JPH09157357A - Epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel useful epoxy resin compsn. which has improved cold curability and excellent weather resistance and mechanical properties by incorporating a hydrogenated bisphenol A glycidyl ether and a specified bisphenol compd. SOLUTION: At least one bisphenol compd. selected from among those represented by the formula (wherein X represents CH2 , CH(CH3 ), C(CH3 )2 , or O; and R<1> and R<2> represent each H or a 1-4 C alkyl) is incorporated in an amt. of 2 to 50 pts.wt. into 100 pts.wt. hydrogenated bisphenol A glycidyl ether which is a colorless and transparent liq. having an epoxy equivalent of 180 to 250 and a viscosity of 10 to 50 P at 25 deg.C and prepd. by addition-reacting a hydrogenated bisphenol A with epichlorohydrin and conducting a ring closing reaction by dehydrochlorination in the presence of a basic compd. Further, a chain, cyclic, or heterocyclic aliph. polyamine curing agent, which can be easily mixed with an epoxy compd. at room temp., can easily cause a curing reaction and can provide a coating film having good weather resistance, is incorporated in such an amt. that the equivalent ratio of active hydrogen in the curing agent to the epoxy group is 0.5 to 1.5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition, and more particularly to an epoxy resin composition having excellent room temperature curability and weather resistance.

[0002]

2. Description of the Related Art Generally, epoxy resin compositions are excellent in mechanical and electrical properties, and have good adhesiveness, solvent resistance, water resistance, heat resistance, etc. Widely used in adhesives, paints and civil engineering.
Particularly, in recent years, in the field of paints and civil engineering and construction, room temperature curable epoxy resin compositions have been used as anticorrosion paints for flooring materials, pavement materials, outdoor storage tanks and pipes that require weather resistance.

As the room temperature curable epoxy resin composition, a general-purpose epoxy resin, bisphenol A diglycidyl ether, and an aliphatic polyamine-based curing agent and epoxy having good weather resistance and capable of curing the epoxy resin even at room temperature. Combinations with resin cure accelerators are known.

As the epoxy resin curing accelerator in the above, carboxylic acid, phenols, alcohols, triphenylphosphite (hereinafter abbreviated as "TPI"), 2,4,6-tris (dimethylaminomethyl).
Phenol (hereinafter abbreviated as "DMP-30"), salicylic acid, and the like are exemplified (Soichi Muroi, Shuichi Ishimura, "Introduction Epoxy Resin" (Kobunshi Kogakukai, 1988), No. 79.
Page, Eiichita "Epoxy Resin High Functionality and Application Development"
(CMC, 1985) p. 13).

However, although bisphenol A diglycidyl ether has excellent physical properties peculiar to epoxy resin, there is room for improvement in weather resistance, and when the cured product is left outdoors or emits ultraviolet rays as a light source. When exposed to water, there is a problem in that gloss decreases and yellowing occurs due to chalking over time.

When hydrogenated bisphenol A diglycidyl ether is applied in place of bisphenol A diglycidyl ether in order to solve such a problem, the weatherability is improved, but the curability at room temperature to low temperature is bisphenol A diglycidyl ether. It is significantly inferior to ether, and it takes a long time to cure, especially in winter construction.

Further, when a carboxylic acid is added as a curing accelerator for an epoxy resin composition comprising a combination of hydrogenated bisphenol A diglycidyl ether and an aliphatic polyamine type curing agent, conversely, at a room temperature, It is not preferable because it causes a decrease in curing reactivity. On the other hand, in the case of adding a small amount of alcohols, TPI, DMP-30, phenol, p-ethylphenol, nonylphenol and other monophenols, the curability at room temperature to low temperature cannot be improved, Increasing the blending amount is not preferable because the mechanical strength such as impact resistance of the cured product tends to decrease. In addition, salicylic acid and hydroquinone,
When polyhydric phenols such as resorcinol, catechol and 2-tert-butylhydroquinone are added, the room temperature curability is improved, but the cured product is markedly colored and the weather resistance is deteriorated, which is not preferable.

Therefore, there has been a strong demand for the development of a compounding formulation which satisfies the room temperature curability, weather resistance and mechanical properties of the epoxy resin composition.

[0009]

DISCLOSURE OF THE INVENTION The present invention has improved room temperature curing properties, excellent weather resistance and mechanical properties, and is used for flooring materials, paving materials,
An object of the present invention is to provide a novel and useful epoxy resin composition suitable for outdoor paints and coating materials.

