JPH0762064A - Thermosetting epoxy resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition excellent in weatherability, adherability, flexibility, etc., useful for coatings, coating agents, or adhesives, comprising a specific alicyclic epoxidized polyester and a thermosetting catalyst. CONSTITUTION:The objective composition comprising (A) an alicyclic epoxidized polyester containing at least three (pref. 3-30 or so) of one or more kinds of bifunctional groups, in the molecule, of the formula (R1 and R2 are each H, 1-5C alkyl or endomethylene), pref. 1-30 in hydroxyl value and ca.700-10000 in number-average molecular weight and (B) a thermosetting catalyst (e.g. boron trifluoride, tetraphenyl phosphonium), and, pref. (C) a hydroxyl-contg. compound (e.g. glycerin, trimethylolethane).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting epoxy resin composition having excellent weather resistance, adhesion and flexibility.

[0002]

2. Description of the Related Art Conventionally, as a typical alicyclic epoxy resin, 3,4-epoxycyclohexylmethyl-3 ',
4'-epoxycyclohexanecarboxylate is known. This product has relatively little change in yellowness when exposed to ultraviolet rays and has excellent weather resistance, but on the other hand, it has relatively strong initial coloring of the cured product, and also has the drawback that the cured product is brittle. There is.

The present inventors have previously proposed, as a new useful alicyclic epoxy resin, an epoxidized polyester having a hydroxyl group (Japanese Patent Application No. 4-106023), and further using the alicyclic epoxy resin as a resin. A photocurable epoxy resin composition as a component has been proposed (Japanese Patent Application No. 4-116979).

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a thermosetting epoxy resin which is excellent in weather resistance and ultraviolet resistance, has the original characteristics of an epoxy resin, and is tough, flexible, and excellent in adhesion to a substrate. It is intended to provide a composition.

[0005]

DISCLOSURE OF THE INVENTION As a result of continuous studies to solve the above problems, the present inventors have found that the alicyclic epoxidized polyester having the above-mentioned specific structure proposed by the present inventors and thermosetting. We have found that an epoxy resin composition containing a catalyst can achieve the intended purpose, and have completed the present invention based on such findings.

That is, in the thermosetting epoxy resin composition according to the present invention, one or more kinds of bifunctional groups represented by the general formula (1) (hereinafter referred to as "epoxycyclohexane groups") are molecules. Alicyclic epoxidized polyester containing 3 or more (preferably about 3 to 50, more preferably about 3 to 30) and having a number average molecular weight of about 700 to about 10,000 (hereinafter referred to as “the present epoxy”). Polyester ”) and a thermosetting catalyst.

[0007]

[Chemical 2] [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an endomethylene group. ]

Usually, most commercially available alicyclic epoxy resins have less than 3 alicyclic epoxy groups in one molecule, which has a drawback that the cured product is brittle. On the other hand, a cured product excellent in flexibility, corrosion resistance and curability can be obtained from the present epoxy polyester having 3 or more epoxy cyclohexane groups in one molecule.

The epoxy polyester has a number average molecular weight of from about 700 to about 10,000, preferably about 100.
It is about 0 to about 5,000. If it is less than 700, the curability is good, but the resulting cured product is brittle, and if it exceeds 10,000, the viscosity of the prepared resin composition is high, and the workability is lowered. Compatibility may also decrease. Most of the alicyclic epoxy resins that are industrially available have a low molecular weight and have problems of working environment such as odor and skin irritation. On the other hand, since the present epoxy polyester has a high molecular weight, it is possible to reduce odor, skin irritation and the like.

Although the present epoxy polyester can be cured alone, it exhibits more excellent curability in the presence of a compound containing a hydroxyl group. The hydroxyl value of the present epoxy polyester is usually about 1 to 150, but the tendency is particularly remarkable when it is 30 or less.

The hydroxyl group-containing compound according to the present invention has 2 or more, more preferably 3 or more hydroxyl groups in one molecule and has a molecular weight (polymer) of about 10,000 or less, preferably about 5,000 or less. Is a compound having a number average molecular weight). When the molecular weight exceeds about 10,000, the workability tends to decrease due to the high viscosity. The hydroxyl value of the compound is about 20 or more, usually about 40 to about 2,000.

