JP2003096271A - Epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition capable of obtaining an epoxy resin cured article that is quickly cured in ordinary temperature or less and has improved toughness, while using conventional inexpensive amine-based epoxy curing agent. SOLUTION: The epoxy resin composition comprises (A) an epoxy resin, (B) a lactam and alcohol, (C) the amine-based epoxy resin curing agent, and (D) a thiocyanate of a compound represented by formula (1) as an curing accelerator [wherein R<1> and R<2> may be the same or different, independently denote the group represented by a 1-8C alkyl, an aryl or a nitrogen-containing heterocyclic group, and in combination denote a group represented by a 2-11C alkylene or -R<3> -R<4> -R<5> -. R<3> and R<5> may be the same or different, and independently denote a 1-8C alkylene; and R<4> denotes an oxygene atom, a sulfer atom, an =NR<6> group or an =NNH2 group. R<6> denotes hydrogen or a 1-8C alkyl].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin composition.

[0002]

2. Description of the Related Art Epoxy resins have excellent electrical insulation, moisture resistance, heat resistance, solder resistance, chemical resistance, durability, adhesiveness, mechanical strength, etc. It is widely used as a paint, an adhesive, a sealing material, etc. in various fields such as electronics, civil engineering and construction. Among them, the bisphenol type epoxy resin is most widely used because of its excellent chemical resistance, adhesiveness and high temperature characteristics.

Curing of the epoxy resin is generally carried out by adding a curing agent to the epoxy resin and heating it. Among such curing agents, typical ones include, for example, diethylenetriamine, triethylenetetramine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, polyamides, dicyandiamide, hexahydrophthalic anhydride, methylnadic acid anhydride, novolac type phenol resin, Amine complexes such as tertiary amines, imidazoles and boron trifluoride are known.

[0004]

Among these curing agents, those which can cure an epoxy resin at room temperature include:
Although amine curing agents such as diethylenetriamine, triethylenetetramine, polyamides and tertiary amines are known, it cannot be said that these curing agents can cure the epoxy resin sufficiently quickly at room temperature or lower, It took a long time such as 4 to 7 days for curing.

The present inventors have hitherto found a compound having an N—N bond such as 1-aminopyrrolidine as a curing agent capable of curing an epoxy resin sufficiently quickly even at room temperature or lower, for example, about 5 ° C. Proposed (Japanese Patent Application No. 11-296872). However, when the bisphenol type epoxy resin is cured using this,
There is a problem that the toughness of the obtained material is insufficient.

Further, these compounds are generally expensive as compared with commonly used amine-based epoxy curing agents, so that there is a problem that usable applications are restricted. An object of the present invention is to provide an epoxy resin cured product with improved toughness which can be rapidly cured even at a room temperature or lower temperature while using a conventionally used inexpensive amine epoxy curing agent. It is to provide a composition that can be obtained.

[0007]

The present invention provides (A) epoxide
For resin, (B) latam and alcohol,
(C) Amine-based epoxy resin curing agent, and further a curing accelerator
And (D) a thiocyanate of a compound represented by the formula (1)
And an epoxy resin composition characterized by containing
It NH_TwoN (R¹) (R^Two) (1) [R in the formula¹, R^TwoAre the same or different and have 1 to 8 carbon atoms.
Rualkyl, aryl, nitrogen-containing heterocyclic group, both bonded to charcoal
Alkylene having a prime number of 2 to 11 or -R^Three-R^Four-R ⁵-In
The groups shown are shown. R^Three, R⁵Are the same or different carbon
Number 1 to 8 alkylene, R^FourIs an oxygen atom, a sulfur atom, a group
= NR⁶Or = NNH_TwoIndicates. R⁶Is hydrogen or carbon number
Represents 1-8 alkyl. ]

The present invention also provides (A) epoxy resin 10
0 parts by weight of (B) latam and alcohol 7 to
50 parts by weight, (C) amine-based epoxy resin curing agent 20 to
100 parts by weight, and further 1 to 50 parts by weight of a thiocyanate of a compound represented by formula (1) (D) as a curing accelerator are added to the epoxy resin composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy resin (A) usable in the present invention is not particularly limited, and various epoxy resins can be used. For example, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin and the like can be exemplified.