[0010]

Means for Solving the Problems As a result of intensive studies to solve such problems, the present inventors have found that an epoxy resin composition which is liquid at room temperature and comprises hydrogenated bisphenol A diglycidyl ether and an aliphatic polyamine-based curing agent. By incorporating a specific bisphenol compound in place of a part or all of conventionally known curing accelerators into the product, the room temperature curability is significantly improved, and a cured product having excellent weather resistance and mechanical properties can be obtained. The present invention has been completed and the present invention has been completed based on such findings.

That is, the epoxy resin composition according to the present invention is a liquid epoxy resin composition containing hydrogenated bisphenol A diglycidyl ether and an aliphatic polyamine-based curing agent at room temperature. 2 to 5 parts by weight of one or more bisphenol compounds represented by the general formula (1).
It is characterized by containing 0 parts by weight.

[0012]

Embedded image [Wherein, X is _{-CH 2 -, - CH (CH} 3) -, - C (C
Represents a or -O- - H _{3) 2.} R ¹ and R ² are the same or different and each represent hydrogen or an alkyl group having 1 to 4 carbon atoms. ]

Specific examples of the bisphenol compound represented by formula (1) include bis (4-hydroxyphenyl) methane (hereinafter abbreviated as "bisphenol F") and bis (2-ethyl-4-hydroxy). Phenyl)
Methane, bis (5-methyl-2-hydroxyphenyl)
Methane, bis (2-hydroxyphenyl) methane, 2-
Hydroxyphenyl-4-hydroxyphenylmethane,
1,1-bis (4-hydroxyphenyl) ethane (hereinafter abbreviated as “bisphenol E”), 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “bisphenol A”), 2, 2-bis (2-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter abbreviated as "bisphenol C"), 2,2-bis (2 -Hydroxyphenyl) propane, 2- (2-hydroxyphenyl) -2- (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) ether, bis (2-hydroxyphenyl) ether and the like are exemplified,
Particularly, bisphenol A, bisphenol F, bisphenol E and bisphenol C are recommended. These bisphenol compounds may be used alone or in combination.

The bisphenol compound according to the present invention is added in a proportion of 2 to 50 parts by weight, preferably 5 to 20 parts by weight, based on the hydrogenated bisphenol A diglycidyl ether. If the amount is less than this range, the room temperature curing property is insufficient, and it takes a long time to cure particularly in winter. On the contrary, if the amount is more than the above range, the weather resistance of the cured product decreases and the desired effect is obtained. It tends to become difficult to handle due to an increase in the viscosity of the epoxy resin composition.

The hydrogenated bisphenol A diglycidyl ether according to the present invention is usually prepared by subjecting hydrogenated bisphenol A to addition reaction with epichlorohydrin, and subjecting the compound to ring closure by dehydrochlorination in the presence of a basic compound. It is an epoxy compound, and is an almost colorless and transparent liquid having an epoxy equivalent of 180 to 250 and a viscosity of about 10 to 50 poise at a temperature of 25 ° C. Incidentally, a part of the hydrogenated bisphenol A diglycidyl ether can be replaced with another epoxy compound for the purpose of optimizing the viscosity of the epoxy resin composition, the adhesiveness of the cured coating film, the mechanical properties and the like.

As such other epoxy compound, 3,
Alicyclic epoxy resins such as 4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate; glycidyl ester type epoxy resins such as hexahydrophthalic acid diglycidyl ester; dihydric phenols such as bisphenol A and bisphenol F Bisphenol type epoxy resin obtained from epichlorohydrin;
Novolak type epoxy resin obtained from polychlorophenol such as phenol novolac resin and epichlorohydrin;
Polyolefin type epoxy resin such as epoxidized product of polybutadiene; glycidyl ether type epoxy resin obtained from dichloroalcohol such as hydrogenated bisphenol F, 1,4-cyclohexanedimethanol, alkylene oxide adduct of bisphenol A and epichlorohydrin;
Examples of reactive diluents such as epoxides of α-olefins, alkyl glycidyl ethers, neodecanoic acid glycidyl esters, neopentyl glycol diglycidyl ethers, 1,6-hexanediol diglycidyl ethers, glycerin polyglycidyl ethers, etc. Is not particularly limited as long as it does not adversely affect the predetermined effects of the present invention, but it is usually preferable to use 30% by weight or less of hydrogenated bisphenol A diglycidyl ether.

The aliphatic polyamine-based curing agent according to the present invention can be easily mixed with an epoxy compound at room temperature, has a relatively good curing reactivity, and has a weather resistance of a coating film. Heterocyclic aliphatic polyamines and mixtures and modified products thereof.