Specific examples of the hydroxyl group-containing compound include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbit, a low condensation product of phenol and formalin,
Low condensation products of cresol and formalin, polymers and copolymers of hydroxyl group-containing (meth) acrylic monomers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol, Examples include polyether polyols and polyester polyols.

The monomers copolymerizable with the hydroxyl group-containing (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylate. Examples are (meth) acrylic acid monomers such as 2-ethylhexyl acrylate, styrene, acrylonitrile, acrylamide, methacrylamide, vinyl acetate, butyl vinyl ether, and the like.

The recommended compounding amount of the hydroxyl group-containing compound is
It is appropriately selected based on the epoxy equivalent of the present epoxy polyester. Specifically, when the equivalent ratio of the hydroxyl group (derived from the hydroxyl group-containing compound and the present epoxidized polyester) to the epoxy group (derived from the present epoxy polyester) is 0.3 to 5, particularly 0.5 to 3. Preferably there is. When the equivalent ratio is less than 0.3, the curability is deteriorated, which is not preferable, and when it exceeds 5, the evaluation of coating film physical properties obtained by comprehensively judging water resistance, curability and weather resistance is deteriorated. Not preferable.

The iodine value of the present epoxy polyester is not particularly specified, but for applications requiring weather resistance such as outdoor use, the iodine value is 4 or less, preferably 2.5.
The following is desirable. When the iodine value exceeds 4, the weather resistance and the ultraviolet resistance are deteriorated, and the material tends to yellow.

The recommended acid value of the present epoxy polyester is preferably 50 or less, more preferably 30 or less. When the acid value exceeds 50, problems such as storage stability and water resistance may occur.

The oxirane oxygen content of the present epoxy polyester is preferably about 0.5 to 10% by weight.

The following compounds are exemplified as the thermosetting catalyst according to the present invention. That is, boron trifluoride, boron trifluoride-n-hexylamine complex, boron trifluoride-monoethylamine complex, boron trifluoride-benzylamine complex, boron trifluoride-diethylamine complex, boron trifluoride-butylamine Complex, boron trifluoride-piperidine complex, boron trifluoride-triethylamine complex, boron trifluoride-aniline complex, boron trifluoride-methanol complex, boron trifluoride-acetylacetone complex, boron trifluoride-diethyl ether complex Such as boron trifluoride complex, phosphorus trifluoride, arsenic pentafluoride, antimony pentafluoride and their amine complexes, zinc chloride, tin chloride, zirconium chloride, antimony chloride, iron chloride, aluminum chloride, zinc bromide, Lewis acids such as tin bromide and antimony bromide and their amine complexes,

The tetraphenylphosphonium, benzyltriethylammonium, N, N-dimethyl -N- onium and a counter anion such as benzyl pyridinium (BF ₄ ^-, P
F ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ^−, etc.), phosphoric acid, phosphorous acid, hydrogen bromide, hydrogen chloride,
Inorganic protonic acid such as sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, organic protonic acid such as benzenesulfonic acid, naphthoquinonediazidesulfonic acid ester such as butyl 1,2-naphthoquinonediazide-4-sulfonate, p
-Toluenesulfonic acid-Nitrobenzylsulfonic acid such as o-nitrobenzyl, diazosulfone such as 1-benzenesulfonyl-1-benzoyldiazomethane, metal such as copper, aluminum, zinc, tin, iron, titanium and zirconium, and methyl acetoacetate A β-ketoester such as ethyl acetoacetate, a malonic acid diester such as dimethyl malonate, a metal complex with a β-diketone such as acetylacetone, an alkoxide compound of the metal and a hydrolyzate thereof.

Quaternary ammonium salts such as tetramethylammonium chloride and tetramethylammonium bromide, inorganic acids such as tetramethylammonium perchlorate, tetra-n-butylammonium phosphate and tetra-n-butylammonium hydrogensulfate. Organic alkyl tetraalkylammonium salts such as tetraalkylammonium salt, tetramethylammonium acetate, tetraethylammonium acetate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide , Cetyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide, monohydroxyethyltrimethylammonium hydroxide, dihydric hydroxide Quaternary ammonium hydroxides such as Russia carboxyethyl dimethyl ammonium are exemplified.

