JP2003238650A - Polyol resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyol resin composition capable of thick film coating and excellent in corrosion resistance and flexibility, and therefore suitable as a cationic electrodeposition coating. <P>SOLUTION: The polyol resin composition comprises a polyol compound obtained by reacting a polyglycidyl ether compound represented by general formula (I) (wherein X and Y are represented by formulae (II) and (III), respectively) with an active hydrogen compound. In formulae (II) and (III), R1 is an alkyl, aryl, alkylaryl or arylalkyl group; R2 is a hydrogen atom or a methyl group; A is a direct bond, an alkylene group, a cycloalkylene group, an alkylene group substituted with a halogen or an alkyl, perfluoroalkyl, cycloalkyl or aryl group, -O-, -S-, -SS-, -SO-, -SO<SB>2</SB>-, -CO-, -C-CO- or -O-CO-; m and n are each 0 or 1 and total up to 1 or 2; p and q are each 0-10 and total up to 1-10; and 1 is 0-5. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyol resin composition, and more particularly to a polyol resin composition containing a specific polyol compound, capable of thick film coating, and excellent in corrosion resistance and suitable for a cationic electrodeposition coating composition. .

[0002]

A polyol compound obtained by adding an active hydrogen compound such as a secondary amine compound to an epoxy resin is combined with a curing agent such as a melamine compound, a phenol compound or an isocyanate compound. It is known that a coating film having excellent anticorrosion properties and adhesion to a substrate can be formed by using the same.

As a coating method for automobiles, cationic electrodeposition coating has become popular because of the advantages that it is possible to perform automatic coating with a uniform film thickness, and because it is water-based, it has a small environmental load. . In the cationic electrodeposition coating, among the above, a polyol resin composition containing a polyol compound obtained by ring-opening an epoxy resin with a secondary amine compound and a blocked isocyanate compound has been used as a coating material.

However, when a polyol resin composition obtained from a general-purpose epoxy resin such as a polyglycidyl ether compound of bisphenol A is used, the coating film has poor impact resistance and throwing power, and a cellosolve system for thickening the film. There are drawbacks such as the need to use a solvent.

Accordingly, it is an object of the present invention to provide a polyol resin composition which is capable of thick film coating, is excellent in corrosion resistance and flexibility and is suitable as a cationic electrodeposition coating composition.

[0006]

Means for Solving the Problems As a result of intensive studies by the present inventors, a polyol resin composition obtained by reacting a specific polyglycidyl ether compound with an active hydrogen compound is a polyol resin composition having excellent corrosion resistance. In particular, a polyol resin composition containing a polyol compound obtained by reacting a specific polyglycidyl ether compound and a secondary amine compound is a thick film when used in a cationic electrodeposition coating composition. The inventors have found that a coating film that can be coated, and that has excellent corrosion resistance and flexibility can be provided, and arrived at the present invention.

That is, the present invention provides a polyol resin composition containing a polyol compound obtained by reacting a polyglycidyl ether compound represented by the following general formula (I) with an active hydrogen compound. In particular, the present invention provides a polyol resin composition in which the active hydrogen compound is at least one selected from secondary amine compounds.

[0008]

[Chemical 3]

[0009]

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

In the above general formula (I) representing the polyglycidyl ether compound according to the present invention, examples of the alkyl group represented by R1 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, Tributyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, cyclohexylmethyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Examples thereof include linear, branched or cyclic groups such as heptadecyl and octadecyl, and these may contain an unsaturated group. Examples of the aryl group represented by R1 include groups such as phenyl and naphthyl. Examples of the alkylaryl group represented by R1 include groups such as phenyl and naphthyl substituted with an alkyl group as exemplified above. Examples of the arylalkyl group represented by R1 include groups such as benzyl, α-methylbenzyl, α, α-dimethylbenzyl and the like. Among these, as R1, a phenyl group which may be substituted with an alkyl group having 4 to 18 carbon atoms or an alkyl group having 1 to 3 carbon atoms has a good balance between low absorbency and low elasticity. It is preferable because the product can be easily obtained.

In the above general formula (I), examples of the alkylene group represented by A include groups such as methylene, ethylene and propylene, and examples of the cycloalkylene group include:
Examples thereof include 1,1-cycloalkylene group and the like, and examples of the substituted alkylene group include groups such as methylmethylene, dimethylmethylene, phenylmethylene, phenylmethylmethylene and cyclohexyl. Among these, it is particularly preferable that A is a group represented by the following general partial structural formula, because in addition to corrosion resistance, a substance excellent in other physical properties can be obtained.