As the glycidyl ether type epoxy resin, bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, biphenyl type,
Naphthalene type, fluorene type, phenol novolac type, cresol novolac type, DPP novolac type, 3
Examples thereof include functional type, tris-hydroxyphenylmethane type, tetraphenylolethane type and the like. Examples of the glycidyl ester type epoxy resin include hexahydrophthalic acid ester type and phthalic acid ester type. Examples of the glycidylamine type epoxy resin include tetraglycidylaminodiphenylmethane, triglycidyl isocyanurate, hydantoin type, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, aminophenol type, aniline type and toluidine type. be able to.

The lactam (B) that can be used in the present invention is not particularly limited, but a compound represented by the general formula (2) is preferable.

[0012]

[Chemical 1] [In the formula, n is an integer of 2 to 7]

Further, ε-caprolactam is particularly preferable. The alcohol (B) usable in the present invention is a curing agent,
Although it is not particularly limited as long as it is compatible with the epoxy resin, an aromatic alcohol having 7 to 10 carbon atoms is preferable, and benzyl alcohol is particularly preferable.
The blending ratio of ramtam and alcohol in the component (B) is, for example, 1: 1 by weight ratio of lactam: alcohol.
A ratio of 9 to 9: 1 can be exemplified, and a ratio of 2: 8 to 8: 2 is preferable.

In the present invention, the alcohol and lactam as the component (B) have a function of remarkably improving the toughness of the cured epoxy resin product due to the synergistic effect of both. The amount of the component (B) used in the present invention is usually 7 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the epoxy resin, which is the total amount of lactam and alcohol.
More preferably, it is 10 to 30 parts by weight.
If the blending amount of the component (B) is too large, the curing rate will be significantly reduced, which is not preferable. Further, if the blending amount of the component (B) is too small, the effect of imparting flexibility cannot be sufficiently exerted, which is not preferable.

In the epoxy resin composition of the present invention, (C) amine type epoxy resin curing agent is used as a curing agent.
Among the amine-based compounds used as the amine-based epoxy resin curing agent, particularly preferred compounds include alkylamines, chain-like aliphatic amines, cyclic amines, aromatic amines, aliphatic aromatic amines and epoxy-modified products thereof, Mannich Examples thereof include modified products and Michael addition modified products.

The alkylamine has the general formula NH
_Two(R⁷) (R in the formula⁷Is a straight or branched chain having 1 to 12 carbon atoms.
Various alkyl groups), for example,
Cylamine, ethylamine, propylamine, isopro
Pyramine, butylamine, sec-butylamine, t
-Butylamine, n-octylamine, 2-ethylhexyl
General formula NH (R⁸) (R⁹) (In the formula
R⁸, R⁹Are the same or different and are straight-chain or
Represents a branched alkyl group), for example,
For example, dimethylamine, diethylamine, dipropylamine
Amine, diisopropylamine, dibutylamine, di-se
c-butylamine, di-t-butylamine, di-n-o
General such as octylamine and di-2-ethylhexylamine
Formula N (R¹⁰) (R ¹¹) (R¹²) (R in the formula¹⁰, R
¹¹, R¹²Are the same or different and are straight chains having 1 to 12 carbon atoms.
Or represents a branched alkyl group), for example,
For example, trimethylamine, tripropylamine, triiso
Propylamine, tributylamine, tri-sec-bu
Tylamine, tri-t-butylamine, tri-n-octyl
Examples include chillamine.

The chain aliphatic amine has the formula (R ¹³ ).
_{^{(R 14) N (CH 2}} ) nN (R 1 5) (R 16) ( ^{wherein, R 13, R 14, R} 15, R 16 are the same or different and each represents a hydrogen atom or a straight-chain having 1 to 6 carbon atoms Or a branched alkyl group, n is a number of 1 to 5), for example, 3- (dimethylamino) propylamine,
3- (diethylamino) propylamine, 3- (methylamino) propylamine, 3- (dibutylamino) propylamine, tetramethylethylenediamine, etc., formula N
(R ¹⁷ ) (R ¹⁸ ) (CH ₂ ) nNH ₂ (wherein R ¹⁷ and R ¹⁸ are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. N is 1 to 1). 5
Indicates the number of. Compounds represented by), such as ethylenediamine, etc., the formula _{^{N (R 1 9) [(}} CH 2) nNH 2] 2 ( ^{wherein, R 19} represents a linear or branched alkyl group having 1 to 6 hydrogen atoms or carbon atoms N is a number of 1 to 5), for example, 3,3′-iminobis (propylamine), N-methyl-3,3′-iminobis (propylamine), a compound represented by the formula: N [(CH ₂ ) nNH ₂ ] ₃ (wherein
n shows the number of 1-5. ) A compound represented by
Tris (2-aminoethyl) amine, etc., formula NH ₂ (CH
₂ ) m [(CH ₂ ) nNH] xNH ₂ (wherein m, n,
x shows the number of 1-5, respectively. ) A compound represented by
For example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and other chain aliphatic amines such as 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, 3-methoxypropylamine, allylamine, diallylamine,
Examples include triallylamine, polyoxypropylenediamine, polyoxypropylenetriamine and the like.

