JPH06207126A - Resin composition for thermosetting powder coating - Google Patents

Abstract

PURPOSE:To obtain a resin composition for thermosetting powder coating, containing a specific epoxy resin, a hydroxyl group-containing polyester resin and a cationic curing catalyst in prescribed amounts, excellent in weather and heat resistance, electrical characteristics and anticorrosive properties without evolving toxic volatiles and useful for outer surfaces of steel pipes, etc. CONSTITUTION:The composition comprises (A) an epoxy resin obtained by reacting (i) a compound having one or more vinyl groups and one epoxy group in one molecule such as 4-vinylcylohexane-1-oxide with (ii) one or more selected from polymers containing polybasic acids (anhydrides), acid-terminated polymers and polymers containing carboxylic acid group and (iii) one or more selected from compounds having one or more active hydrogens, providing a resin having vinyl group and further epoxidizing the resultant resin, (B) a hydroxyl group- containing polyester resin and (C) a cationic curing catalyst such as N,N- dimethyl-N-benzylanilinium antimony hexafluoride in an amount of 0.05-3.0wt.% [based on the total amount of the components (A) and (B)].

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention shows stable powder properties in a resin composition for powder coatings, is sufficiently crosslinked under relatively mild curing conditions, and the resulting cured product has excellent heat resistance,
The present invention relates to a resin composition for thermosetting powder coatings having weather resistance.

[0002]

2. Description of the Related Art Typical powder coatings include urethane-curable polyester powder coatings, glycidyl-curing polyester powder coatings, epoxy resin-curing powder coatings, and urethane-curing coatings contain hydroxyl groups. When the resin is crosslinked with a block polyisocyanate compound, the blocking agent is released and vaporized during the baking process, which causes problems such as smoke during baking, odor, and foaming of the coating film during thick film coating. Also, glycidyl curing type (TGIC etc.) and epoxy resin curing type are used, but this requires a relatively high temperature for baking, and if the temperature is low, sufficient flowability cannot be obtained and the finish of the coating film There is a problem with the appearance.

[0003]

From such a situation,
As a result of examination by the present inventors, by using the epoxy resin of Claims 1 to 11, a hydroxyl group-containing polyester resin and a cation curing catalyst, stable resin properties are exhibited in a resin composition for powder coating, and when baking, It has been found that the curing temperature can be lowered and the problems of generation of harmful scattered substances can be solved, and that the obtained cured product can obtain a polyester powder coating having excellent weather resistance and heat resistance. It was

[0004]

Means for Solving the Problems That is, the present invention provides "(A) (a) a compound having at least one vinyl group and one epoxy group in one molecule, and (b) a polybasic acid anhydride. ,
At least one selected from polybasic acids, acid-terminated polymers, and polymers containing carboxylic acid groups, and (c) at least one selected from compounds having one or more active hydrogens.
The amount of the component (C) in the composition, which further comprises an epoxy resin (B) a hydroxyl group-containing polyester resin (C) obtained by epoxidizing a resin having a vinyl group obtained by reacting a seed with a cation curing catalyst. Is 0.05 to 3.0 with respect to the total amount of the components (A) and (B).
It is a resin composition for thermosetting powder coatings, characterized in that it is in weight%. "

In the above, (a), (b),
It has been clarified that the characteristics of the epoxy resin can be changed and various characteristics can be given by combining various kinds of (c).

Next, the present invention will be described in more detail.

The powder coating composition of the present invention comprises two kinds of resins and a resin composition containing a cation curing catalyst as essential components.

The epoxy resin (A) which is one of the essential components of the resin composition for thermosetting powder coating material of the present invention will be described.

The compound having one epoxy group and one or more vinyl groups in one molecule used in the present invention is represented by the following formula: << i is an integer of 1 to 5, R ¹ and R ⁴ are hydrogen atoms or alkyl groups having 1 to 50 carbon atoms or substituted phenyl groups,
R ² and R ³ are each a hydrogen atom or an alkyl group having 1 to 50 carbon atoms, and R ² and R ³ may be wrapped around a ring.

Specific examples of the compound represented by the above formula are the compounds shown below.

4-vinylcyclohexene-1-oxide, 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide, limonene monoxide, trivinylcyclohexane monoxide, divinylbenzene monoxide, butadiene monooxide. Oxide and 1,2-epoxy-
9-decene etc.

