KR20110055656A - Heat-cured epoxy resin composition - Google Patents

Abstract

Provision of the thermosetting epoxy resin composition excellent in sclerosis | hardenability. In the thermosetting epoxy resin composition containing an epoxy resin (A), an aromatic polyamine compound (B), and a compound represented by the following formula (I), the gelation time is within 3 minutes at 150 ° C, characterized in that the thermosetting epoxy resin Composition. (In formula, R <^1> , R <^2> represents a hydrogen atom and an alkyl group, respectively.)

Description

Thermosetting epoxy resin composition {HEAT-CURED EPOXY RESIN COMPOSITION}

The present invention relates to a thermosetting epoxy resin composition.

The composition which used the aromatic diamine compound as a hardening | curing agent of an epoxy resin can obtain the hardened | cured material with high glass transition temperature.

The applicant of this application proposes patent document 1 as a two-component curable resin composition which was excellent in the storage stability of the 1st liquid containing an epoxy resin previously, and has a fast hardening rate in room temperature or less.

Moreover, the epoxy resin composition containing curable epoxy resin, the hardening | curing agent for epoxy resins, and tris (4-methylphenyl) phosphine triphenylborane is proposed (refer patent document 2). .

Moreover, when triphenyl phosphine is used with respect to the phenol type resin as a hardening | curing agent of an epoxy resin, it is known that the hardening time of a composition becomes short.

Patent Document 1: Japanese Patent Application Laid-Open No. 2007-326906 Patent Document 2: Japanese Patent Application Laid-Open No. 2006-290946

However, when using an aromatic diamine compound as a hardening | curing agent for an epoxy resin, there existed a fault that the hardening time under the conditions of hardening temperature of 80-250 degreeC is long.

Moreover, this inventor discovered that when triphenylphosphine is used as a hardening accelerator with respect to the phenol resin as a hardening | curing agent of an epoxy resin, hardening time cannot be shortened.

Furthermore, the epoxy resin composition which uses trisphenylphosphine triphenylborane or tris (4-methylphenyl) phosphine triphenyl borane as a hardening accelerator with respect to the phenol resin as a hardening | curing agent of an epoxy resin is a triphenyl phosphate. The inventors have found that the curing time (gelling time) is long, similarly to the case where the pin is used for a phenolic resin as a curing agent of an epoxy resin.

Then, an object of this invention is to provide the epoxy resin composition excellent in sclerosis | hardenability.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, when using the compound represented by following formula (I) as a hardening accelerator with respect to the aromatic diamine compound as a hardening | curing agent of an epoxy resin, especially hardening time is short, What was able to be the composition excellent in sclerosis | hardenability was found, and this invention was completed.

(In formula, R <^1> , R <^2> represents a hydrogen atom and an alkyl group, respectively.)

That is, in this invention, in the thermosetting epoxy resin composition containing an epoxy resin (A), an aromatic polyamine compound (B), and the compound represented by following formula (I), gelation time is less than 3 minutes at 150 degreeC. A thermosetting epoxy resin composition is provided.

(In formula, R <^1> , R <^2> represents a hydrogen atom and an alkyl group, respectively.)

The thermosetting epoxy resin composition of this invention is excellent in sclerosis | hardenability.

The present invention will be described in detail below.

The present invention,

In the thermosetting epoxy resin composition containing an epoxy resin (A), an aromatic polyamine compound (B), and a compound represented by the following formula (I), the gelation time is within 3 minutes at 150 ° C, characterized in that the thermosetting epoxy resin Composition.

(In formula, R <^1> , R <^2> represents a hydrogen atom and an alkyl group, respectively.)

Hereinafter, the thermosetting epoxy resin composition of this invention may be called "composition of this invention."

An epoxy resin (A) is demonstrated below.

The epoxy resin (A) contained in the composition of the present invention is not particularly limited as long as it is a compound having two or more epoxy groups. For example, a conventionally well-known thing is mentioned. Specifically, for example, bisphenol A epoxy resin, dicyclopentadiene type epoxy resin, diaminodiphenylmethane type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy A resin, a biphenyl type epoxy resin, and a hydrogenated biphenol type epoxy resin are mentioned.