Examples of the cyclic amine include bis (4-amino-3-methyldicyclohexyl) methane,
Diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpyrazine, 3,
9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, m-xylenediamine, isophoronediamine, mensendiamine,
1,4-bis (2-amino-2-methylpropyl) piperazine, N, N′-dimethylpiperazine, pyridine, picoline, 1,8-diazabicyclo [5,4,0] -7-undecene, benzylmethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 2- (dimethylaminomethyl) phenol, 2-methylimidazole,
2-ethyl-4-methyl imidazole etc. can be illustrated.

Examples of aromatic amines include metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfine, diaminodiethyldimethyldiphenylmethane, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene and the like. . Further, as the aliphatic aromatic amine, for example, α- (m /
Examples thereof include p-aminophenyl) ethylamine and the like. Further, triethylenetetramine, diaminodiphenyl sulfone, polyamides, dicyandiamide, hexahydrophthalic anhydride, methylnadic acid anhydride, novolac type phenol resin, amine complex such as boron trifluoride and the like can be used.

The amount of component (C) used in the present invention is not particularly limited, but the type of epoxy resin, the type and amount of other additives, and the intended epoxy resin composition. It may be appropriately selected from a wide range according to various conditions such as use / physical properties and curing conditions (designed curing time, curing temperature, curing place, etc.), but usually 0.1 to 1 per 1 equivalent of epoxy resin It is preferable to use it in an equivalent amount, preferably about 0.6 to 1 equivalent. The weight ratio to the epoxy resin is 10 to 200 parts by weight, preferably 20 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin.
It is preferable that the amount is about parts by weight.

Further, in the present invention, as a curing accelerator
(D) The thiocyanate of the compound represented by the formula (1)
To meet. NH_TwoN (R¹) (R^Two) (1) [R in the formula¹, R^TwoAre the same or different and have 1 to 8 carbon atoms.
Rualkyl, aryl, nitrogen-containing heterocyclic group, both bonded to charcoal
Alkylene having a prime number of 2 to 11 or -R^Three-R^Four-R ⁵-In
The groups shown are shown. R^Three, R⁵Are the same or different carbon
Number 1 to 8 alkylene, R^FourIs an oxygen atom, a sulfur atom, a group
= NR⁶Or = NNH_TwoIndicates. R⁶Is hydrogen or carbon number
Represents 1-8 alkyl. ]

Examples of the alkyl having 1 to 8 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, s-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, n. −
Hexyl, isohexyl, heptyl, octyl and the like can be mentioned. Examples of the alkylene having 2 to 11 carbon atoms include ethylene, propylene, butylene, hexylene, octylene, decamethylene, undecamethylene and the like. Examples of the alkylene having 1 to 8 carbon atoms include methylene, ethylene, propylene, butylene, hexylene and octylene. Examples of the aryl include phenyl, tolyl, naphthyl and the like. Examples of the nitrogen-containing heterocyclic group include pyridyl, piperidinyl, pyrazolyl and the like.

Specific examples of the compound represented by the formula (1) include 1-aminopyrrolidine (1-AP), 1-aminopiperidine, 1-aminohomopiperidine (AHP), 1-
Aminopiperazine, N-amino-N'-methylpiperazine (AMPI), N-aminomorpholine (AMP), N
-Aminothiomorpholine, 1,1-dimethylhydrazine (UDMH), 1,1-diethylhydrazine, 1,1-dipropylhydrazine, 1,1-dibutylhydrazine, monomethylhydrazine, monoethylhydrazine, monopropylhydrazine, monoisopropyl Hydrazine, monobutylhydrazine, mono-tert-butylhydrazine,
1-ethyl-1-methylhydrazine, 1-methyl-1-
Examples thereof include propylhydrazine, 1-butyl-1-methylhydrazine, 1-methyl-1-phenylhydrazine, 1,1-diphenylhydrazine, monophenylhydrazine and 2-hydrazinopyridine.