The thermosetting catalyst according to the present invention may be used alone or
The heat curing catalyst can be used in an appropriate combination of two or more kinds (the total amount when two or more kinds are used).
Is about 0.05 to 10% by weight, preferably about 0.1 to 5% by weight, based on the total weight of the resin components. If it is used in a small amount, it may not be sufficiently cured, and if it exceeds 10% by weight, problems such as storage stability, solubility, water resistance, and transparency may occur.

The epoxy polyester has the general formula (2):
A polyester having a number average molecular weight of about 700 to about 10,000 (hereinafter referred to as "the present", containing three or more difunctional groups represented by the formula (hereinafter referred to as "cyclohexene group") in the molecule. Polyester ") can be industrially produced by epoxidizing it with, for example, hydrogen peroxide or a peracid such as peracetic acid.

[0023]

[Chemical 3] [In the formula, R ¹ and R ² are the same as those in the general formula (1). ]

The present polyester is obtained by polyesterification of a dibasic acid having a cyclohexene group or its acid anhydride (hereinafter referred to as "main acid component") and a polyhydric alcohol.

Examples of the main acidic component include alicyclic dibasic acids represented by the general formula (3) and acid anhydrides thereof, specifically, Δ ⁴ -tetrahydrophthalic acid and 3-methyl-Δ. ^Four
Examples thereof include tetrahydrophthalic acid, 4-methyl-Δ ⁴ -tetrahydrophthalic acid, Δ ⁴ -nadic acid, methyl-Δ ⁴ -nadic acid and their acid anhydrides.

[0026]

[Chemical 4] [In formula, it is the same as R < ¹ >, R < ² > and General formula (1). ]

The polyhydric alcohol has 2 to 55 carbon atoms.
And dihydric alcohols having 3 to 24 carbon atoms and having 3 or more carbon atoms.

Examples of such dihydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 2,2-diethyl-1,3-propane. Diol, 2-butyl-1,
3-propanediol, 1,3-butanediol, 1,
4-butanediol, 1,5-pentanediol, 3-
Methyl-1,5-pentanediol, 2-methyl-2,
4-pentanediol, 2,2,4-trimethyl-1,
3-pentanediol, 1,6-hexanediol, 2
-Ethyl-1,3-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, bisphenol A, hydrogenated bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, hydrogenated bisphenol A Examples thereof include ethylene oxide adducts, propylene oxide adducts of hydrogenated bisphenol A, bisphenol F, hydrogenated bisphenol F, and the like.

Examples of trihydric or higher alcohols include glycerin, trimethylolethane, trimethylolpropane,
Examples include pentaerythritol, dipentaerythritol, sorbit, low condensation products of phenol and formalin, low condensation products of cresol and formalin, and the like.

In order to improve the physical properties of the cured product, other dibasic acid, tribasic or higher polybasic acid and its acid anhydride (hereinafter referred to as "sub-acid component") are used together for polyesterification. Further, it is also possible to use a monovalent organic acid or a monohydric alcohol in combination for polyesterification in order to block hydroxyl groups or carboxylic acid groups at the molecular ends.

Examples of the auxiliary acid component include the following aromatic polyvalent carboxylic acids and their acid anhydrides, as well as aliphatic polyvalent carboxylic acids, alicyclic polyvalent carboxylic acids and their acid anhydrides. Saturated aliphatic polycarboxylic acids, alicyclic polycarboxylic acids and their acid anhydrides are preferred for applications where importance is attached to weather resistance.

Such aromatic polycarboxylic acid is, for example,
It is represented by the general formula (4) or (5).

[0033]

[Chemical 5] [In formula, m is an integer of 2-4. ]

[0034]

[Chemical 6] [In the formula, l and p are the same or different and each is an integer of 1 to 2, and X is directly bonded or -O-, -S-, -SO.
_{-, - SO 2 -, -} CH 2 -, - C (CH 2) 3 -, -CO
A group represented by-is shown. ]

Specific compounds include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, benzophenonedicarboxylic acid, diphenylsulfonetetracarboxylic acid, diphenylsulfonedicarboxylic acid, biphenyltetracarboxylic acid. Acid, biphenyl dicarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl ether dicarboxylic acid, bis (3,4-dicarboxyphenyl) sulfoxide, 2,2-bis (3,4-dicarboxyphenyl) propane and their acid anhydrides, etc. It is illustrated.