An epoxy resin (A) can be used individually or in combination of 2 types or more, respectively.

An aromatic polyamine compound (B) is demonstrated below.

The aromatic polyamine compound (B) contained in the composition of this invention is a compound with which 2 or more amino groups couple | bonded with the aromatic hydrocarbon group.

In this invention, an aromatic polyamine compound (B) is used as a hardening | curing agent. An aromatic polyamine compound (B) can react with an epoxy resin (A).

When the composition of this invention contains an aromatic thiirane compound (C), an aromatic polyamine compound (B) can react with an epoxy resin (A) and an aromatic thiirane compound (C).

When the composition of this invention contains an aromatic thiirane compound (C), an aromatic polyamine compound (B) preferentially reacts with an aromatic thiirane compound (C) in the composition of this invention, and produces | generates an NH group. The generated NH group can react with the epoxy resin (A). The amino group which an aromatic polyamine compound (B) has may react with an epoxy resin (A) directly.

The aromatic hydrocarbon group is not particularly limited. The aromatic hydrocarbon group may have a substituent. As a substituent, an alkyl group and an alkoxy group are mentioned, for example. The aromatic hydrocarbon group may have a heteroatom such as, for example, an oxygen atom, a nitrogen atom, or a sulfur atom.

As an aromatic hydrocarbon group, what is represented by a following formula is mentioned, for example.

In formula, R <^2> is at least 1 sort (s) chosen from the group which consists of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group, and a sulfide group.

As an alkylene group, a methylene group and an ethylene group are mentioned, for example.

R ² can be at least two selected from the group consisting of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group and a sulfide group.

It is preferable that an aromatic polyamine compound (B) is an aromatic diamine compound from a viewpoint of being excellent in sclerosis | hardenability. An aromatic diamine compound is a compound with which two amino groups couple | bonded with an aromatic hydrocarbon group.

As an aromatic polyamine compound (B), what is represented by Formula (II) is mentioned, for example. In the formula (II), two amino groups are bonded to the benzene ring.

[In formula (II), R <^3> , R <^4> is an alkyl group, respectively, R <^5> is at least 1 sort (s) chosen from the group which consists of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group, and a sulfide group. M and n are each an integer of 0 to 4.]

The aromatic polyamine compound represented by Formula (II) can have R <^3> , R <^4> as a substituent.

Examples of the alkyl group include 1 to 6 carbon atoms. For example, a methyl group, an ethyl group, and a propyl group are mentioned. From the viewpoint that the alkyl group is more excellent in storage stability and fast curing property, a methyl group and an ethyl group are preferable.

Examples of the alkylene group include those having 1 to 6 carbon atoms. For example, a methylene group and an ethylene group are mentioned. The methylene group is preferable from the viewpoint that the alkylene group is more excellent in storage stability and fast curing property.

It is preferable that they are an integer of 0-2 from a viewpoint that m and n are excellent in storage stability and fast hardenability, respectively.

It is preferable that the arrangement of the amino group is para position with respect to R ⁵ from the viewpoint of being superior in storage stability and fast curing property.

The aromatic hydrocarbon group is not particularly limited as long as it is divalent. The aromatic hydrocarbon group may have a substituent such as, for example, a methyl group.

When the aromatic hydrocarbon group and the alkylene group are combined, the combination of the aromatic hydrocarbon and the alkylene group is not particularly limited. For example, the alkylene group which has an aromatic hydrocarbon group is mentioned. Specifically, for example, when two alkylene groups are bonded via an aromatic hydrocarbon, when an aromatic hydrocarbon is bonded as a side chain of the alkylene group, The case where an aromatic hydrocarbon group and an alkylene group couple | bond, and an aromatic hydrocarbon group and an alkylene group couple | bond with two benzene rings represented by Formula (II), respectively is mentioned. As an aromatic hydrocarbon, a benzene ring and naphthalene are mentioned, for example. The aromatic hydrocarbon may have a substituent such as a methyl group.

As an aromatic polyamine compound (B), the compound represented by following formula (4) and methylene bis (2-ethyl-6-methylaniline) (methylene bis (2-ethyl-6-methylaniline)) are mentioned, for example. have.