Specifically, ethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,
1,3,6-Trisaminomethylhexane, N-benzylethylenediamine, trimethylhexamethylenediamine, dimethylaminopropylamine, diethylaminopropylamine, aminoethylethanolamine, diethyleneglycol bispropylenediamine, menthenediamine, isophoronediamine, norbornanediamine. ,
N-aminoethylpiperazine, diaminodicyclohexylmethane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-bis (aminomethyl) cyclohexane, 3,9-bis (3-aminopropyl) -2,4.
Examples thereof include addition modified products of 8,10-tetraoxaspiro [5,5] undecane and mixtures thereof, epoxy compounds, acrylonitrile, unsaturated compounds such as acrylic acid esters, and the like, preferably isophoronediamine,
1,3-bis (aminomethyl) cyclohexane, N-benzylethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and mixtures thereof, Epoxy compound (for example, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether,
Examples of addition modified products include 1,6-hexanediol diglycidyl ether and neopentyl glycol diglycidyl ether.

Commercially available curing agents containing such preferred aliphatic polyamine-based curing agents as main components include trade names "Fujicure FXK-825" and "Fujicure # 4233".
(These are manufactured by Fuji Kasei Kogyo Co., Ltd.), "Sunmide IM-54
4 "(manufactured by Sanwa Chemical Industry Co., Ltd.)," Daitokural I-13
21 "," Daitokural B-1616 "(all manufactured by Daito Sangyo Co., Ltd.)," Epomate B-002 "(manufactured by Yuka Shell Epoxy Co., Ltd.)," Sumikyua AF "(manufactured by Sumitomo Chemical Co., Ltd.) and the like. .

The compounding amount of the aliphatic polyamine-based curing agent is not particularly limited as long as a predetermined effect can be obtained, but usually, the equivalent ratio of active hydrogen in the curing agent to the epoxy group is 0.5 to 1. 0.5, preferably about 0.7 to 1.2.

Other additives may be added to the epoxy resin composition according to the present invention. As such other additives, conventionally known curing accelerators, plasticizers, dyes, pigments,
Antioxidant, UV absorber, light stabilizer, flame retardant, filler,
Leveling agents, antifoaming agents, anti-sagging agents, various additives such as solvents and substrates are exemplified, and the application amount thereof is not particularly limited as long as it does not adversely affect the predetermined effects of the present invention. It is applied in the desired range.

Examples of the curing accelerator include phosphorous acid phenyl esters such as triphenyl phosphite, diphenyl hydrogen phosphite and diphenyl monodecyl phosphite, polyhydric alcohols such as trimethylol propane and glycerin, 2, 4, 6 -Tris (dimethylaminomethyl) phenol, cellulose acetate butyrate, etc. are exemplified,
Usually hydrogenated bisphenol A diglycidyl ether 1
0 to 10 parts by weight, preferably 0 to 5 parts by weight
Applied in parts by weight.

As the plasticizer, polybasic acid esters such as dioctyl phthalate, dibutyl phthalate and dioctyl adipate, polyhydric alcohol esters such as diethylene glycol dibenzoate, diethylene glycol dioctoate and glycerol tributyrate, 9, 10-epoxy octyl stearate, epoxidized vegetable oil, 4,
Examples include epoxidized esters such as dioctyl 5-epoxyhexahydrophthalate, and phosphoric acid esters such as triphenyl phosphate, trioctyl phosphate, and diphenyl monoisopropyl phosphate. Usually, 100 parts by weight of hydrogenated bisphenol A diglycidyl ether is added. On the other hand, it is applied at 0 to 50 parts by weight, preferably 0 to 20 parts by weight.

Examples of the dyes and pigments include titanium oxide, carbon black, iron oxide, yellow lead, disazo yellow, quinophthalone yellow, monoazo red, benzimidazolone red, phthalocyanine blue, and the like, which are usually hydrogenated. 0 to 50 parts by weight, preferably 0 to 100 parts by weight of bisphenol A diglycidyl ether
~ 20 parts by weight applied.

Examples of antioxidants include hindered phenolic antioxidants such as dibutylhydroxytoluene, dilaurylthiodipropionate, sulfur antioxidants such as 2-mercaptobenzimidazole, tridecyl phosphite and trilauryl tritiate. Examples of the phosphite ester such as oposphite are usually applied in an amount of 0 to 5 parts by weight, preferably 0 to 1 part by weight, based on 100 parts by weight of hydrogenated bisphenol A diglycidyl ether.

Examples of the ultraviolet absorber include benzotriazole compounds such as 2 (2'-hydroxy-5'-methylphenyl) benzotriazole, benzophenone compounds such as 2,4-dihydroxybenzophenone, and salicylate compounds such as phenyl salicylate. Examples of the compound include 0 to 5 parts by weight, preferably 0 to 5 parts by weight, based on 100 parts by weight of hydrogenated bisphenol A diglycidyl ether.
Applied at 1 part by weight.