The aliphatic and alicyclic polycarboxylic acid is represented by, for example, the general formula (6).

[0037]

[Chemical 7] [In the formula, n is an integer of 2 to 4, R ³ may have an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or a halogen atom,
It represents a saturated or unsaturated aliphatic hydrocarbon residue having 1 to 36 carbon atoms or a saturated alicyclic hydrocarbon residue having 4 to 30 carbon atoms. ]

Specific compounds include maleic acid, fumaric acid, malonic acid, succinic acid, dodecenylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, dodecanedioic acid, Citric acid, isocitric acid, aconitic acid, tartaric acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetetracarboxylic acid, tricarboxycyclopentylacetic acid, cyclopentanetetracarboxylic acid, cyclobutanetetracarboxylic acid, 3,5,6-tricarboxylic acid Examples include carboxynorbornane-2-acetic acid, het acid, tetrabromophthalic acid, tricarballylic acid, butanetetracarboxylic acid, and acid anhydrides thereof.

The monohydric alcohol has 1 to 2 carbon atoms.
The alcohol of 4 is illustrated, but specific examples include butanol, isobutanol, isoamyl alcohol, hexanol, cyclohexanol, heptanol, 2-ethylhexanol, octanol, nonyl alcohol, decanol, isodecanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, Stearyl alcohol, oleyl alcohol and the like can be mentioned.

Examples of monovalent organic acids include carboxylic acids having 1 to 24 carbon atoms, and specific examples include caproic acid and
Caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid,
Examples thereof include oleic acid and linoleic acid.

A main acid component (a) and a polyhydric alcohol (d) which are essential constituents, and a sub-acidic component (b), a monovalent organic acid (c) or a monovalent component which is optionally used in combination. Typical blending ratios (molar basis) of alcohol (e) are as follows. By using the components (b), (c), and (e) together, side reactions such as addition of water, a catalyst, and a cocatalyst to the produced epoxy group are suppressed, and water in the post-treatment water washing step is further suppressed. It is possible to avoid problems such as deterioration of separability. This is particularly important in epoxidized polyesters having hydroxyl groups.

(A) :( b) = 100: 0 to 40:60 [(a) + (b)] :( c) = 100: 0 to 30:70
(Preferably 100: 0 to 50:50) (d) :( e) = 100: 0 to 20:80 (preferably 100: 0 to 40:60) (a) :( b) is lower than 40:60. Then, the number of epoxycyclohexane groups in the molecule is reduced, so that the performance is lowered when it is applied as a component of the epoxy resin, which is a problem.

On the other hand, the hydroxyl groups contained in the components (b), (d) and (e) are 0.8 to 1.5 times equivalent to the carboxyl groups contained in the components (a), (b) and (c). , Preferably 0.9 to 1.4 times equivalent.

The thermosetting epoxy resin composition according to the present invention may be used in combination with other epoxy compounds. In that case, the compounding ratio of this epoxy polyester is
It is 30% by weight or more, preferably 50% by weight or more, based on the total weight of the present epoxy polyester and other epoxy compounds. If it is less than 30% by weight, the comprehensive evaluation of the physical properties of the coating film such as curability, weather resistance and flexibility tends to deteriorate, which is not preferable.

Examples of other epoxy compounds mentioned above include bisphenol type epoxy resins such as bisphenol A.diglycidyl ether and bisphenol F diglycidyl ether, 3,4-epoxycyclohexylmethyl-
3 ', 4'-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexylmethyl)
Alicyclic epoxy resins such as adipate and vinyl hexenedioxide, novolac type epoxy resins, glycidyl ester of neoic acid, glycidyl ester type epoxy resins such as diglycidyl ester of hexahydrophthalic acid or tetrahydrophthalic acid, hydrogenated bisphenol A and hydrogen Bisphenol F diglycidyl ether type epoxy resin,
Examples thereof include glycidyl ethers obtained from alcohols such as 1,4-cyclohexanedimethanol, alkylene oxide addition alcohols of bisphenol A, and polypropylene glycols.