[0012]

[Chemical 4]

In the above general partial structural formula, examples of the alkyl group having 1 to 4 carbon atoms represented by R3 and R4 include groups such as methyl, ethyl, propyl and butyl.

In the above general formula (I), m and n are 1 or 2 in total, and p and q are 1 to 10 in total.
If it exceeds the respective ranges, it may not be possible to obtain a product having a good balance of heat resistance, flexibility and the like, which is not preferable.

The polyglycidyl ether compound represented by the above general formula (I) is obtained by reacting an oxyalkylene adduct of a bisphenol compound with an alkyl monoglycidyl ether using a Lewis acid catalyst to form epichlorohydrin on the hydroxyl group. It can be produced by reacting in the presence of an alkali and a phase transfer catalyst.

Here, examples of the Lewis acid catalyst include boron trifluoride, complexes thereof, and stannic chloride. Examples of the alkali include metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide. Examples of the interlayer transfer catalyst include, for example, tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride,
N, N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N
-Methylpyrrolidinium bromide, N-benzyl-N-
Methylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium bromide, N-butyl-N-methylmorpholinium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methyl Morpholinium bromide, N-methyl-N-benzylpiperidinium chloride, N-methyl-N-benzylpiperidinium bromide, N, N-dimethylpiperidinium iodide,
N-methyl-N-ethylpiperidinium acetate, N
-Methyl-N-ethylpiperidinium iodide and the like can be mentioned.

The polyol compound used in the present invention is
It is obtained by reacting the polyglycidyl ether compound represented by the general formula (I) with an active hydrogen compound. Examples of the active hydrogen compound include amine compounds and phenol compounds. Among the,
It is preferable to use at least one selected from secondary amine compounds.

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 mentioned, and in particular, when an alkanolamine compound is used, a polyol resin composition having excellent properties can be obtained, which is preferable.

In obtaining the polyol compound used in the present invention, the reaction ratio of the polyglycidyl ether compound represented by the general formula (I) and the active hydrogen compound is such that the latter has a ratio to the epoxy group possessed by the former. The ratio of active hydrogen groups contained is preferably 1.1 to 0.7, and particularly preferably 1.0 to 0.9.

The reaction between the polyglycidyl ether compound represented by the general formula (I) and the active hydrogen compound is carried out in the presence of the above-mentioned catalyst when a phenol compound is used as the active hydrogen compound. For example 80-25
It may be carried out at a temperature of 0 ° C. When an amine compound is used as the active hydrogen compound, for example, 60 to 1 without a catalyst is used.
It can be carried out at a temperature of 50 ° C.

In the polyol resin composition of the present invention,
The polyol compound obtained by reacting the polyglycidyl ether compound represented by the general formula (I) with an active hydrogen compound may be used alone, but is active with a polyepoxy compound other than the polyglycidyl ether compound. It is preferable to use it in combination with a polyol compound obtained by reacting with a hydrogen compound (hereinafter, also referred to as other polyol compound) because various physical properties can be improved.

Here, as the polyepoxy compound other than the polyglycidyl ether compound represented by the general formula (I), which can provide other polyol compound, the polyglycidyl ether represented by the general formula (I) is used. Aromatic polyglycidyl ether compounds other than the compounds (hereinafter, also referred to as other aromatic polyglycidyl ether compounds) are preferable. Examples of the other aromatic polyglycidyl ether compounds include hydroquinone, resorcin, pyrocatechol, polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as phloroglucinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), Methylene bis (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, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin Novolak, bisphenol A novolak, bisphenol F novolak,
Examples thereof include polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as terpene diphenol.

Here, the polyol compound obtained by reacting the polyglycidyl ether compound represented by the general formula (I) with an active hydrogen compound is 5 to 50% by mass, particularly 1
0 to 40% by mass, and 95 to 50% by mass of a polyol compound obtained by reacting the other aromatic polyglycidyl ether compound with an active hydrogen compound, particularly 90 to 6
The content of 0% by mass is preferable because it provides a material with higher corrosion resistance and higher flexibility.