In formula, R <^2> is at least 1 sort (s) chosen from the group which consists of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group, and a sulfide group.

It is preferable that an aromatic polyamine compound (B) is a compound represented by Formula (4) and methylene bis (2-ethyl-6-methylaniline) from a viewpoint that it is excellent in sclerosis | hardenability and is excellent in storage stability.

Among them, R ² is preferred in terms of excellent high than the curing, an alkylene group, a carbonyl group, a fluorenyl group, more preferably a methylene group, a carbonyl group, a fluorene group.

In addition, when the composition of this invention contains an aromatic thiirane compound (C), it is preferable that R <^2> is an alkylene group, a carbonyl group, and a fluorene group from a viewpoint of being excellent in sclerosis | hardenability, and it is a methylene group and a carbonyl group More preferred.

An aromatic polyamine compound (B) can be used individually or in combination of 2 types or more, respectively.

The aromatic polyamine compound (B) is not particularly limited in terms of its preparation. A commercial item can be used as an aromatic polyamine compound (B).

From the viewpoint that the amount of the aromatic polyamine compound (B) is more excellent in curability and the glass transition temperature (glass transition point) of the cured product is higher, the epoxy resin (A) has the equivalent number of active hydrogens of the aromatic polyamine compound (B). It is preferable that it is 0.5-2.5 equivalent with respect to an epoxy group, and it is more preferable that it is 0.7-2.0 equivalent.

In addition, the aromatic polyamine compound (B) has an amino group as a group containing active hydrogen. Amino groups have two active hydrogens per nitrogen atom.

The compound represented by Formula (I) is demonstrated below.

In the composition of the present invention, the compound represented by formula (I) is used as a curing accelerator or a curing accelerator (a curing accelerator when the composition of the present invention further contains an aromatic thiirane compound (C)).

The compound represented by Formula (I) contained in the composition of this invention has the following structures.

In formula, R <^1> , R <^2> represents a hydrogen atom and an alkyl group, respectively.

R ¹ represents a hydrogen atom or an alkyl group. R ² represents a hydrogen atom or an alkyl group.

R ¹ and R ² may be the same or different. Two or more R <^1> may be same or different. ^Two or more R <^2> may be same or different.

It is preferable that the number of carbon atoms is 1-6, and, as for an alkyl group, it is more preferable that it is 1-3, from a viewpoint that it is excellent in sclerosis | hardenability and glass transition temperature becomes high. As an alkyl group, a methyl group, an ethyl group, and a propyl group are mentioned specifically ,.

As a compound represented by Formula (I), the compound represented by Formula (1) and the compound represented by Formula (2) are mentioned, for example.

In formula, Ph represents a phenyl group or a phenylene group. In addition, Ph in Me-Ph- in Formula (2) is a phenylene group.

The composition of this invention contains the compound represented by Formula (1) and / or the compound represented by Formula (2) as a compound represented by Formula (I) from a viewpoint that it is excellent in sclerosis | hardenability and a glass transition temperature becomes high. It is preferable.

The compound represented by Formula (1) and the compound represented by Formula (2) are demonstrated below.

In the composition of the present invention, the compound represented by the formula (1) or the compound represented by the formula (2) is a curing accelerator or a curing accelerator (when the composition of the present invention further contains an aromatic tee compound (C) Is used as a curing accelerator).

The compound name of the compound represented by Formula (1) is triphenylphosphine triphenylborate, and it may be called "TPP-S" in this specification.

The compound name of the compound represented by Formula (2) is tris-para-methylphenylphosphine triphenylborate, and this may be called "TPTP-S" in this specification. In Formula (2), a methyl group can couple to an ortho position, a meta position, and a para position, respectively.

The compound represented by formula (I) is not particularly limited with respect to its preparation.

The compound represented by the formula (1) is not particularly limited with respect to its preparation. A commercial item can be used as a compound represented by Formula (1). The same applies to the compound represented by the formula (2).

The compound represented by Formula (I) can be used individually or in combination of 2 types or more, respectively.