As the light stabilizer, bis (2,2,6,6)
-Tetramethyl-4-piperidyl) sebacate and other hindered amine compounds are exemplified, and usually, relative to 100 parts by weight of hydrogenated bisphenol A diglycidyl ether,
It is applied at 0 to 5 parts by weight, preferably 0 to 1 part by weight.

Examples of the flame retardant include antimony trioxide, chlorinated paraffin, chlorinated diphenyl, phosphoric acid esters, etc., and usually 0 to 20 parts by weight to 100 parts by weight of hydrogenated bisphenol A diglycidyl ether, It is preferably applied at 0 to 5 parts by weight.

As the filler, zinc dust, metal powder such as aluminum flakes, lead suboxide, calcium carbonate, hydrated alumina, barium carbonate, kaolin, silica powder, talc,
Barium sulfate, diatomaceous earth, wollastonite, glass beads, glass microballoons, glass fiber, organic fiber,
Examples thereof include polymer particles, hydrous potassium aluminum silicate, metal oxide-coated mica, etc., and usually 0-2 with respect to 100 parts by weight of hydrogenated bisphenol A diglycidyl ether.
00 parts by weight, preferably 0 to 100 parts by weight are applied.

Examples of the leveling agent and defoaming agent include isoparaffin, liquid paraffin, silicone oil, polysiloxane oligomer, fluorine compound, copolymer of acrylic acid ester and vinyl compound, and the like.
It is applied in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, based on 100 parts by weight of hydrogenated bisphenol A diglycidyl ether.

Examples of the anti-sagging agent include colloidal silica, hydrogenated castor oil-based wax, polyethylene wax, amide wax, organic bentonite, aluminum stearate, zinc stearate, and the like. Usually, hydrogenated bisphenol A diglycidyl ether 100 is used. It is applied in an amount of 0 to 20 parts by weight, preferably 0 to 5 parts by weight, based on parts by weight.

As the solvent, methanol, ethanol,
Alcohols such as butanol, 2-ethylhexanol and benzyl alcohol, ether alcohols and ethers such as butyl cellosolve, hexyl cellosolve, butyl carbitol, propylene glycol monomethyl ether and dioxane, esters of butyl acetate, cellosolve acetate, methoxybutyl acetate, etc. And ether esters, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, hexane, mineral spirits, aliphatic hydrocarbons such as ethyl cyclohexane, aromatic hydrocarbons such as toluene and xylene, and the like. Bisphenol A diglycidyl ether 10
0 to 100 parts by weight, preferably 0 to 5 parts by weight
Applied at 0 parts by weight.

BEST MODE FOR CARRYING OUT THE INVENTION

As a method for preparing the epoxy resin composition according to the present invention, when the epoxy compound containing hydrogenated bisphenol A diglycidyl ether as a main component and the aliphatic polyamine-based curing agent are mixed, one or both of them is previously prepared. After dissolving the bisphenol compound, each may be mixed, or the bisphenol compound may be dissolved in another additive and mixed with the epoxy compound and the curing agent.

The epoxy resin composition thus obtained is
Resin mortar flooring for gas stations and factories, permeable paving materials for roads and parks, casting materials for vehicle-related parts and accessories, building materials, bridges, storage tanks, weatherproof anticorrosive paints for pipelines, traffic, etc. Especially useful as paint.

[0035]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples. The cured physical properties of the epoxy resin composition obtained in each example were measured and evaluated by the following methods.

Touch-drying time Epoxy resin composition was applied to a steel plate (JIS G 3141, S
PCC-SB) to a film thickness of about 0.7 mm,
The touch-drying time when kept under the conditions of 10 ° C. and 25 ° C. is measured according to JIS K 5400.

Pencil hardness The epoxy resin composition is applied to a steel plate, and the temperature is 10 ° C. and 25 ° C.
At 24 hours, the pencil scratch value (scratch) when held for 24 hours is measured according to JIS K 5400.

A coating film obtained by applying the accelerated weathering epoxy resin composition to a steel plate and curing it at 25 ° C. for 7 days was used with a weatherometer (manufactured by Toyo Seiki Seisakusho) and a xenon burner of 0.
39watt / cm ² , black panel temperature 63 ° C, humidity 60
% RH, 100 to 2 under the condition of 18 min sprinkling / 120 min
Observe appearance changes such as yellowing and gloss of the coating film when exposed for 00 hours.