[Chemical 1] Compounds such as allyl glycidyl ether

[Chemical 2] And compounds such as glycidyl styryl ether.

Further, the following compounds can also be used.

[0013]

[Chemical 3]

[Chemical 4] These may be used alone or in combination of two or more.

If desired, ethylene oxide,
Propylene oxide, cyclohexene oxide, styrene oxide, monoepoxides such as α-olefin epoxide, vinyl cyclohexene dioxide, 3,4-
A diepoxide such as epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate may be used at the same time as the compound having one epoxy group and one or more vinyl groups in one molecule.

The polybasic acid anhydrides or polybasic acids (b) used in the present invention include aromatic polybasic acids and acid anhydrides thereof, and aliphatic polybasic acids and acid anhydrides thereof. Examples of aromatic polybasic acids and acid anhydrides thereof include:
Examples include phthalic anhydride, isophthalic acid, terephthalic acid and trimellitic anhydride. Examples of the aliphatic polybasic acid and its acid anhydride include tetrahydrophthalic acid, 4-methylhexahydrophthalic acid, hexahydrophthalic acid, adipic acid, maleic acid, and their acid anhydrides, fumaric acid and sebacic acid. , Dodecane diacid, and their acid anhydrides.

The acid-terminated polymer used in the present invention is an acid-terminated polymer obtained by reacting a polybasic acid with polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polycyclohexene glycol, polyvinyl cyclohexene glycol or the like. Examples include ethers, acid-terminated polyesters, acid-terminated polybutadienes and acid-terminated polycaprolactones.

Further, an acrylic copolymer having a carboxylic acid group can be used instead of the acid terminal polymer, and it contains a polybasic acid anhydride, a polybasic acid, an acid terminal polymer, and a carboxylic acid group. These polymers may be used alone or in combination of two or more.

Next, as the compound (c) having active hydrogen used in the present invention, alcohols, phenols, carboxylic acids, amines, thiols, hydroxyl-terminated polymers, and hydroxyl groups can be used. The polymer etc. which are contained are mentioned. The alcohols are monovalent, divalent, trivalent or higher, and include, for example, methanol, ethanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol, Examples include hexanediol, glycerin, butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerol, triglycerol and the like.

In addition, neopentyl glycol, neopentyl glycol ester of hydroxyhyvalic acid, dipentaerythritol, 1,4-cyclohexanedimethanol, trimethylpentanediol, 1,3,5-tris (2-hydroxyethyl) cyanuric acid, Hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct and the like can also be used.

Examples of the phenols include phenol, cresol, catechol, pyrogallol, hydroquinone,
Hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, ethylene oxide adduct of bisphenol A, propione oxide adduct of bisphenol A, phenol Resin and cresol-novolak resin.

Examples of the hydroxyl group-terminated polymer used in the present invention include polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polycyclohexene glycol and polyvinyl cyclohexene glycol, hydroxyl group-terminated polyesters, hydroxyl group-terminated polybutadiene, Examples include hydroxyl-terminated polycaprolactone and polycarbonate diol. Further, an acrylic copolymer having a hydroxyl group or the like can be used instead of the hydroxyl group-terminated polymer.

The carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecane diacid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid. Acid, terephthalic acid, etc.

Further, compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid and oxycaproic acid, can also be mentioned.

The amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine,
Examples include octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine and ethanolamine.

As the thiols, methyl mercaptan,
Mercapto such as ethyl mercaptan, propyl mercaptan, phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol ester of mercaptopropionic acid, for example, ethylene glycol dimercaptopropionic acid ester, trimethylolpropane trimercaptopropionic acid, pentaerythritol pentamercaptopropionic acid Etc.

Further, as the compound having active hydrogen, polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, Styrene-maleic acid copolymer resin, alkyd resin, polyester polyol resin,
Examples include polyester carboxylic acid resins, polycaprolactone polyol resins, polypropylene polyols, polytetramethylene glycol, and the like.

The compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples thereof include allyl alcohol, acrylic acid, methacrylic acid,
There are 2-hydroxyethyl methacrylate, 3-cyclohexenemethanol, tetrahydrophthalic acid and the like.

Any compound can be used as long as it is a compound having these active hydrogens, and two or more kinds thereof may be mixed.