Further, in the present invention, when the polyglycidyl ether compound represented by the general formula (I) is produced, the amount of alkyl monoglycidyl ether used is reduced to m.
It is also possible to use a mixture of a compound in which at least one of n and n is 1 and a compound in which both m and n are 0. In that case, m + n is preferably 0.1 to 1,
It is particularly preferably 0.2 to 0.8.

The polyol resin composition of the present invention is curable by using a curing agent together with the polyol compound obtained by reacting the polyglycidyl ether compound represented by the general formula (I) with an active hydrogen compound. The polyol resin composition can be provided. The amount of the curing agent used is preferably an amount such that the hydroxyl group of the polyol compound and the reactive group of the hydroxyl group of the curing agent are equal to each other, but may actually be increased or decreased for convenience of handling. The curing agent can be used without particular limitation as long as it is usually used as a curing agent for polyol resin, for example, melamine, methylol melamine, methyl melamine, butyl melamine, melamine resin. , Urea resin, benzoguanamine, guanamine resin, melamine-formaldehyde resin, phenol resin, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated TDI, hydrogenated MDI, isophorone diisocyanate (IPDI), isocyanate resin,
Examples thereof include a blocked polyisocyanate compound obtained by modifying a urethane prepolymer resin obtained by reacting an isocyanate compound with a general polyol with a blocking agent such as ε-caprolactam, oxime, phenol and alcohol. In the present invention, it is preferable to use a blocked polyisocyanate compound among these.

In the polyol resin composition of the present invention, if necessary, a curing catalyst; a reactive or non-reactive diluent such as monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol and coal tar. (Plasticizer); glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, fine powder silica, titanium dioxide, carbon black, graphite,
Fillers or pigments such as iron oxides and bituminous substances; thickeners; thixotropic agents; flame retardants; antifoaming agents; rust preventives; colloidal silica, colloidal alumina, etc. Furthermore, sticky resins such as xylene resin and petroleum resin can be used together.

The polyol resin composition of the present invention is particularly suitable for use as a cationic electrodeposition coating composition because it has excellent corrosion resistance and is capable of thick film coating. In addition, for example, concrete, cement mortar, Paint or adhesive for various metals, leather, glass, etc .; adhesive tape for packaging, adhesive label, frozen food label, removable label, POS label, adhesive wallpaper, adhesive for adhesive flooring agent; art paper, coated paper, lightweight coated paper , Cast coated paper,
Coated paperboard, carbonless copying machines, processed paper such as impregnated paper; natural fiber, synthetic fiber, glass fiber, carbon fiber, metal fiber, etc. sizing agent, anti-fray agent, fiber processing agent such as processing agent; sealing material, It can be used in a wide range of applications such as cement admixtures and building materials such as waterproofing materials.

Next, a preferred embodiment of using the polyol resin composition of the present invention as a cationic electrodeposition coating composition will be described below.

A polyol resin of the present invention containing a polyol compound obtained by reacting a polyglycidyl ether compound represented by the general formula (I) with an active hydrogen compound, and further containing a blocked polyisocyanate compound as a curing agent. The composition is suitably used as a cationic electrocoating material. The cationic electrodeposition coating composition is preferably prepared by dispersing the polyol compound used in the present invention in an aqueous medium containing a blocked polyisocyanate compound as a curing agent, a pigment dispersion paste and the like, and a neutralizing agent.

Examples of the neutralizing agent include inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid and lactic acid, and organic acids.

The blocked polyisocyanate compound can be obtained by modifying the urethane prepolymer obtained by reacting the polyisocyanate compound and the polyol resin with a blocking agent as described above. Examples of the polyisocyanate compound include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated TDI, hydrogenated MDI, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), xylylene diisocyanate (XDI), Norbornane diisocyanate (NB
DI) and the like. As the polyol resin,
Examples thereof include polyether polyol, polyester polyol, polytetramethylene glycol polyol, polylactone polyol, castor oil and the like. Examples of the blocking agent include phenol-based blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam-based blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-butyrolactam; aceto. Active methylene-based blocking agents such as ethyl acetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol, methyl glycolate, butyl glycolate, Alcohol-based blocking agents such as diacetone alcohol, methyl lactate and ethyl lactate; formaldoxime, acetaldoxime, acetoxime Methyl ethyl ketoxime, diacetyl monoxime, oxime blocking agents such as cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t
-Butyl mercaptan, thiophenol, methylthiophenol, ethylthiophenol, and other mercaptan blocking agents; acetic acid amide, benzamide, and other amide blocking agents; succinimide, maleic imide, and other imide blocking agents; imidazole, 2-ethyl Examples thereof include imidazole-based blocking agents such as imidazole.