If desired, the thermosetting epoxy resin composition according to the present invention may include a curing accelerator, a solvent, a pigment, a filler, a coupling agent, an antioxidant, an ultraviolet absorber, a plasticizer, and a flow control agent. , Cellulose acetate butyrate,
Petroleum resin, phenol resin, etc. can be added.

The thermosetting epoxy resin composition thus obtained can be easily crosslinked and cured at a temperature of 200 ° C. or lower, and is useful for paints, adhesives, inks, casting materials, sealing materials and the like. It is applied to a wide variety of fields by appropriately selecting the method of use according to its application. For example, casting, potting, dipping method, etc. when used as a resin sealant, and air spray, roll coating, brush coating when used as a paint,
A method such as electrostatic air spray can be applied.

[0048]

EXAMPLES The present invention will be described in detail below with reference to examples. In addition, the number average molecular weight (M
In n), the measurement results obtained by liquid chromatography are analyzed and expressed in terms of polystyrene.

The number of cyclohexene groups (X), the number of epoxycyclohexene groups (Z) and the conversion rate (%) contained in one molecule were calculated according to the following equations. X = (IV [PE] / IV [THPA]) × Mn [PE] × (1 / Mw
[THPA]) Z = [(OX-OX / 16) × 253.8 / IV [PE]] × X × [Mn [E
PE] / Mn [PE]] conversion rate (%) = (1-IV [EPE] / IV [PE]) × 100 The symbols in the above formulas are as follows. IV [PE]: Iodine value of polyester IV [THPA]: Iodine value of tetrahydrophthalic anhydride Mn [PE]: Number average molecular weight of polyester Mn [EPE]: Number average molecular weight of epoxidized polyester Mw [THPA]: Tetrahydroanhydride Molecular weight of phthalates OX-OX: Oxylan oxygen content (wt%)

Production Example 1 Δ ⁴ -tetrahydrophthalic anhydride (hereinafter "THPA")
Is abbreviated. ) 532 g (3.5 mol), isophthalic acid 249 g (1.5 mol), trimethylolpropane 26
9 g (2 mol), 1,4-butanediol 450 g (5
Polyester prepared using 360 g (2.5 mol) of 2-ethylhexanoic acid as a raw material (acid value 1.
2, hydroxyl value 60.0, iodine value 57.0, Mn2,0
00, X4.5 pieces) 100 g of epoxidized polyester at 65 ° C. with a 60% hydrogen peroxide aqueous solution, which is a highly viscous liquid epoxidized polyester (oxirane oxygen 2.1% by weight, iodine value 1.7, Mn2). , 400, Z3.1, hereinafter referred to as "epoxy polyester 1").

Production Example 2 Instead of the epoxy polyester 1, 3-methyl-Δ ⁴ −
Tetrahydrophthalic anhydride 581 g (3.5 mol), isophthalic acid 249 g (1.5 mol), trimethylolpropane 269 g (2 mol), 1,4-butanediol 4
50 g (5 mol) and 2-ethylhexanoic acid 360 g
Polyester prepared using (2.5 mol) as a raw material (acid value 5.3, hydroxyl value 64.0, iodine value 49.
5, Mn2,200, X4.3) is a highly viscous liquid epoxidized polyester (oxirane oxygen 2.2% by weight, iodine value 1.9, Mn2,60).
0, Z 3.6, hereinafter referred to as "epoxy polyester 2". ) Got.

Production Example 3 Instead of the epoxy polyester 1, 760 g of THPA
(5 mol), trimethylolpropane 202 g (1.5
Mol), neopentyl glycol 208 g (2 mol) and 2-ethylhexanol 390 g (3 mol) as a raw material prepared polyester (acid value 2.3, hydroxyl value 4
7.8, iodine value 89.8, Mn 1,200, X4.2
Highly viscous liquid epoxidized polyester (oxirane oxygen 4.7% by weight, iodine value 1.8, Mn 1,300, Z 3.8 pieces, hereinafter referred to as “epoxy polyester 3”) obtained by epoxidizing the above. Obtained.