It is preferable that it is 1-30 mass parts with respect to 100 mass parts of epoxy resins (A) from the viewpoint that the quantity of the compound represented by Formula (I) is more excellent in curability, and the glass transition temperature of hardened | cured material is high, and it is 3-10 mass It is more preferable to deny it.

In the present invention, the equivalent number of active hydrogens of the aromatic polyamine compound (B) is 0.5 to 2.5 equivalents to the epoxy group of the epoxy resin (A) from the viewpoint of being superior in curability and having a high glass transition temperature of the cured product. , It is preferable that the quantity of the compound represented by Formula (I) is 1-30 mass parts with respect to 100 mass parts of epoxy resins (A).

The microcapsules will be described below.

In the composition of this invention, any one or both of the compound represented by the said Formula (I) and the said aromatic polyamine compound is contained as a microcapsule contained by a thermoplastic resin, and it is quick hardenable. It can be set as a one-component composition which is more excellent in storage stability while maintaining.

In the present invention, the microcapsule has either or both of the compound represented by the formula (I) and the aromatic polyamine compound as a core, and has a thermoplastic resin as a shell.

It is preferable that the compound or aromatic polyamine compound represented by Formula (I) is solid (or melting | fusing point exceeds 70 degreeC) in 25-70 degreeC from a viewpoint that it is easy to microencapsulate when manufacturing a microcapsule. It is preferable that the core of a microcapsule is a compound represented by Formula (I), and aromatic diamine from a viewpoint that it is easy to encapsulate micro.

When both the compound represented by the formula (I) and the aromatic polyamine compound are contained as a microcapsule contained by the thermoplastic resin, the composition of the present invention includes the compound represented by the formula (I) contained by the thermoplastic resin. The microcapsule and the microcapsule containing the aromatic polyamine compound by the thermoplastic resin may be contained. Moreover, the compound represented by Formula (I) and an aromatic polyamine compound may be contained in one microcapsule.

The thermoplastic resin used as the shell is not particularly limited. For example, urethane resin; Styrene butadien elastomers; Poly vinyl acetal resins; Phenoxy resins; Poly methyl methacrylate (PMMA) resins; Poly vinyl alcohol; (Meth) acrylic monomers such as alkyl esters having 1 to 8 carbon atoms, such as acrylic esters, itaconic acid esters and crotonic acid esters A part or all of the hydrogen atoms of the alkyl group of the ester is substituted with an allyl group, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile ( monofunctional monomers such as methacrylonitrile, vinyl acetate, ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, Polymers obtained from polyfunctional monomers such as divinyl benzene, bisphenol-A di (meth) acrylate, and methylene bis (meth) acrylamide Can be .

A thermoplastic resin can be used individually or in combination of 2 types or more, respectively.

Among them, urethane resins, styrene butadiene elastomers, and polyvinyl acetal resins from the viewpoint of being superior in storage stability and fast curing property, excellent in film forming property and mechanical strength, and capable of maintaining the glass transition temperature of the obtained cured product. It is preferable that it is at least 1 sort (s) chosen from the group which consists of polyvinyl alcohol and phenoxy resin.

The urethane resin is not particularly limited as long as it is a compound having a urethane bond. For example, what is obtained by reaction of polyhydric isocyanates and polyhydric amines, what is obtained by reaction of polyhydric isocyanates, and water, what is obtained by reaction of polyhydric isocyanate, and polyhydric alcohol, polyhydric isocyanates, and polyvalent amines And what is obtained by reaction with polyhydric alcohol is mentioned.