When used as a cationic electrodeposition coating composition, a cationic or nonionic surfactant or an organic solvent may be used in the polyol resin composition of the present invention to disperse the resin components and the like. .

Examples of the above-mentioned cationic surfactants include primary to tertiary amine salts; pyridinium salts; quaternary ammonium salts and the like.

Examples of the nonionic surfactants include polyoxyethylene alkyl ether; polyoxyethylene alkylaryl ether; sorbitan fatty acid ester; polyoxyethylene sorbitan fatty acid ester; fatty acid monoglyceride; trimethylolpropane fatty acid ester; polyoxyethylene. Oxypropylene copolymers; examples thereof include condensation products of ethylene oxide with fatty acid amines, amides or acids.

Examples of the organic solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone and cyclohexanone; tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and the like. Ethers;
Esters such as ethyl acetate and n-butyl acetate; alcohols such as iso or n-butanol, iso or n-propanol and amyl alcohol; ether alcohols such as methyl cellosolve, ethyl cellosolve and butyl cellosolve. To be

[0036]

EXAMPLES Hereinafter, the resin composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Production Examples 1 to 7 show production examples of the polyglycidyl ether compound represented by the general formula (I) and a polyol resin composition containing the same, and Comparative Production Examples 1 to 3 are represented by the general formula (I). An example of producing a polyol resin composition using a compound other than the polyglycidyl ether compound will be described. Reference Production Example 1 shows a production example of a blocked polyisocyanate compound. Moreover, Examples 1-7 and Comparative Examples 1-
In No. 3, a cationic electrodeposition coating composition (curable polyol resin composition) was produced using these, and its performance was evaluated.

[Production Example 1] Adeka polyether BPX-11 (Asahi Denka Kogyo Co., Ltd.) was placed in a four-necked flask equipped with a cooling pipe, a stirring device, a dropping device, a thermometer, and a nitrogen gas introducing device.
(Manufactured by bisphenol A propylene oxide 2 mol adduct) (172 g) was charged and stirred and heated. 1.0 g of boron trifluoride diethyl ether complex was added as a catalyst, and 125 g of alkyl (C12-13) monoglycidyl ether (epoxy equivalent 250) was added thereto at 60 to 70 ° C.
Was added dropwise over 1 hour, and the mixture was aged for 1.5 hours to carry out an addition reaction. After confirming the disappearance of the oxirane ring in the system by the amount of hydrochloric acid absorbed, the boron trifluoride ethyl ether complex was deactivated with 3 g of 48 mass% caustic soda. 370 g of epichlorohydrin and 1.0 g of 50 mass% tetramethylammonium chloride aqueous solution were added thereto, and the pressure was reduced to 5
Epichlorohydrin was refluxed at 0 to 60 ° C., and 85 g of 48 mass% caustic soda was added dropwise to carry out reflux dehydration. After the dropping, the mixture was refluxed and dehydrated for 3 hours to allow the dehydration reaction to proceed. The produced sodium chloride was removed by filtration, and 280 g of a pale yellow transparent liquid polyglycidyl ether compound (EP-1)
(Yield 93%) was obtained. The obtained polyglycidyl ether compound (EP-1) has an epoxy equivalent of 410 and a viscosity of 1.
000 mPa · s (25 ° C.), chlorine content saponifiable to 0.
It was 05 mass% (m + n = 1, p + q = 2, l =
0). Obtained polyglycidyl ether compound (EP-
1) 30 g, Adeka Resin EP-5400 (manufactured by Asahi Denka Co., Ltd .; bisphenol A polyglycidyl ether,
Epoxy equivalent 1000, hydroxyl value 150) 70 g, and diethanolamine 15 g were charged and reacted at 120 ° C. for 5 hours to give a polyol resin composition having a hydroxyl value of 300 (P
-1) was created.

[Production Example 2] 410 g of the polyglycidyl ether compound (EP-1) obtained in Production Example 1 and 57 g of bisphenol A were polymerized at 120 ° C. for 5 hours in the presence of 0.25 g of triphenylphosphine under a nitrogen stream. Let
A solid polyglycidyl ether compound (EPH-1) having an epoxy equivalent of 950 and a hydroxyl value of 73 was obtained (m + n =
1, p + q = 2, l = 1). 30 g of the obtained polyglycidyl ether compound (EPH-1), adecaresin EP
-5400 70 g and diethanolamine 10 g were charged and reacted at 120 ° C. for 5 hours to prepare a polyol resin composition (P-2) having a hydroxyl value of 257.