Among these compounds, 1-aminopyrrolidine (1-AP), 1-aminohomopiperidine (AH
P), N-amino-N'-methylpiperazine (AMP
I) and N-aminomorpholine (AMP) are particularly preferred.

The thiocyanate salt of the compound represented by the formula (1) is prepared by adding the compound represented by the formula (1) to the aqueous solution of ammonium thiocyanate in an approximately equimolar amount and diluting the produced ammonia and water. It can be manufactured by reacting for about 30 minutes to 5 hours while gradually heating to about 80 ° C. while leaving.

The thiocyanate of the compound represented by the above formula (1) used in the present invention can be used in the form of powder or liquid as it is, but it is used in the form of aqueous solution or organic solvent solution or dispersion. You can also Here, examples of the organic solvent include lower alcohols such as methanol, ethanol, and isopropanol, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, ethers, polar solvents, and halogenated hydrocarbons. Examples thereof include hydrogens. It may also be a solution or dispersion of water and a suitable organic solvent. Among these various forms, it is preferable to use it in a powder state.

In the present invention, the ratio of the thiocyanate of the compound represented by the formula (1) (D) to be added as the curing accelerator is 1 to 50 parts by weight based on 100 parts by weight of the epoxy resin. The proportion is preferably 5 to 30 parts by weight. In particular, it is preferable to use it by adding it in an amount of preferably 5 to 50 parts by weight with respect to 100 parts by weight of the amine-based curing agent, because the curing rate can be improved without substantially changing the physical properties of the cured product. . Furthermore, it is preferable to use the thiocyanate of the compound represented by the formula (1) in a ratio of about 0.5 to 1 mol with respect to 10 mol of the amine curing agent.

The epoxy resin composition of the present invention may be mixed with a curing agent or a reaction accelerator which has been conventionally used within a range that does not impair its preferable characteristics. Examples of such a curing agent include hexahydrophthalic anhydride, methylnadic acid anhydride, novolac type phenol resin, and resole type compound. Examples of the curing accelerator include tri-n-butylamine, benzylmethylamine, 2,4,6-tris (dimethylaminomethyl).
Tertiary amines such as phenol, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, imidazoles such as 2-phenylimidazole, 1,8-diazabicyclo [5,4,0]- 7-undecene and the like can be mentioned. These curing agents and curing accelerators may be used alone or in combination of two or more. When using these curing accelerators in combination,
Generally, the total amount of the curing accelerator is about 0.1 to 1 part by weight, preferably 0.2 to 100 parts by weight of the epoxy resin.
It is recommended to add about 0.6 parts by weight.

If desired, the epoxy resin composition of the present invention may contain a filler, a reinforcing material and the like which have been conventionally added. Examples of the filler include silica, fused quartz, calcium carbonate, barium carbonate, barium sulfate, hydrated alumina, alumina, magnesium hydrate,
Examples thereof include zircon, cordierite, silicon nitride, boron nitride, aluminum nitride and the like. Examples of the reinforcing material include talc, mica, glass fiber, potassium titanate fiber, titanium dioxide fiber, wollastonite, zonotolite, zinc silicate fiber, aramid fiber, carbon fiber, boron fiber and the like. Type of filler and reinforcing material so that the epoxy resin cured product exhibits desired physical properties,
The amount of addition and the like can be adjusted appropriately, but usually, the filler and the reinforcing material are added in an amount of 20 to 100 parts by weight of the epoxy resin.
It is preferable to add about 160 parts by weight, preferably about 50 to 120 parts by weight. Each of the filler and the reinforcing material may be used alone or in combination of two or more.

Further, various additives may be added to the epoxy resin composition, if necessary. Examples of such additives include pigments (particulate titanium dioxide, carbon black, rouge, yellow iron oxide, etc.), viscosity modifiers, leveling agents, defoamers, coupling agents, plasticizers, diluents, flame retardants. (Magnesium hydroxide, aluminum hydroxide, antimony oxide, alkyl phosphates, phosphazenes), organic solvents and the like.

