JPS6365112B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a coating resin composition. In particular, the present invention relates to a coating resin composition having excellent mechanical properties such as adhesion and flexibility, and chemical resistance. Tar urethane paints and tar epoxy paints are used for metal products and concrete structures such as ships, steel structures, and water treatment plants.Tar urethane paints are usually used in low temperatures such as winter, and tar epoxy paints are used in high temperatures such as summer. are used, and different base resins are used for both. For this reason, paint users had to purchase and store base resins for summer and winter use separately. In reality, the conventionally commonly used bisphenol A type epoxy resin can be used satisfactorily for tar epoxy paints, but cannot be used for tar urethane due to its low reactivity. Naturally, if the epoxy group was reacted with amine or phenol, it could not be used for tar epoxy. An object of the present invention is to provide a bituminous-containing coating composition that can be cured well with an epoxy resin curing agent, a polyisocyanate curing agent, or a combination thereof. That is, the present invention includes () the general formula (In the formula, R ¹ is hydrogen or a methyl group, R ² is an alkylene group having 3 to 10 carbon atoms, Ar is a divalent aromatic residue obtained by removing the hydroxyl group from an aromatic dihydroxy compound, and n is an average of 1.5 to 15 The number of m is 0.5 on average
15) Compound () Polyisocyanate curing agent or active organic curing agent () Contains bituminous substances, Component () is Component () and Component ()
50 to 150% by weight based on the total amount of Component () is the ratio of the hydroxyl equivalent of the compound of Component () to the isocyanate group equivalent of the polyisocyanate curing agent, or the ratio of the epoxy equivalent of the compound of Component () to the active organic curing agent It relates to a coating resin composition in which the active hydrogen equivalent ratio of 0.5 to 1.2 is blended. The compound of general formula (1), which is an essential component of the composition of the present invention, has the general formula (In the formula, R ¹ , Ar, and n are the same as the general formula (1)) (In the formula, R ² is the same as in general formula (1).) It can be obtained by reacting lactones represented by the following formula. Here, as the divalent phenol compound for obtaining the epoxy resin represented by the general formula (2), mononuclear polyvalent phenols having one aromatic nucleus and polynuclear polyvalent phenols having two or more aromatic nuclei are used. be. Examples of such mononuclear polyhydric phenols include resorcinol, hydroquinone, pyrocatechol, phloroglucinol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and the like. In addition, as an example of polynuclear polyvalent phenol, the general formula (In the formula, Ar' is an aromatic divalent hydrocarbon such as naphthylene group and phenylene group, and phenylene group is preferred for the purpose of the present invention. Y' and Y ₁ may be the same or different, and methyl group , n-propyl group, n
- an alkyl group, preferably with up to 4 carbon atoms, such as butyl, n-hexyl, n-octyl, or a halogen atom, i.e. chlorine, bromine, iodine or fluorine, or a methoxy group, methoxy Alkoxy groups such as methyl, ethoxy, ethoxyethyl, n-butoxy, amyloxy 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. l and z are integers having values ranging from 0 (zero) to a maximum value corresponding to the number of hydrogen atoms in the aromatic ring (Ar') that can be substituted by a substituent, and can be the same or different values. R ³ is for example