[Production Example 3] 40 g of the polyglycidyl ether compound (EPH-1) obtained in Production Example 2, 60 g of ADEKA RESIN EP-5400 and 10 g of diethanolamine were charged and reacted at 120 ° C. for 5 hours to give a hydroxyl value of 254. A polyol resin composition (P-3) was prepared.

Production Example 4 20 g of the polyglycidyl ether compound (EPH-1) obtained in Production Example 2, 80 g of ADEKA RESIN EP-5400, and 10 g of diethanolamine were charged and reacted at 120 ° C. for 5 hours to give a hydroxyl value of 267. A polyol resin composition (P-4) was prepared.

[Production Example 5] 172 g of Adeka polyether BPX-11 was placed in a four-necked flask equipped with a cooling tube, a stirrer, a dropping device, a thermometer, and a nitrogen gas introducing device, and stirred and heated. 1.0 g of boron trifluoride diethyl ether complex was added as a catalyst, and 186 g of 2-ethylhexyl monoglycidyl ether was added thereto in an amount of 60 to 70.
Add dropwise over 1 hour at ℃, and age for 1.5 hours,
An addition reaction was performed. After confirming the disappearance of the oxirane ring in the system by the amount of hydrochloric acid absorbed, the boron trifluoride ethyl ether complex was deactivated with 3 g of 48 mass% caustic soda. Then, 370 g of epichlorohydrin and 1.0 g of a 50 mass% tetramethylammonium chloride aqueous solution were added, epichlorohydrin was refluxed at 50 to 60 ° C. under reduced pressure, and 85 g of 48 mass% caustic soda was added dropwise to carry out reflux dehydration. After the dropping, the mixture was refluxed and dehydrated for 3 hours to allow the dehydration reaction to proceed. The produced sodium chloride was removed by filtration, and a pale yellow transparent liquid polyglycidyl ether compound (EP-2) 440
g (yield 95%) was obtained. The obtained polyglycidyl ether compound (EP-2) had an epoxy equivalent of 460, a viscosity of 1500 mPa · s (25 ° C.), and a saponifiable chlorine content of 0.03 mass% (m + n = 2, p + q = 2, l
= 0). Obtained polyglycidyl ether compound (EP
-2) 460 g and bisphenol A 57 g under a nitrogen stream in the presence of triphenylphosphine 0.25 g 12
Polymerization reaction was carried out at 0 ° C. for 5 hours to obtain a solid polyglycidyl ether compound having an epoxy equivalent of 1,000 and a hydroxyl value of 65 (E
PH-2) was obtained (m + n = 2, p + q = 2, l =
1). Obtained polyglycidyl ether compound (EPH
-2) 30 g, ADEKA RESIN EP-5400 70 g,
And 10 g of diethanolamine were charged, and the mixture was heated at 120 ° C. for 5
The reaction was carried out for a period of time to prepare a polyol resin composition (P-5) having a hydroxyl value of 258 (solid content).