The polyhydric isocyanate used when manufacturing a urethane resin should just be a compound which has two or more isocyanate groups in a molecule | numerator. Specifically, for example, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate (2,4-tolylene diisocyanate) , 2,6-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate -4,4'-diisocyanate), 3,3'-dimethoxy-4,4'-biphenyl diisocyanate (3,3'-dimethoxy-4,4'-biphenyl diisocyanate), 3,3'-dimethyldi 3,3'-dimethyl diphenyl methane-4,4'-diisocyanate, 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate Aromatic polyisocyanates such as (4,4'-dimethyl diphenyl methane-2,2 ', 5,5'-tetraisocyanate); Polyisocyanate in which an isocyanate group is bonded to an alkylene group having an aromatic hydrocarbon group such as xylene-1,4-diisocyanate; Trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate (butylene-1, Aliphatic polyisocyanates such as 2-diisocyanate) and lysine isocyanate; Alicyclic polyisocyanates such as cyclohexylene-1,2-diisocyanate, cyclohexylene-1,4-diisocyanate; Adducts of hexamethylene diisocyanate with hexane triol, adducts of 2,4-tolylene diisocyanate with Brenz catechol , Adducts of tolylene diisocyanate and hexane triol, adducts of tolylene diisocyanate and trimethylol propane, adducts of xylene diisocyanate and trimethylolpropane, hexa And adducts of methylene diisocyanate and trimethylolpropane.

Among them, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, xylene diisocyanate and the like from the viewpoint of being superior in storage stability and fast curing property and excellent in film formation and mechanical strength. Aromatic polyisocyanates are preferred.

Polyhydric isocyanates can be used individually or in combination of 2 types or more, respectively.

The polyhydric amines used when manufacturing a urethane resin should just be a compound which has a 2 or more amino group in a molecule | numerator. Specifically, for example, diethylene triamine, triethylene tetramine, tetraethylene pentamine, 1,6-hexamethylene diamine, Aliphatic polyamines such as 1,8-octamethylene diamine, 1,12-dodecamethylene diamine; aromatic polyamines such as o-phenylene diamine, m-phenylene diamine and p-phenylene diamine; polyamines having an amino group bonded to an alkylene group having an aromatic hydrocarbon group such as o-xylene diamine, m-xylene diamine, and p-xylene diamine; Mentan diamine, bis (4-amino-3-methyl cyclohexyl) methane, isophorone diamine, 1,3-diamino cyclo Alicyclic polyamines such as hexane (1,3-diamino cyclohexan); And spiroacetal diamines.

Polyhydric amines can be used individually or in combination of 2 types or more, respectively.

The polyhydric alcohol used when using a urethane resin may be either aliphatic, aromatic, or alicyclic. For example, catechol, resorcinol, 1,2-dihydroxy-4-methylbenzene, 1,3-dihydroxy-5 -Methylbenzene (1,3-dihydroxy-5-methylbenzene), 3,4-dihydroxy-1-methylbenzene (3,4-dihydroxy-1-methylbenzene), 3,5-dihydroxy-1-methyl Benzene (3,5-dihydroxy-1-methylbenzene), 2,4-dihydroxy ethylbenzene, 1,3-naphthalene diol, 1,5- 1,5-naphthalene diol, 2,7-naphthalene diol, 2,3-naphthalene diol, o, o'-biphenol (o , o'-biphenol, p, p'-biphenol, bisphenol A, bis- (2-hydroxy phenyl) methane ), Xylene diol, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5 -Pentane diol (1,5-pentane diol), 1,6-hexane diol (1,6-hexane diol), 1,7-heptane diol (1, 7-heptane diol, 1,8-octane diol, 1,1,1-trimethylol propane, hexane triol, pentaerythritol ), Glycerin (glycerin), sorbitol (sorbitol) and the like.

Polyhydric alcohol can be used individually or in combination of 2 types or more, respectively.

Styrene butadiene elastomer is not particularly limited. For example, a conventionally well-known thing is mentioned.

It is preferable that the weight average molecular weight of styrene butadiene elastomer is 12,000-50,000 from a viewpoint that it is excellent in storage stability and fast hardening property.

In addition, in this invention, a weight average molecular weight shall be the weight average molecular weight of polystyrene conversion by gel permeation chromatography (GPC) which uses tetrahydrofuran as a solvent.

The polyvinyl acetal resin is not particularly limited. For example, polyvinyl formal resin, polyvinyl butyral resin can be mentioned.

It is preferable that it is 10,000-60,000 from a viewpoint that the weight average molecular weight of polyvinyl acetal resin is excellent in storage stability and fast hardenability.

The polyvinyl alcohol is not particularly limited. For example, a conventionally well-known thing is mentioned. It is preferable that it is 10,000-150,000 from a viewpoint that the weight average molecular weight of polyvinyl alcohol is more excellent in storage stability and fast hardenability.