The epoxy resin used in the present invention includes the compound (a) having at least one vinyl group and one epoxy group in the above molecule, a polybasic acid anhydride, a polybasic acid, and an acid terminal polymer. And a vinyl group-containing resin obtained by reacting at least one selected from the polymer (b) containing a carboxylic acid group and at least one selected from the compound (c) having active hydrogen. Obtained by epoxidation with an epoxidizing agent.

The starting materials (a), (b),
The charging ratio of (c) is 1 to 99 parts by weight of (a), preferably 30 to 80 parts, 99 to 1 part by weight of (b), preferably 20 to 70 parts, and 0 to 99 parts by weight of (c). Parts, preferably 0 to 30 parts.

The component (c) may not be used depending on the case. When the component (c) is not used, it is necessary to control the molecular weight while detecting the dehydration amount by controlling the reaction time, the degree of reduced pressure, the reaction temperature and the like.

When the amount of the component (a) used is relatively small, the epoxy group content in the target epoxy resin is small. The molar ratio of component (a) / component (b) is
It is 0.4 to 5.0, preferably 0.5 to 3.0.

When the proportion of component (a) is high, the proportion of hydroxyl groups at the terminals increases, and when there are hydroxyl groups and carboxyl group terminals, all terminals become hydroxyl groups as the dehydration reaction proceeds.

On the contrary, when the ratio of the component (b) is high, the ratio of the terminal being a carboxyl group is large, and in the case where the hydroxyl group end and the carboxyl group end are present, all the terminals become carboxyl groups as the dehydration reaction proceeds. . However, (a)
If the ratio of the components is unnecessarily large, part of the component (a) will remain unreacted. Further, when the ratio of the component (b) becomes unnecessarily large, the component (b) remains without reacting.

In the reaction for synthesizing the resin having a vinyl group, a catalyst for promoting the ring-opening reaction of the epoxy group with a carboxyl group and, if necessary, a catalyst for promoting the (dehydration) esterification reaction may be used in combination. Good.

As the catalyst for promoting the ring-opening reaction of an epoxy group with a carboxyl group which can be used in the present invention, a tertiary amine such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine and tri-n-octylamine, tetramethylammonium chloride. , Quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide, alkylureas such as tetramethylurea, and alkylguanidines such as tetramethylguanidine.

The catalyst for promoting the ring-opening reaction that can be used in the present invention may be used alone or in combination of two or more kinds. This catalyst is 0.1 to 5.0 relative to the epoxy compound.
%, Preferably 0.5 to 3.0% by weight. The ring-opening reaction is 50 to 200 ° C, preferably
It is carried out at 100 to 180 ° C.

Examples of the catalyst for promoting the (dehydration) esterification reaction that can be used in the present invention include Sn compounds such as tin octylate and dibutyltin laurate, and Ti compounds such as tetrabutyl titanate.

The catalyst for promoting the (dehydration) esterification reaction used in the present invention may be used alone or in combination of two or more kinds. This catalyst is 0-100 with respect to the reaction system.
It is recommended to use 0 ppm, preferably 50 to 500 ppm.

This (dehydration) esterification reaction is 180 to 2
Perform at 40 ° C.

The epoxy group ring-opening reaction with a carboxyl group and the (dehydration) esterification reaction may be carried out sequentially, but after the raw materials and the catalyst have been charged all at once, the reaction temperature is raised stepwise in accordance with the progress of the reaction. Method is preferred. If necessary, after the component (c) and the catalyst are charged at once,
The components (a) and (b) may be dropped.

The resin having a cyclic olefin or vinyl group thus synthesized is reacted with an epoxidizing agent to synthesize the resin having an epoxy group of the present invention. As peracids,
Examples thereof include hydroperoxides.

Examples of peracids include formic acid, peracetic acid, perbenzoic acid and trifluoroperacetic acid. Of these, peracetic acid is industrially produced in large quantities and is available at low cost.
It is also a preferred epoxidizing agent because of its high stability.

Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide and the like.

In the epoxidation, a catalyst can be used if necessary.

For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst. In the case of hydroperoxides, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. You can

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature according to the physical properties of the equipment and raw materials. The reaction temperature range that can be used depends on the reactivity of the epoxidizing agent used. For peracetic acid, which is a preferred epoxidizing agent, 0 to 70 ° C. is preferable.