Impact resistance of a coating film obtained by coating an epoxy resin composition containing no impact pigment on a steel sheet to a film thickness of about 100 μm and curing it at 25 ° C. for 7 days. According to JIS K 5400 (Dupont type), a weight is dropped from a height of 500 mm and cracks and peeling of the coating film are examined.

Example 1 Licarezin HBE-100 (manufactured by Shin Nippon Rika Co., Ltd., hydrogenated bisphenol A diglycidyl ether, epoxy equivalent 2
11, hereinafter abbreviated as "HBE-100". ) Add 8 parts by weight of bisphenol A to 100 parts by weight, and add 1 at 80 ° C.
It was dissolved by stirring for a time. To this, 30 parts by weight of titanium oxide (rutile type) as a pigment, and then 45 parts by weight of a modified product of N-benzylethylenediamine (active hydrogen equivalent 87, abbreviated as "NBEA" hereinafter) as an aliphatic polyamine-based curing agent. An epoxy resin composition was prepared by blending, and the coating film was evaluated for touch dry time, pencil hardness and accelerated weather resistance. On the other hand, the impact resistance of the epoxy resin composition prepared without adding titanium oxide was evaluated. Table 1 shows the obtained results.

Example 2 To 45 parts by weight of NBEA, 10 parts by weight of bisphenol A and 5 parts by weight of bisphenol F were added and dissolved by stirring at 90 ° C. for 1 hour. To this, 30 parts by weight of titanium oxide and 100 parts by weight of "HBE-100" were blended to prepare an epoxy resin composition, and cured physical properties were evaluated in the same manner as in Example 1. Table 1 shows the obtained results.

Example 3 An epoxy resin composition was prepared in the same manner as in Example 1 except that bisphenol C was used instead of bisphenol A, and the cured physical properties of this were evaluated. Table 1 shows the obtained results.

Comparative Example 1 An epoxy resin composition was prepared in the same manner as in Example 1 except that bisphenol A was not added, and the cured physical properties of this composition were evaluated. Table 1 shows the obtained results.

Comparative Example 2 In Example 1, the hydrogenated bisphenol A diglycidyl ether was replaced with a general-purpose bisphenol A diglycidyl ether (hereinafter abbreviated as "DGEBA". Epoxy equivalent 188), and bisphenol A was blended. The cured physical property when not doing was evaluated. Table 1 shows the obtained results.

Comparative Example 3 In Example 3, when the compounding amount of bisphenol C was increased to 60 parts by weight, the epoxy resin composition immediately after compounding had a very high viscosity and was difficult to handle.

[0046]

[Table 1]

Comparative Examples 4 to 8 In Example 1, instead of bisphenol A, trimethylolpropane (hereinafter abbreviated as "TMP"), T.
The cured physical properties when PI, salicylic acid, phenol or resorcin were blended were evaluated. Table 2 shows the obtained results.

[0048]

[Table 2]

Examples 4 to 5 In Example 1, the type of the aliphatic polyamine-based curing agent is a modified product of isophoronediamine (active hydrogen equivalent 120, hereinafter abbreviated as "IPDA") or 1,3-bis (amino). Modified product of methyl) cyclohexane (equivalent active hydrogen 8
1, hereinafter abbreviated as "BAC". ), And the cured physical properties were evaluated when the compounding amount of the bisphenol compound was changed. Table 3 shows the obtained results.

Comparative Examples 9 to 11 In Examples 4 to 5, the cured physical properties were evaluated when the bisphenol compound was not compounded or the compounding amount was too small.
Table 3 shows the obtained results.

[0051]

[Table 3]

[0052]

The epoxy resin composition according to the present invention has significantly improved curability at low temperatures while maintaining excellent weather resistance, mechanical properties and the like. It can also be applied to applications such as coatings that are difficult to heat cure and require weather resistance.

Claims (2)

[Claims] 1. An epoxy resin composition which is liquid at room temperature and contains hydrogenated bisphenol A diglycidyl ether and an aliphatic polyamine-based curing agent, is represented by the general formula (1) per 100 parts by weight of hydrogenated bisphenol A diglycidyl ether. An epoxy resin composition comprising 2 to 50 parts by weight of one or more bisphenol compounds represented. Embedded image [Wherein, X is _{-CH 2 -, - CH (CH} 3) -, - C (C
Represents a or -O- - H _{3) 2.} R ¹ and R ² are the same or different and each represent hydrogen or an alkyl group having 1 to 4 carbon atoms. ] 2. The bisphenol compound is bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane and / or 2,2-. 2. Bis (3-methyl-4-hydroxyphenyl) propane.
The epoxy resin composition according to the above.