[Formula] -O-, -S-, -SO-, -SO ₂ , - (S) _o - (n is an integer of 2 to 6) or an alkylene group such as a methylene group, an ethylene group, a 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, isopropylidene group, isobutylidene group, amylidene group, isoamylidene group , 1-phenylethylidene group, ω-(halogenated dicyclopentadienyl)alkylidene group or cycloaliphatic group such as 1,4-cyclohexylene group, 1,3-
Cyclohexylene group, cyclohexylidene group, halogenated alkylene group, halogenated alkylidene group, halogenated cycloaliphatic group, or alkoxy- and aryloxy-substituted alkylidene group, or alkoxy- and aryloxy-substituted alkylidene group substituted alkylene groups or alkoxy- and aryloxy-substituted cycloaliphatic groups, such as methoxymethylene groups,
Ethoxymethylene group, ethoxyethylene group, 2-
Ethoxytrimethylene group, 3-ethoxypentamethylene group, 1,4-(2-methoxycyclohexane) group, phenoxyethylene group, 2-phenoxytrimethylene group, 1,3-(2-phenoxycyclohexane) group or alkylene group such as phenylethylene group, 2-phenyltrimethylene group,
1,7-phenylpentamethylene group, 2-phenyldecamethylene group or aromatic group such as phenylene group, naphthylene group or halogenated aromatic group such as 1,4-(2-chlorophenylene) group,
1,4-(2-fluorophenylene) groups or alkoxy- and aryloxy-substituted aromatic groups such as 1,4-(2-methoxyphenylene) groups,
1,4-(2-ethoxyphenylene) group, 1,4
-(2-n-propoxyphenylene) group, 1,4
-(2-phenoxyphenylene) group or alkyl-substituted aromatic group such as 1,4-(2-methylphenylene) group, 1,4-(2-ethylphenylene) group, 1,4-(2-n -propylphenylene) group, 1,4-(2-n-butylphenylene) group
group, 1,4-(2-n-dodecylphenylene) group,
formula (R ⁴ is a hydrogen atom, a halogen atom, or a carbon number of 1 to
6 alkyl group), a group represented by the formula (wherein R ⁵ is a hydrogen atom or a hydrocarbon group optionally substituted with a hydroxyl group or an epoxy group), or R ³ is a divalent group such as a divalent hydrocarbon group such as It can also be a ring fused to one of the above Ar′ groups, as in the case of the compound represented by R ³
can also be a polyalkoxy group, such as a polyethoxy group, a polypropoxy group, a polythioethoxy group, a polybutoxy group, a polyphenylethoxy group, or R ³ can be, for example, a polydimethylsiloxy group,
It can be a group containing a silicon atom, such as a polydiphenylsiloxy group, a polymethylphenylsiloxy group, or R ³ can be an aromatic ring, a tertiary amino group, an ether bond, a carbonyl group, or a sulfur or sulfoxide group. There are polynuclear dihydric phenols, which can be two or more alkylene or alkylidene groups separated by a sulfur-containing bond. Particularly preferable polynuclear dihydric phenols have the general formula (In the formula, Y′ and Y ₁ have the same meanings as above, l′ and
z′ has a value of 0 to 4, and R ⁶ is preferably an alkylene or alkylidene group having 1 to 3 carbon atoms or a formula