At 0 ° C. or lower, the reaction is slow, and at 70 ° C., decomposition of peracetic acid occurs.

In the tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate system, which is an example of hydroperoxide, it is 2 for the same reason.
0 degreeC-150 degreeC is preferable.

The solvent can be used for the purpose of reducing the viscosity of the raw material and stabilizing it by diluting the epoxidizing agent.
In the case of peracetic acid, aromatic compounds, ethers, esters and the like can be used.

The charged molar ratio of the epoxidizing agent to the unsaturated bond can be changed according to the purpose such as how much unsaturated bond is desired to remain.

When a compound having a large number of epoxy groups is intended, the epoxidizing agent is preferably added in an equimolar amount or more with respect to the unsaturated group.

However, it is usually disadvantageous in excess of 2 times the molar amount in view of economical efficiency and side reactions, and in the case of peracetic acid, 1 to 1.5 times the molar amount is preferable.

The composition of interest can be removed from the reaction crude liquid by chemical engineering means such as concentration.

The other essential component of the thermosetting powder coating resin composition of the present invention is (B) a hydroxyl group-containing polyester resin. Such a resin has a polybasic acid component and a polyhydric alcohol.
When a polyester is produced from a polyol component, it can be easily produced by using a polyvalent alcohol component in excess.

In the polymerization reaction composition, the polybasic acid component and the polyhydric alcohol component may be essentially stoichiometric, but for example, 1 mol of the polybasic acid component to 1 mol of the polybasic acid component. It is preferably from 0 to 1.5 mol.

Polybasic acid components include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic anhydride, naphthalenedicarboxylic acid, 4,4'-diphenylcarboxylic acid, adipic acid, sebacic acid, succinic acid, azelaic acid, dodecanedioic acid. , Cyclohexanedicarboxylic acid, fumaric acid,
Examples thereof include maleic anhydride, tetrahydrophthalic anhydride, trimellitic acid, pyromellitic acid and their anhydrides.

As the polyhydric alcohol component, ethylene glycol, propylene glycol, butanediol, trimethylene glycol, diethylene glycol, dipropylene glycol, cyclohexane dimethanol, 1,6
-Hexanediol, 1,8-octanediol, 1,
Examples thereof include 9-nonanediol, 1,10-decanediol, glycerin, trimethylolpropane, trimethylolethane and pentaerythritol.

The hydroxyl group-containing polyester resin of the present invention is
The polybasic acid component and the polyhydric alcohol component can be prepared by a known polymerization method such as a transesterification method or an esterification followed by a solution polycondensation reaction. Known catalysts and the like are used, for example, dibutyltin oxide, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, tetraisopropyl titanate, etc. You may. These catalysts have a total polyester content of 0.
01 to 0.5% by weight is preferable.

In addition, in the above-mentioned polymerization method, the polybasic acid component and the polyhydric alcohol component may be added at the same time and polymerized, or each may be added and polymerized in plural times. The component (A) is used in a ratio of 10 to 80 parts by weight per 100 parts by weight of the component (B).

Next, the (C) cationic curing catalyst used in the present invention will be explained.

Many cationic curing catalysts are known. For example, a Lewis acid such as BF ₃ is used as a cation curing catalyst, but has a very short pot life by itself, and is used as an amine complex for practical use. BF ₃ - amine complex, monoethylamine, triethylamine, piperidine, ethanol - triethanolamine BF _3, such as - there is an amine complex. Also known are sulfonium salt type, ammonium salt type, pyridinium salt type compounds having a benzyl group, α-substituted benzyl ammonium salts, and heterocyclic ammonium salts.

Further, phosphonium salt type and iodonium salt type cationic curing catalysts are also known. In the present invention, these known cationic curing catalysts can be used. These are generally SbF ₆ ⁻ , BF ₄ ⁻ , AsF.
₆ ^-, PF ₆ ^- nitrogen to an anion component, such as sulfur,
It is an onium salt of phosphorus or iodine. Typical examples of these are given below.