[Production Example 6] 172 g of Adeka polyether BPX-11 was charged into a four-necked flask equipped with a cooling tube, a stirring device, a dropping device, a thermometer, and a nitrogen gas introducing device, and the mixture was stirred and heated. 1.0 g of boron trifluoride diethyl ether complex was added as a catalyst, and 75 g of phenyl glycidyl ether (epoxy equivalent 150) was added thereto.
The mixture was added dropwise at 70 ° C. over 1 hour and aged for 1.5 hours to carry out an addition reaction. After confirming the disappearance of the oxirane ring in the system by the amount of hydrochloric acid absorbed, 48 g by mass of caustic soda 3 g
The boron trifluoride ethyl ether complex was deactivated. Then, 370 g of epichlorohydrin and 1.0 g of 50% by mass tetramethylammonium chloride aqueous solution were added thereto, and epichlorohydrin was refluxed at 50-60 ° C. under reduced pressure, and 4
The mixture was refluxed and dehydrated while dropping 85 g of 8 mass% caustic soda. After the dropping, the mixture was refluxed and dehydrated for 3 hours to allow the dehydration reaction to proceed. The generated sodium chloride was removed by filtration, and a pale yellow transparent liquid polyglycidyl ether compound (EP-3)
315 g (yield 92%) was obtained. The obtained polyglycidyl ether compound (EP-3) had an epoxy equivalent of 35.
0, the viscosity was 2000 mPa · s (25 ° C.), and the content of saponifiable chlorine was 0.01% by mass (m + n = 1, p + q =
2, l = 0). The obtained polyglycidyl ether compound (EP-3) (350 g) and bisphenol A (57 g) were polymerized under a nitrogen stream in the presence of triphenylphosphine (0.25 g) at 120 ° C. for 5 hours to give a solid having an epoxy equivalent of 820 and a hydroxyl value of 83. An epoxy resin (EPH-3) was obtained (m + n = 1, p + q = 2, l = 1). 30 g of the obtained polyglycidyl ether compound (EPH-3), 70 g of ADEKA RESIN EP-5400, and 11 g of diethanolamine were charged and reacted at 120 ° C. for 5 hours to give a polyol resin composition (P-6) having a hydroxyl value of 275 (solid content). )
It was created.

[Production Example 7] Adeka polyether BPX-22 (Asahi Denka Kogyo Co., Ltd.) was placed in a four-necked flask equipped with a cooling pipe, a stirring device, a dropping device, a thermometer, and a nitrogen gas introducing device.
(Manufactured by bisphenol A polypropylene oxide 4 mol adduct) (230 g) was charged and stirred and heated. 1.0 g of boron trifluoride diethyl ether complex was added as a catalyst, and 150 g of phenylglycidyl ether (epoxy equivalent 150) was added dropwise thereto at 60 to 70 ° C. over 1 hour, followed by aging for 1.5 hours to carry out addition reaction. went. After confirming the disappearance of the oxirane ring in the system by the amount of hydrochloric acid absorbed, the boron trifluoride ethyl ether complex was deactivated with 3 g of 48 mass% caustic soda. Then, 370 g of epichlorohydrin and 1.0 g of 50% by mass tetramethylammonium chloride aqueous solution are charged therein, and epichlorohydrin is refluxed at 50-60 ° C. under reduced pressure to give 48% by mass of caustic soda 85.
The mixture was refluxed and dehydrated while dropping g. After the dropping, the mixture was refluxed and dehydrated for 3 hours to allow the dehydration reaction to proceed. The generated sodium chloride was removed by filtration to obtain 440 g (yield 95%) of a pale yellow transparent liquid polyglycidyl ether compound (EP-4). Obtained polyglycidyl ether compound (EP-
4) has an epoxy equivalent of 510 and a viscosity of 1800 mPa · s.
(25 ° C.), and the content of saponifiable chlorine was 0.01% by mass (m + n = 2, p + q = 4, l = 0). The resulting polyglycidyl ether compound (EP-4) (510 g) and bisphenol A (57 g) were subjected to a polymerization reaction at 120 ° C. for 5 hours in the presence of triphenylphosphine under a nitrogen stream to give a solid having an epoxy equivalent of 1100 and a hydroxyl value of 59. A polyglycidyl ether compound (EPH-4) was obtained (m +
n = 2, p + q = 4, l = 1). 30 g of the obtained polyglycidyl ether compound (EPH-4), 70 g of ADEKA RESIN EP-5100 (manufactured by Asahi Denka Co., Ltd .; bisphenol A polyglycidyl ether, epoxy equivalent 450, hydroxyl value 107), and diethanolamine 19 g were charged, 120 The reaction was carried out at 5 ° C for 5 hours to prepare a polyol resin composition (P-7) having a hydroxyl value of 335.

Comparative Production Example 1 Adeka Resin EP-54
00 100 g and diethanolamine 10 g were charged and reacted at 120 ° C. for 5 hours to prepare a polyol resin composition (PX) having a hydroxyl value of 93.