The epoxy resin composition of the present invention is, for example,
It can be applied to metal, synthetic resin, cement, ceramics, knitted or woven fabric (glass cloth, etc.) made of inorganic or organic fibers, coating of paper and the like, adhesion, repair, and production of molded products using these as a base material. Specifically, the epoxy resin composition of the present invention is impregnated into various shaped articles, or the above epoxy resin composition is applied to the surface of the article, the gaps between articles or the like, or after coating or injection, It can be left as it is and cured. Usually, heating is not required for curing, but depending on the composition, heating may be performed at about 40 to 120 ° C. Further, the epoxy resin composition of the present invention can be molded into a molded product having an arbitrary shape by molding according to a normal molding method such as cast molding or injection molding. According to the present invention, it is possible to obtain an excellent effect that an epoxy resin composition having a markedly improved curing rate can be obtained by using a general-purpose amine curing agent.

[0032]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the invention is not limited thereto.

Examples 1 to 9 (A) Bisphenol A type epoxy resin as epoxy resin (trade name: Epicoat 828, epoxy equivalent: 19)
0, manufactured by Japan Epoxy Resin Co., Ltd.), in a proportion shown in Table 1, (B) lactam as ε-caprolactam (CAP, manufactured by Wako Pure Chemical Industries, Ltd.) and alcohol as benzyl alcohol (BzOH, pure Wako). (Chemical Industry Co., Ltd.), (C) Amine-based epoxy resin curing agent modified aliphatic polyamine (trade name: ADEKA HARDNER EH220, manufactured by Asahi Denka Kogyo Co., Ltd.), (D) of the compound represented by Formula (1) As thiocyanate, 1-aminopyrrolidine-thiocyanate (1-AP-SCN,
After mixing Otsuka Chemical Co., Ltd., steel plate (thickness 0.8)
mm) to give a thickness of 0.3 mm to obtain a test piece. A curing rate test was conducted at room temperature (20 ° C.) according to JIS K5400. The results are shown in Table 1. Further, after curing at room temperature for one day, a bending test was conducted according to JIS K5400. The results are also shown in Table 1.

Comparative Examples 1 to 5 As shown in Table 1, the same procedures as in Examples 1 to 9 were carried out except that one or both of (B) lactam and alcohol were not blended. The results are shown in Table 1.

[0035]

[Table 1]

[0036]

EFFECTS OF THE INVENTION According to the present invention, it is possible to rapidly cure even at room temperature or lower temperature while improving the toughness while using a conventionally used inexpensive amine epoxy curing agent. A composition capable of obtaining a cured product of an epoxy resin can be obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takashi Kitajima             463 Kagasuno, Kawauchi Town, Tokushima City, Tokushima Prefecture             Gaku Co., Ltd. Tokushima Factory (72) Inventor Ryohiro Nabeshima             463 Kagasuno, Kawauchi Town, Tokushima City, Tokushima Prefecture             Gaku Co., Ltd. Tokushima Factory F-term (reference) 4J002 CD001 EC007 EU016                 4J036 DA04 DC18 FA04 FA10

Claims (2)

[Claims] 1. An epoxy resin (A), and a resin (B)
Mutam and alcohol, (C) amine epoxy resin hard
Represented by the formula (1) (D) as an agent and a curing accelerator
The compound is characterized by containing a thiocyanate salt.
Poxy resin composition. NH_TwoN (R¹) (R^Two) (1) [R in the formula¹, R^TwoAre the same or different and have 1 to 8 carbon atoms.
Rualkyl, aryl, nitrogen-containing heterocyclic group, both bonded to charcoal
Alkylene having a prime number of 2 to 11 or -R^Three-R^Four-R ⁵-so
The groups shown are shown. R^Three, R⁵Are the same or different carbon
Number 1 to 8 alkylene, R^FourIs an oxygen atom, a sulfur atom, a group
= NR⁶Or = NNH_TwoIndicates. R⁶Is hydrogen or carbon number
Represents 1-8 alkyl. ] 2. The total amount of (B) lamtam and alcohol is 7 to 50 relative to 100 parts by weight of (A) epoxy resin.
Parts by weight, (C) amine-based epoxy resin curing agent 20 to 10
The epoxy resin composition according to claim 1, wherein 0 part by weight and 1 to 50 parts by weight of the thiocyanate of the compound represented by formula (1) (D) are further added as a curing accelerator.