1) Quaternary ammonium salt type compound: N, N-dimethyl-N-benzylanilinium antimony hexafluoride N, N-diethyl-N-benzylanilinium boron tetrafluoride N, N-dimethyl-N- Benzylpyridinium hexafluoride N, N-dimethyl-N- (4-chlorobenzyl) anilinium antimony hexafluoride N, N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid N, N-dimethyl-N- (4- Methoxybenzyl) pyridinium antimony hexafluoride N, N-diethyl-N- (4-methoxybenzyl) pyridinium antimony hexafluoride N, N-dimethyl-N- (4-methoxybenzyl) toludinium antimony hexafluoride N, N- Diethyl-N- (4-methoxybenzyl) toludinium 6 Antimony 2) Sulfonium salt type: triphenylsulfonium tetrafluoroboron triphenylsulfonium hexafluoride antimony triphenylsulfonium hexafluoride arsenic tri (4-methoxyphenyl) sulfonium hexafluoride diphenyl (4-phenylthiophenyl) ) Sulfonium 6-arsenic fluoride p-t-butylbenzyl tetrahydrothiophenium 6
Antimony Fluoride 3) Phosphonium salt type compound: Ethyltriphenylphosphonium 6 antimony fluoride Tetrabutylphosphonium 6 antimony fluoride 4) Iodonium salt type compound: Diphenyliodonium 6 arsenic difluoride Di-4-chlorophenyliodonium 6 Arsenic Fluoride Di-4-bromophenyliodonium 6-arsenic di-p-tolyl iodonium 6-arsenic arsenic Phenyl (4-methoxyphenyl) iodonium 6-arsenic arsenide The component (C) is (A). It is used in an amount of 0.05 to 3% by weight based on the total amount of the component and the component (B). If it is less than 0.05% by weight, the catalytic effect will not appear, and if it is too much, it will adversely affect the physical properties of the coating such as coloring and deterioration of water resistance.

In the present invention, the epoxy resin may be mixed with other epoxy resins as long as the characteristics of the epoxy resin as the component (A) are not impaired. Here, the other epoxy resin is, for example, epibis type epoxy, bisphenol F epoxy,
Examples include novolac epoxy and alicyclic epoxy.

Usually, after mixing the above components, a heating roll is used.
80 to 1 by a melt-kneader such as an extruder or an extruder.
The mixture is kneaded at about 20 ° C., sufficiently kneaded, cooled, and then ground using a grinder or the like.

The resin composition for a thermosetting powder coating material of the present invention contains various additives, fillers, pigments, silicone-based or acrylic-based flow regulators and antistatic agents, if necessary, in addition to the above. , An ultraviolet absorber, a light stabilizer, an antioxidant and the like may be contained.

The powder coating composition can be produced by any known method.

[0069]

The powder coating material of the present invention thus obtained is excellent in weather resistance, heat resistance, and electric characteristics, and therefore, it is used for corrosion protection of steel pipe outer surface coating, container coating, building materials, etc. It is very useful for insulation of other electric and electronic parts.

The present invention will be described in detail below with reference to examples.

Example Synthesis Example 1 << Synthesis of Polymer Having Vinyl Group >> In a reactor equipped with a condenser, a stirrer, a reflux condenser and a nitrogen inlet tube, 74.1 g (1.0 mol) of butanol was added.
Hexahydrophthalic anhydride (hereinafter referred to as HHPA) 9
25.2 g (6.0 mol) and 3.72 g of tetramethylammonium chloride were charged.

While the nitrogen gas was being introduced, the temperature of the reactor was raised and the reaction was carried out with continuous stirring. When the reaction temperature reached 85 ° C, the temperature increase was stopped. As the reaction between butanol and HHPA proceeded, the temperature inside the system rose to 140 ° C.
It was confirmed from gas chromatography (hereinafter referred to as GC) analysis that butanol was a trace amount.

Thereafter, the temperature in the reaction system was maintained at 100 ° C., and 4-vinylcyclohexene-1-oxide (hereinafter,
744.0 g (6.0 mol) represented by VCM) was added dropwise over 1 hour to react.

After the completion of dropping, the mixture was aged at 150 ° C. for 2 hours. It was confirmed by GC analysis that VCM was in a trace amount. At this point, the conversion rate of VCM is 99.
It was 6%.

This crude reaction liquid was taken out of the system, cooled on a release paper at room temperature to give an iodine value of 86.9 (g / 100).
A polymer [A1] having a vinyl group of g) was obtained.

Synthesis Example 2 A reactor equipped with the same apparatus as in Synthesis Example 1 was charged with 62.1 g (1.0 mol) of ethylene glycol, HHPA925.
2 g (6.0 mol) and 3.50 g of triethylamine were charged.