[Comparative Production Example 2] 172 g of Adeka polyether BPX-11 was charged into a four-necked flask equipped with a cooling tube, a stirrer, a dropping device, a thermometer, and a nitrogen gas introducing device, and stirred and heated. 370 g of epichlorohydrin and 1.0 g of a 50 mass% tetramethylammonium chloride aqueous solution were added, epichlorohydrin was refluxed at 50-60 ° C. under reduced pressure, and 85 g of 48 mass% caustic soda was added dropwise for dehydration under reflux. After the dropping, reflux and dehydrate for 3 hours,
The dehydration reaction proceeded. The generated sodium chloride was removed by filtration to obtain 245 g (yield 95%) of a pale yellow transparent liquid polyglycidyl ether compound (EP-Y). The obtained polyglycidyl ether compound (EP-Y) is
Epoxy equivalent 260, viscosity 3500 mPa · s (25
° C) and the content of saponifiable chlorine was 0.01% by mass (m
+ N = 0, p + q = 2). 260 g of the obtained polyglycidyl ether compound (EP-Y), bisphenol A8
Triphenylphosphine 0.25g under nitrogen stream
In the presence of a polymer at 120 ° C. for 5 hours to give a solid polyglycidyl ether compound (EPH-Y) having an epoxy equivalent of 1000 and a hydroxyl value of 139 (m + n = 0, p + q =
4, l = 2) was obtained. 30 g of the obtained polyglycidyl ether compound (EPH-Y), ADEKA RESIN EP-54
00 g and diethanolamine 10 g were charged and reacted at 120 ° C. for 5 hours to prepare a polyol resin composition (PY) having a hydroxyl value of 279 (solid content).

[Comparative Production Example 3] 200 g of Adeka Polyether BPX-12 was charged into a four-necked flask equipped with a cooling tube, a stirrer, a dropping device, a thermometer, and a nitrogen gas introducing device, and stirred and heated. 370 g of epichlorohydrin and 1.0 g of a 50 mass% tetramethylammonium chloride aqueous solution were added, epichlorohydrin was refluxed at 50-60 ° C. under reduced pressure, and 85 g of 48 mass% caustic soda was added dropwise for dehydration under reflux. After the dropping, reflux and dehydrate for 3 hours,
The dehydration reaction proceeded. The produced sodium chloride was removed by filtration to obtain 270 g (yield 95%) of a pale yellow transparent liquid polyglycidyl ether compound (EP-Z). The obtained polyglycidyl ether compound (EP-Z) is
Epoxy equivalent 300, viscosity 2500 mPa · s (25
° C) and the content of saponifiable chlorine was 0.01% by mass (m
+ N = 0, p + q = 3, l = 0). 300 g of the obtained polyglycidyl ether compound (EP-Z) and 57 g of bisphenol A were polymerized at 120 ° C. for 5 hours in the presence of 0.25 g of triphenylphosphine under a nitrogen stream,
A solid polyglycidyl ether compound (EPH-Z) having an epoxy equivalent of 730 and a hydroxyl value of 94 was obtained (m + n =
1, p + q = 3, l = 1). 30 g of the obtained polyglycidyl ether compound (EPH-Z), ADEKA RESIN EP
-5400 70 g and diethanolamine 12 g were charged and reacted at 120 ° C. for 5 hours to prepare a polyol resin composition (PZ) having a hydroxyl value of 290.

[Reference Production Example 1] TDI-100 (365 g) was charged in a four-necked flask equipped with a cooling tube, a stirrer, a dropping device, a thermometer, and a nitrogen gas introducing device, and stirred and heated. Adeka polyether BPX-11 285 g 8
The solution was gradually added dropwise over 1 hour so that the temperature of 0 to 100 ° C could be maintained. After completion of dropping, reaction was carried out at 80 to 100 ° C. for 3 hours. The NCO% at this point was 16.5%. Then, 375 g of ε-caprolactam was added from 100 ° C to 140
It was charged over 1 hour so that the temperature up to ℃ could be maintained. After completion of dropping, the mixture is reacted at 140 to 150 ° C. for 3 hours, and NCO%
To obtain a blocked polyisocyanate compound (BI) having a softening point of 100%.

[Examples 1 to 7 and Comparative Examples 1 to 3] A curable polyol was prepared by using the polyol resin composition obtained above and a polyol resin composition for comparison and having a composition as shown in Table 1. A resin composition (coating for cationic electrodeposition) was prepared. Using the obtained cationic electrodeposition coating, a zinc phosphate-treated steel sheet was electrodeposited at 150 V and baked at 180 ° C. for 30 minutes as a test piece, and the film thickness, corrosion resistance, and tape peeling were performed as follows. And the impact resistance was evaluated.
The results of these evaluations are shown in Table 1.