Production Example 4 Instead of the epoxy polyester 1, 760 g of THPA
(5 mol), trimethylolpropane 202 g (1.5
Polyester) (acid value 2.8, hydroxyl value 50.5, iodine value 91.mol), 1,6-hexanediol 295 g (2.5 mol) and 2-ethylhexanol 260 g (2 mol) as raw materials. 2, Mn 2,000, X
High viscosity liquid epoxidized polyester obtained by epoxidizing (7.2 pieces) (oxirane oxygen 4.8% by weight, iodine value 1.7, Mn2,100, Z6.3 pieces, hereinafter referred to as "epoxy polyester 4"). ) Got.

Production Example 5 THPA 760 g instead of Epoxy Polyester 1
(5 moles), trimethylolpropane 269 g (2 moles), 1,4-butanediol 180 g (2 moles) and 2-ethylhexanol 260 g (2 moles) as a raw material prepared polyester (acid value 2.3, hydroxyl group). Value 5
8.8, iodine value 95.1, Mn2,600, X9.6
To obtain a highly viscous liquid epoxidized polyester (oxirane oxygen: 4.9% by weight, iodine value: 2.0, Mn: 2,650, Z: 8.0, hereinafter referred to as “epoxy polyester 5”). It was

Production Example 6 Instead of the epoxy polyester 1, 760 g of THPA
(5 mol), trimethylolpropane 188 g (1.4
Polyester prepared using 224 g (1.9 mol) of 1,6-hexanediol and 338 g (2.6 mol) of 2-ethylhexanol as raw materials (acid value 2.
4, hydroxyl value 21.5, iodine value 90.4, Mn1,8
00, X6.4), a highly viscous liquid epoxidized polyester (oxirane oxygen: 4.9% by weight, iodine value: 2.2, Mn: 1,900, Z: 5.8),
Hereinafter referred to as "epoxy polyester 6". ) Got.

Production Example 7 292 g (2 mol) of adipic acid, 269 g (2 mol) of trimethylolpropane, 90 g of 1,4-butanediol
(1 mol) and 216 g (1 mol) of 2-ethylhexanoic acid are esterified to give a hydroxyl group-containing compound having an acid value of 0.3, a hydroxyl value of 210.0 and Mn850 (hereinafter referred to as "hydroxyl group-containing compound 1"). Obtained.

Thermal curing method 1. When the boron trifluoride-monoethylamine complex (thermosetting catalyst 1) is used as the thermosetting catalyst, the present epoxy polyester and other epoxy resin are used when used in combination with the predetermined epoxy polyester (other epoxy resin or hydroxyl group-containing compound). Of epoxy resin or hydroxyl group-containing compound) 1)
00 parts by weight, boron trifluoride-monoethylamine complex 2.5 parts by weight, toluene 48 parts by weight and methyl isobutyl ketone 36 parts by weight were mixed and mixed sufficiently. The prepared resin composition was applied on a standard test plate of 150 × 50 × 0.3 mm so that the film thickness after curing would be about 20 μm, and cured at 100 ° C. for 15 minutes and then at 160 ° C. for 30 minutes.

2. When tetra-n-butylammonium hydroxide (thermosetting catalyst 2) is used as the thermosetting catalyst, the present epoxy polyester and other epoxy resin (when used in combination with another epoxy resin or a hydroxyl group-containing compound) are used. 100 parts by weight of epoxy resin or hydroxyl group-containing compound, 15 parts by weight of 10% tetra-n-butylammonium hydroxide in methanol, 40 parts by weight of toluene and 30 parts of methyl isobutyl ketone.
The ingredients were blended so as to be part by weight and thoroughly mixed. The prepared resin composition was applied on a standard test plate of 150 × 50 × 0.3 mm so that the film thickness after curing would be about 20 μm, and cured at 80 ° C. for 15 minutes and further at 150 ° C. for 30 minutes.