After reacting in the same manner as in Synthesis Example 1, 140 ° C.
Then, 744.0 g (6.0 mol) of VCM was added dropwise and reacted in the same manner.

The same operation as in Synthesis Example 1 was conducted to obtain an iodine value of 8
Polymer having a vinyl group of 7.0 (g / 100 g) [A
2] was obtained.

Synthesis Example 3 A reactor equipped with the same apparatus as in Synthesis Example 1 was charged with trimethylol.
134.2 g of rupropane (hereinafter referred to as TMP) (1.
0 mol), HHPA 925.2 g (6.0 mol),
3.50 g of tetramethylguanidine was charged.

After reacting in the same manner as in Synthesis Example 1, 180 ° C.
Then, 744.0 g (6.0 mol) of VCM was added dropwise and reacted in the same manner.

The same operation as in Synthesis Example 1 was conducted to obtain an iodine value of 8
Polymer having a vinyl group of 4.2 (g / 100 g) [A
3] was obtained.

Synthesis Example 4 Tris-2- was added to a reactor equipped with the same apparatus as in Synthesis Example 1.
Hydroxyethyl isocyanurate (hereinafter referred to as THEIC
261.2 g (1.0 mol), methylhexakihydrophthalic anhydride (hereinafter referred to as MHHPA) 10
08 g (6.0 mol), tetraethylenediamine 3.
72g was charged.

After reacting in the same manner as in Synthesis Example 1, 120 ° C.
Then, 744.0 g (6.0 mol) of VCM was added dropwise and reacted in the same manner.

The same operation as in Synthesis Example 1 was conducted to obtain an iodine value of 7
Polymer having a vinyl group of 5.0 (g / 100 g) [A
4] was obtained.

Synthesis Example 5 << Synthesis Example of Epoxy Resin >> In a reactor equipped with a condenser, a stirrer, a reflux condenser, a nitrogen introducing pipe and a dropping funnel, 1000 g of an ethyl acetate solution of the polymer [A1] (solid content: 45 %), And 392 g of a peracetic acid (hereinafter, referred to as AP) ethyl acetate solution (hereinafter, referred to as APE, AP concentration is 30%) was charged to the dropping funnel,
The inside of the reaction system was kept at 35 ° C. and added dropwise for 1 hour. After completion of dropping, the system was kept at 40 ° C. and aged for 5 hours. At this time, the conversion rate of AP was 97.5%.

The obtained reaction crude liquid was added with a 3% NaOH aqueous solution 1
It was washed with 500 ml × 2, 1500 ml of distilled water. At this time, the neutralization and washing temperatures were in the range of 40 to 50 ° C. The reaction crude liquid subjected to the water washing treatment was subjected to low boiling point removal at 140 to 150 ° C. and 5 mmHg or less using a thin film evaporator to obtain an epoxy resin [B1] having an epoxy equivalent of 330. The obtained resin [B1] was analyzed by gel permeation chromatography (hereinafter referred to as GPC). GP
The C analysis was performed using CR-4A manufactured by Shimadzu Corporation.
As a result of GPC analysis, MN = 1590 (in terms of police),
The MW / MN was 1.77.

Synthesis Example 6 A polymer [A] was placed in a reactor equipped with the same device as in Synthesis Example 5.
1000 g (45% solid content) of ethyl acetate solution of 2] was charged, and 395 g of APE (AP concentration 30%) to which 0.05 wt% of potassium hexametaphosphate was added to AP was charged to a dropping funnel to react. Keep the system at 40 ℃ 1
Dropped over time.

The same operation as in Synthesis Example 1 was carried out to obtain epoxy equivalent 315, MN = 1979 (polystyrene conversion), MW / MN
= 1.67 of epoxy resin [B2] was obtained.

Synthesis Example 7 The polymer [A] was placed in a reactor equipped with the same apparatus as in Synthesis Example 5.
1000 g (solid content 35%) of 3] was charged, and an ethyl acetate solution of perbenzoic acid (concentration 30%) 53 was added.
5 g of sodium dioctyltripolyphosphate added in an amount of 0.05% by weight with respect to perbenzoic acid was charged into the dropping funnel, and the reaction system was kept at 40 ° C. and added dropwise for 1 hour.