【formula】

[Formula] or

It is a polynuclear divalent phenol represented by a saturated group represented by the formula: Q is 0 or 1). Examples of such dihydric phenols include 2,2-bis-(4-
hydroxyphenyl)propane, 2,4'-dihydroxydiphenylmethane, bis(2-hydroxyphenyl)methane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-2,6-dimethyl-3- methoxyphenyl)methane, 1,1
-bis(4-hydroxyphenyl)ethane, 1,
2-bis(4-hydroxyphenyl)ethane,
1,1-bis(4-hydroxy-2-chlorophenyl)ethane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)ethane, 1,3-bis(3-methyl-4-hydroxyphenyl)ethane enyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3
-phenyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(2-
Isopropyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxynaphthyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxyphenyl)pentane , 2,2-bis(4-hydroxyphenyl)heptane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, 1,2-bis(4-
Hydroxyphenyl)-1,2-bis(phenyl)
Bis(hydroxyphenyl) alkanes such as propane, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane or 4,4'-dihydroxybiphenyl, 4,4'-dihydroxyoctachlorobiphenyl , 2,2'-dihydroxybiphenyl, dihydroxybiphenyl such as 2,4'-dihydroxybiphenyl or bis-(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, chlor-2, 4-dihydroxydiphenylsulfone, 5-chloro-4,4'-dihydroxydiphenylsulfone, 3'-chloro-
Di(hydroxydiphenyl) sulfones such as 4,4'-dihydroxydiphenyl sulfone or bis(4-hydroxyphenyl) ether, 4,3'-
(or 4,2'- or 2,2'-dihydroxydiphenyl)ether, 4,4'-dihydroxy-2,6
- Dimthyl diphenyl ether, bis(4-hydroxy-3-isobutylphenyl) ether, bis(4-hydroxy-3-isopropylphenyl) ether, bis(4-hydroxy-3-chlorophenyl) ether, bis(4-hydroxy-3-isobutylphenyl) ether, -Hydroxy-
3-fluorophenyl) ether, bis(4-hydroxy-3-bromphenyl) ether, bis(4-hydroxynaphthyl) ether, bis(4-fluorophenyl) ether,
-hydroxy-3-chlornaphthyl) ether,
bis(2-hydroxybiphenyl) ether,
4,4'-dihydroxy-2,6-dimethoxy-diphenyl ether, 4,4'-dihydroxy-2,
Di(hydroxyphenyl) ethers such as 5-diethoxydiphenyl ether are included, and 1,1
-bis(4-hydroxyphenyl)-2-phenylethane, 1,3,3-trimethyl-1-(4-
hydroxyphenyl)-6-hydroxyindan,
2,4-bis(p-hydroxyphenyl)-4-
Methylpentane is also suitable. Furthermore, another group of preferred polynuclear dihydric phenols has the general formula: (Here, R ⁸ is a methyl or ethyl group, R ⁷ is an alkylidene group having 1 to 9 carbon atoms or other alkylene group, and p is 0 to 4), for example, 1,4-bis(4- hydroxybenzyl)benzene, 1,4-bis(4-hydroxybenzyl)tetramethylbenzene, 1,4-bis(4-hydroxybenzyl)tetraethylbenzene, 1,4-
Bis(p-hydroxycumyl)benzene, 1,3
-bis(p-hydroxycumyl)benzene and the like. In addition, as the lactones represented by general formula (3),
For example, propiolactone, butyrolactone, δ
-Valerolactone, γ-valerolactone, ε-caprolactone, etc. are preferably used. The reaction between lactones and hydroxyl groups in epoxy resins is usually carried out using basic catalysts (alkali, tertiary amines, etc.) or acidic catalysts (para-toluenesulfonic acid, sulfuric acid, etc.)
The reaction is carried out at a temperature of 50 to 200°C, preferably 80 to 120°C. The reaction ratio between the hydroxyl groups and lactones in the epoxy resin can be arbitrarily selected, and is 0.5 to 15, preferably 1 to 5 lactones per equivalent of hydroxyl groups.
It is equivalent. The polyisocyanate curing agent used in the composition of the present invention may be commercially available, such as toluene diisocyanate, xylylene diisocyanate, crude diphenylmethane diisocyanate,
Examples include hexamethylene diisocyanate, lysine diisocyanate methyl ester, trimethylolpropane toluene diisocyanate 3-mole adduct, and high molecular weight polyisocyanates (prepolymers) obtained from these and various active hydrogen compounds. The blending ratio of the polyisocyanate curing agent is 0.5 between the hydroxyl group equivalent and the isocyanate group equivalent.
A ratio of ~1.2, preferably 0.7 to 1.0 is good. As the active organic curing agent for epoxy resin used in the composition of the present invention, all curing agents for ordinary epoxy resin coatings can be used, such as aliphatic polyamines, aromatic polyamines, alicyclic modified polyamines, Examples include polyamides, amino resins, carboxylic acids, and the like. The blending ratio of the active organic curing agent is such that the ratio of the epoxy equivalent of the compound of component () to the active hydrogen equivalent of the active organic curing agent is 0.5 to 1.2. Further, as the bituminous substance used in the composition of the present invention, coal tar, coal tar pitch, various types of cuttlefish tar, swollen charcoal, asphalt, white tar, etc. can be used, and the proportion used is the resin component (and) It can be used in any proportion, but preferably 50 to 150% by weight. The coating composition of the present invention may optionally contain additives such as fillers, diluents, dehydrating agents, etc. in addition to the above-mentioned essential components. EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited by these Examples. In the examples, parts mean parts by weight. Example 1 115 parts of butyrolactone was added to 500 parts of bisphenol A diglycidyl ether (epoxy equivalent: 500, hydroxyl equivalent: 430) to obtain resin A-1. Resin A-1 has an epoxy equivalent of 620 and a hydroxyl equivalent of 530.
It was from. Example 2 340 parts of caprolactone was added to 500 parts of bisphenol F diglycidyl ether (epoxy equivalent: 1000, hydroxyl equivalent: 340) to obtain resin A-2. Resin A-2 has an epoxy equivalent of 1680 and a hydroxyl equivalent
It was from 570. Example 3 Resin A-3 was obtained by adding 240 parts of δ-valerolactone to 500 parts of bisphenol A diglycidyl ether (epoxy equivalent: 2000, hydroxyl equivalent: 310). Resin A-3 has an epoxy equivalent of 3100 and a hydroxyl equivalent
It was 470. Tar urethane paints and tar epoxy paints were prepared using the resins A-1 to A-3 obtained in Examples 1 to 3 with the following formulations, and a coating test was conducted. The results are shown in Tables 1 and 2.

【table】

【table】

Claims (1)

[Claims] 1. As an essential component, () General formula (In the formula, R ¹ is hydrogen or a methyl group, R ² is an alkylene group having 3 to 10 carbon atoms, Ar is a divalent aromatic residue obtained by removing the hydroxyl group from an aromatic dihydroxy compound, and n is an average of 1.5 to 15 The number of m is 0.5 on average
15) Compound () Polyisocyanate curing agent or active organic curing agent () Contains bituminous substances, Component () is Component () and Component ()
50 to 150% by weight based on the total amount of Component () is the ratio of the hydroxyl equivalent of the compound of Component () to the isocyanate group equivalent of the polyisocyanate curing agent, or the ratio of the epoxy equivalent of the compound of Component () to the active organic curing agent A resin composition for coating, which is blended in such a proportion that the active hydrogen equivalent ratio of is 0.5 to 1.2.