Weather resistance: Weatherometer (manufactured by Toyo Seiki Seisakusho; xenon burner 0.39 W / cm ² (340n
m)), black panel temperature 63 ° C, 60% R
After testing for 500 hours under the conditions of H, 18 dispersed water / 120 minutes, the sample having almost no change in appearance is indicated by ◯, the sample having a slight change by Δ, and the sample having a change by x.

Adhesiveness (cross-cut tape method): JIS K 5
According to 400. A cut that penetrates the coating film on the test piece and reaches the bare ground is made on a grid (1 × 1 mm square, 100 pieces), and an adhesive tape is peeled off on the grid and the coating film after peeling The state of adhesion is visually observed.

Impact resistance (impact deformation test): JIS K 5
According to 400. A ball with a radius of 6.35 mm impacts the surface of the coating film, and the impact resistance when impact deformation occurs, cracks,
Check if it can be peeled off. It is evaluated by the falling distance of a falling body with a mass of 500 g.

Flex resistance: According to JIS K 5400.
The test piece is bent with the coating film outside, and the resistance to cracking due to the difference in elongation between the upper surface and the lower surface of the coating film produced at this time is examined. The smaller the bending diameter, the larger the difference in elongation.

Pencil scratch test: JIS K 5400
According to. The scratch resistance of the coating film is examined by breaking the coating film when the hardness of the pencil lead is changed.

Comparative Epoxy Resin 1 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (epoxy equivalent;
135, manufactured by Daicel Chemical Industries, Ltd., trade name Celoxide 2021)

Comparative epoxy resin 2 Bisphenol A diglycidyl ether (epoxy equivalent: 190, manufactured by Yuka Shell Co., Ltd., trade name Epicoat 828

Examples 1 to 9 Various kinds of epoxy resin compositions were prepared by applying the thermosetting catalyst 1, and these were cured by a predetermined method. The obtained cured products had weather resistance, adhesion and impact resistance. The bending resistance and pencil scratch strength were evaluated. The results obtained are shown in Table 1.

Comparative Example 1 A resin composition was prepared by using the comparative epoxy resin 1 as a resin component and applying the thermosetting catalyst 1. The resin composition was cured by a predetermined method, and the characteristics of the cured product were evaluated. The obtained results are first
Shown in the table.

Comparative Example 2 A resin composition was prepared by using the comparative epoxy resin 2 as a resin component and applying the thermosetting catalyst 1. The resin composition was cured by a predetermined method, and the characteristics of the cured product were evaluated. The obtained results are first
Shown in the table.

Examples 10 to 18 Applying the thermosetting catalyst 2 to prepare epoxy resin compositions,
This was cured by a predetermined method, and the resulting cured product was evaluated for weather resistance, adhesion, impact resistance, flex resistance and pencil scratch strength. The results obtained are shown in Table 2.

Comparative Example 3 A resin composition was prepared by using the comparative epoxy resin 1 as a resin component and applying the thermosetting catalyst 2, and the resin composition was cured by a predetermined method. However, in this case, the curability was poor and the physical properties could not be evaluated.

Comparative Example 4 A resin composition was prepared by using the comparative epoxy resin 2 as a resin component and applying the thermosetting catalyst 2, and the resin composition was cured by a predetermined method. However, in this case, the curability was poor and the physical properties could not be evaluated.

[Table 1]

[Table 2]

[0072]

EFFECT OF THE INVENTION The thermosetting epoxy resin composition according to the present invention can be easily cured, has excellent weather resistance and ultraviolet resistance, has the original characteristics of the epoxy resin such as adhesiveness, and is tough. It has excellent flexibility and can be used in paints, inks, coating materials, adhesives, lining materials, casting materials, sealing materials, etc.

Claims (3)

[Claims] 1. A molecule containing three or more of one or more kinds of bifunctional groups represented by the general formula (1), having a hydroxyl value, and having a number average molecular weight of about 700 to 10, A thermosetting epoxy resin composition comprising an alicyclic epoxidized polyester of 000 and a thermosetting catalyst. [Chemical 1] [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an endomethylene group. ] 2. The thermosetting epoxy resin composition according to claim 1, which is used together with a hydroxyl group-containing compound. 3. The thermosetting epoxy resin composition according to claim 2, wherein the alicyclic epoxidized polyester has a hydroxyl value of 1 to 30.