The same operation as in Synthesis Example 1 was carried out to obtain epoxy equivalent 336, MN = 2540 (polystyrene conversion), MW / MN
Thus, an epoxy resin [B3] having a ratio of 1.98 was obtained.

Synthesis Example 8 A polymer [A] was placed in a reactor equipped with the same apparatus as in Synthesis Example 5.
4] was charged with 800 g of ethyl acetate solution (solid content: 60%), and benzoic acid (concentration: 30%) solution of ethyl acetate 660 was added.
Sodium pyrophosphate is added to g with respect to perbenzoic acid of 0.0
The mixture added with 5% by weight was placed in a dropping funnel, and the inside of the reaction system was kept at 50 ° C. and added dropwise for 1 hour. The same operation as in Synthesis Example 5 was performed to obtain an epoxy equivalent of 380 and MN = 3570.
An epoxy resin [B4] having a MW / MN = 2.68 (in terms of polysty) was obtained.

Synthesis Example 9 << Synthesis of Polyester Resin >> 37.3 parts of ethylene glycol and 32.4 parts of neopentyl glycol were placed in a reactor equipped with a heating device, a stirrer, a nitrogen inlet tube, and a fractionating column. , Glycerin 11.5 parts, dimethyl terephthalate 90.8 parts, and zinc acetate 0.5
Under a nitrogen stream while removing the produced methanol out of the system, the temperature was gradually raised to 210 ° C. to perform the transesterification reaction, and once cooled to 170 ° C., 71.7 parts of terephthalic acid and 1 part of dibutyltin dioxide was added and the temperature was raised to 240 ° C. over 3 hours to carry out a dehydration esterification reaction. The reaction was completed when the resin acid value was 2.0. A polyester resin having a hydroxyl value of 77.6 (KOHmg / g) was obtained. This polyester resin is abbreviated as P1.

Synthesis Example 10 76.2 parts of neopentyl glycol, 3.8 parts of trimethylolpropane, 75.1 parts of dimethyl terephthalate,
A reaction was performed in the same manner as in Synthesis Example 1 except that 60.0 parts of terephthalic acid was used to obtain a polyester resin having a hydroxyl value of 53 (KOHmg / g). This polyester resin is abbreviated as P2.

Synthesis Example 11 77.2 parts of ethylene glycol, dimethyl terephthale
109.8 parts, trimellitic anhydride 10.1 parts, isophthalic acid 57.5 parts, and terephthalic acid 14.1 parts were reacted in the same manner as in Synthesis Example 1 to obtain a hydroxyl value of 42.5.
(KOHmg / g) polyester resin was obtained. This polyester resin is abbreviated as P3.

GV110 (hydroxyl value 49 (KOHmg / g)), GV150 as commercially available hydroxyl-terminated polyester resin
(Hydroxyl value 34 (KOHmg / g)) was used. These polyester resins are abbreviated as P4 and P5, respectively. Above, manufactured by Nippon Yupica Co., Ltd.

Cationic curing catalyst: SI-L150 (manufactured by Sanshin Chemical Industry Co., Ltd.) BF ₃ -PIP (piperidine complex) << Preparation of powder coating and method for preparing coating film >> 100 to 105 of the formulations shown in Table 1 were used. The mixture was melt-kneaded at 0 ° C., cooled, pulverized, and then passed through a 150-mesh sieve to give a passing product as a powder coating.

The obtained powder was coated on a zinc phosphate-treated steel sheet by an electrostatic coating method to a thickness of about 50 μm, and baked for 30 minutes in a hot air circulation type oven set at 180 ° C. to obtain a coating film for testing. .

<< Evaluation of Cured Coating Film >> The obtained coating film was evaluated by the following methods. The results are shown in Table 2.

Appearance evaluation: Visual evaluation of smoothness of coating film appearance ○: Good Δ: Fairly good ×: Poor solvent resistance: Xylol rubbing test, visual evaluation of coating film surface ○: No scratches or blurring △: There are slight traces ×: Scratches and blurring are generated Water resistance: Evaluation of test film after immersing the test plate in a constant temperature water bath at 50 ° C for 240 hours, such as gloss and blister ○: Good △: Fairly good ×: Poor Impact resistance: An impact test was carried out at 500 g using a DuPont type impact tester. The drop height (cm) that does not show any abnormality in the coating film was shown.

