene.

[Production Example 2] Bisphenol A is added with ethylene oxide to form a glycidyl ether, resulting in a round liquid epoxy resin (epoxy equivalent =
s1a) + so part and Bigen 7Z/-A/Suru*:/ 17
dimethylamine was added as a catalyst, and the mixture was heated and stirred at 180° C. for 15 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 1900. Further, 10 parts of jetanolamine was added and stirred at 110°C for 3 hours to obtain a polyether polyol resin (1[). The hydroxyl equivalent of the 0-mosquito polyether polyol resin was 21°, and aromatic solvents such as xylene and toluene were used. Optionally dissolved in

[Production Example 5] Bisphenol] FK Sodium hydroxide was added as a catalyst to 150 parts of a liquid epoxy resin (epoxy equivalent = 3100) obtained by adding propylene oxide and converted to glycidyl ether (epoxy equivalent = 3100) and 742 parts of bisphenol, and the mixture was heated and stirred at 150°C for 16 hours. . The obtained high molecular weight epoxy resin is
The epoxy equivalent was 2,500. Furthermore, 10 parts of benzoic acid was added and heated and stirred at 170°C for 7 hours to obtain polynyfkytt.
A polyether polyol resin (candle) was obtained.The polyether polyol resin had an O hydroxyl content of 1540, and was optionally dissolved in an aromatic solvent such as xylene or toluene.

[Production Example 4] Adeka Resin IP4100 manufactured by Asahi Denka Kogyo obtained from bisphenol A and epichlorohydrin (epoxy equivalent =
1?0) Sodium hydroxide was added as a catalyst to 150 parts of bisphenol and 5 parts of bisphenol, and the mixture was heated and stirred at 180°C for 5 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 975. Add 19 parts of phenol to 20 parts
The mixture was heated and stirred at 0° C. for 6 hours to obtain a polyether polyol resin (ml). The hydroxyl equivalent of the cough polyether polyol resin is 296, and it cannot be dissolved in an aromatic solvent such as acetic acid, xylene, or toluene alone, and requires the addition of a ketone solvent or an alcohol solvent.

[Production Example 5] 1 jo part of Asahi Denka Kogyo's Adecare yKP5100 (epoxy equivalent = 4so) obtained from bisphenol A and epichlorohydrin, 12 parts of Bisphe/-kB', and dimethylamine as a catalyst were added, and the mixture was heated and stirred at 150°C for 6 hours. 90 The obtained high molecular weight epoxy resin had an epoxy equivalent of 1,100. Furthermore, jetanolamine 17
9 and stirred at 150° C. for 2 hours to obtain polyether polyol resin (V). The hydroxyl equivalent of the cough polyether polyol resin is 210, and it cannot be dissolved in an aromatic solvent such as xylene or toluene alone, so it is necessary to add a ketone solvent or an alcohol solvent.

[Production Example 6] Sodium hydroxide was added as a catalyst to 150 g of Asahi Denka Kogyo's Adekal Resin 11174900 (-c boxy 4 amount = 187) obtained by mixing bisphenol 1 and epichlorohydrin and 770 parts of bisphenol, and the mixture was heated and stirred at 150°C for 15 hours. .

The obtained high molecular weight epoxy resin has an epoxy equivalent of 23
00 and nine.

Further, 12 parts of benzoic acid was added and the mixture was heated and stirred at 170°C for 7 hours to obtain polyether polyol resin (9). The hydroxyl equivalent of the polyether polyol resin is 280, and it cannot be dissolved in an aromatic solvent such as xylene or toluene alone, so it is necessary to add a ketone solvent or an alcohol solvent.

(2) Preparation and evaluation of coating resin composition [! ] to IJ) to prepare coating resin compositions having the compositions shown in Tables 1 and 2.

In order to evaluate their performance, the coatings were coated and dried for 7 days at room temperature, and then the physical properties of the coatings were tested. The results were as shown in Tables 1 and 2.

Claims (1)

[Claims] A high molecular weight epoxy resin is obtained by reacting a substituted or unsubstituted glycidyl etherified product of an alkylene oxide adduct of dihydric phenol with dihydric phenol, and reacting this with a compound having a group reactive with the KIK epoxy group. Coating 11 characterized in that it contains a polyether polyol resin, a compound having more than one incyanate group, and a historical substance and/or its substitute.
Fat composition.