(Film Thickness) The film thickness (unit: μm) was measured with a precision electromagnetic thickness meter VL-30B type manufactured by Kett Scientific Laboratory.

(Corrosion resistance) The coating film after 240 hours of SST was
It was visually evaluated according to the following evaluation criteria. Evaluation criteria ○: No change, △: A little damage is seen in the coating film, ×: Large damage is seen in the coating film

(Tape peeling) After 240 hours of SST, the cross-cut portion was tested with cellophane tape and evaluated according to the following evaluation criteria. Evaluation Criteria ◯: No peeling of the coating film, Δ: Partial peeling around the cross-cut of the coating film, ×: Complete peeling of the coating film

(Impact resistance) The test piece was placed in an atmosphere of 25 ° C. with the coating film side facing upward, and a weight of 1 kg was used.
It was dropped from a height of cm and evaluated according to the following evaluation criteria. Evaluation criteria ◯: The coating film is not destroyed, ×: The coating film is destroyed

[0053]

[Table 1]

As is clear from Table 1, when a polyol resin composition obtained from an ordinary bisphenol A type epoxy resin is used as a cationic electrodeposition coating, it is difficult to form a thick film and the impact resistance is poor. Only things can be done (Comparative Example 1). Further, when a polyol resin composition obtained from a polyglycidyl ether compound of a propylene oxide adduct of bisphenol A is used as a cationic electrodeposition coating, it is possible to slightly thicken the film, but the impact resistance is poor (Comparative Example 2). When the amount of propylene oxide adduct added is further increased, the effect of thickening the film is slightly improved,
Although the impact resistance is also improved, the corrosion resistance is reduced (Comparative Example 3).

On the other hand, when the polyol resin composition obtained from the specific polyglycidyl ether compound of the present invention is used as a cationic electrodeposition coating composition, a thick film can be obtained and physical properties such as corrosion resistance and impact resistance can be obtained. An excellent coating film can be formed.

[0056]

The polyol resin composition according to the present invention is
When used as a coating for cationic electrodeposition, it is possible to provide a coating film which can be made thicker and has excellent corrosion resistance and impact resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 175/08 C09D 175/08 (72) Inventor Ryo Ogawa 20 Asahiden, Showa Onuma, Minami Saitama-gun, Saitama-gun Chemical Industry Co., Ltd. F term (reference) 4J002 CD20W CD20Y GH01 4J034 BA03 BA07 DA01 DA03 DB03 DB08 DC02 DF01 DF11 DG00 DG06 DK02 DK03 DK05 DK08 DK09 EA12 HA01 HA02 HA07 HC03 HC12 HC17 HC22 HC46 HC52 HC53 HC61 HC73 HC61 HC64 HC67 HC67 HC67 HC67 HC67 HC67 HC67 HC67 HC67 HC67 HC67 HC67 HC67 HC67 HC67 HD06 HD07 HD12 HD15 JA42 RA07 4J036 AC01 AC02 AC03 AC05 AD01 AD04 AD05 AD07 AD08 AD15 AD20 AD21 AF06 AF08 AF16 AF27 CA06 CA28 CB04 CB10 CB22 DC27 JA04 4J038 DG131 DG302 PA04

Claims (7)

[Claims] 1. A polyol resin composition comprising a polyol compound obtained by reacting a polyglycidyl ether compound represented by the following general formula (I) with an active hydrogen compound. [Chemical 1] 2. The polyol resin composition according to claim 1, wherein in the general formula (I), A is a group represented by the following general partial structural formula. [Chemical 2] 3. The general formula (I), wherein R1 is an alkyl group having 4 to 18 carbon atoms, or a phenyl group optionally substituted by 1 to 3 alkyl groups. Polyol resin composition. 4. A polyol compound obtained by reacting a polyglycidyl ether compound represented by the general formula (I) with an active hydrogen compound in an amount of 5 to 50% by mass, and an aromatic polyglycidyl compound other than the polyglycidyl ether compound. The polyol resin composition according to any one of claims 1 to 3, which comprises 95 to 50 mass% of a polyol compound obtained by reacting an ether compound with an active hydrogen compound. 5. The active hydrogen compound is at least one selected from secondary amine compounds.
4. The polyol resin composition according to any one of 4 above. 6. The polyol resin composition according to claim 1, further comprising a blocked polyisocyanate compound. 7. The polyol resin composition according to claim 6, which is used as a cationic electrodeposition coating composition.