Weather resistance: Sunshine weatherometer
Appearance of coating film after 500 hours Table 1 Example No. Comparative Example No. 1 2 3 4 5 6 7 8 14 15 15 Resin B1 27 − − − − − − − − − Resin B2 − 26 − − − − − − − − Resin B3 − − 28 − 45 35 31 34 16 44 Resin B4 − − − 30 − − − − − − Resin P1 − − − − 55 − − − − − Resin P2 − − − − − 65 − − − − Resin P3 − − − − − − 69 − − − Resin P4 − − − − − − − 66 − − Resin P5 73 74 72 70 84 56 SI-L150 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Benzoin 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Acronal 4F 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Example No. Comparative Example No. 9 10 11 12 12 13 16 17 Resin B1 − − − − − − − − Resin B2 − − − − − − − Resin B3 45 35 31 31 28 28 16 44 Resin B4 − − − − − − − Resin P1 55 − − − − − − Resin P2 − 65 − − − − − Resin P3 − − 69 − − − − Resin P4 − − − 66 − − − Resin P5 − − − − 72 84 56 BF ₃ -PIP 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Benzoin 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Acronis 4F 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Table 2 Example No. Comparative Example No. 1 2 3 4 5 6 7 8 14 15 15 Appearance ○ ○ ○ ○ ○ ○ ○ ○ ○ △ Solvent resistance ○ ○ ○ ○ ○ ○ ○ ○ × △ Water resistance ○ ○ ○ ○ ○ ○ ○ ○ × △ Impact resistance 35 35 35 35 35 35 35 35 20 25 Weather resistance ○ ○ ○ ○ ○ ○ ○ ○ △ △ Example No. Comparative Example No. 9 10 11 12 13 14 16 17 17 Appearance ○ ○ ○ ○ ○ ○ △ △ △ Solvent resistance ○ ○ ○ ○ ○ ○ × △ Water resistance ○ ○ ○ ○ ○ ○ × △ Impact resistance 35 30 35 30 30 30 20 25 Weather resistance Gender ○ ○ ○ ○ ○ ○ △ △

Claims (11)

[Claims] 1. (A) (a) a compound having at least one vinyl group and one epoxy group in one molecule, and (b) a polybasic acid anhydride, a polybasic acid, an acid terminal polymer, And at least one selected from polymers containing a carboxylic acid group,
(C) Epoxy resin obtained by further epoxidizing a resin having a vinyl group obtained by reacting at least one selected from compounds having one or more active hydrogens (B) Hydroxyl group-containing polyester resin (C ) A cationic curing catalyst, and the amount of the component (C) in the composition is 0.05 to 3.0 with respect to the total amount of the components (A) and (B).
A resin composition for a thermosetting powder coating, characterized in that the content is% by weight. 2. The resin composition for thermosetting powder coating composition according to claim 1, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is 4-vinylcyclohexene-1-oxide. . 3. The compound having one or more vinyl groups and one epoxy group in one molecule is 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide. 1. The resin composition for thermosetting powder coating composition of 1. 4. The resin composition for thermosetting powder coating composition according to claim 1, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is limonene monoxide. 5. A compound having at least one vinyl group and one epoxy group in one molecule is represented by the following formula: The resin composition for a thermosetting powder coating according to claim 1, which is a compound represented by << n is an integer of 0 to 30 >>. 6. A compound having at least one vinyl group and one epoxy group in one molecule is represented by the following formula: The resin composition for thermosetting powder coating according to claim 1, which is a compound represented by << n1 and n2 are integers from 0 to 30 >>. 7. A compound having at least one vinyl group and one epoxy group in one molecule is represented by the following formula: The resin composition for thermosetting powder coating according to claim 1, which is a compound represented by << Ph is a substituted phenyl group and n is an integer of 0 to 30. 8. A compound having one or more active hydrogens,
The resin composition for a thermosetting powder coating composition according to claim 1, which is an alcohol, a hydroxyl group-terminated polymer, or a polymer containing a hydroxyl group. 9. The resin composition for thermosetting powder coating composition according to claim 1, wherein the acid-terminated polymer is an acid-terminated polyester. 10. The resin composition for thermosetting powder coating composition according to claim 8, wherein the hydroxyl-terminated polymer is a hydroxyl-terminated polyester. 11. The resin composition for thermosetting powder coating composition according to claim 8, wherein the hydroxyl-terminated polymer is a hydroxyl-terminated polyether.