The phenoxy resin is not particularly limited. For example, it is a high molecular weight epoxy resin with a molecular weight of 10,000 or more selected from bisphenol A and / or bisphenol F.

The microcapsules are not particularly limited in terms of their preparation. For example, a conventionally well-known thing is mentioned.

Microcapsules may be used alone or in combination of two or more.

Especially, the microcapsule which contains the compound represented by Formula (I) is preferable from a viewpoint of being excellent in storage stability and fast hardenability.

In addition, from the viewpoint of better storage stability and fast curing property, and excellent film forming property and mechanical strength, the shell material is selected from the group consisting of urethane resin, styrene butadiene elastomer, polyvinyl acetal resin, polyvinyl alcohol and phenoxy resin. Microcapsules comprising at least one of the above are preferred.

In the present invention, when the core contains a microcapsule having the compound represented by formula (I), the aromatic polyamine compound may be microencapsulated or may not be microencapsulated.

In addition, when containing the microcapsule which has an aromatic polyamine compound as a core, the compound represented by Formula (I) may be microencapsulated, or may not be microencapsulated.

1-20 mass% of the whole composition from a viewpoint that the thermoplastic resin in a microcapsule can maintain the glass transition temperature of an epoxy resin and the hardened | cured material obtained, and is excellent in storage stability and fast hardening property, and is excellent in film forming property and mechanical strength. Is preferably.

It is preferable that the average particle diameter (diameter) of a microcapsule is 0.1-50 (unit: micron) from a viewpoint of being excellent in storage stability and quick hardening property. In this invention, the average particle diameter is measured using the particle size distribution measuring apparatus SALD-7100 (made by Shimadzu Seisakusho).

It is preferable that the thickness of the shell in a microcapsule is 0.01-10 (unit: micron) from a viewpoint that it is excellent in storage stability and quick hardening property, and is excellent in film forming property and mechanical strength. In the present invention, the thickness of the shell is measured using a particle size distribution measuring device SALD-7100 (manufactured by Shimadzu Corporation).

The composition of the present invention may further contain an aromatic thiirane compound (C).

The aromatic thiirane compound (C) which can be contained in the composition of this invention is an aromatic hydrocarbon compound which has a thiirane group and an aromatic hydrocarbon group.

In the present invention, the aromatic thiirane compound (C) is used as a curing accelerator. In addition, in this invention, an aromatic thiirane compound (C) can be used instead of a part of aromatic polyamine compound (B).

An aromatic thiirane compound (C) reacts with an aromatic polyamine compound (B), and produces | generates an SH group. The resulting SH group can react with the epoxy resin (A).

Aromatic thio is not particularly limited to the aromatic hydrocarbon group of the compound (C). For example, a phenyl group and a naphthyl group are mentioned. The aromatic hydrocarbon group may have a substituent. As a substituent, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group is mentioned, for example. An aromatic hydrocarbon group may have a hetero atom, such as an oxygen atom, a nitrogen atom, and a sulfur atom, for example.

In the aromatic thiirane compound (C), the thiirane group and the aromatic hydrocarbon group can be bonded through an organic group.

An organic group is a hydrocarbon group which may have a hetero atom, such as an oxygen atom, a nitrogen atom, and a sulfur atom, for example. The hydrocarbon group is not particularly limited.

Examples of the organic group include -O-CH _2- , -O-CH ₂ -CH = CH-, and -O-CO-CH _2- .

From the viewpoint that the amount of the aromatic thiirane compound (C) is more excellent in curability, the equivalent number of SH groups generated from the aromatic thiirane compound (C) is 0.3 to 1.0 with respect to the epoxy group of the epoxy resin (A). It is preferable that it is and it is more preferable that it is 0.4-0.7.

The composition of this invention is an additive further, if necessary other than an epoxy resin (A), an aromatic polyamine compound (B), the compound represented by Formula (I), and the aromatic thiirane compound (C) which can be used as needed. It may contain.

The composition of this invention is necessary other than an epoxy resin (A), an aromatic polyamine compound (B), an aromatic thiirane compound (C), and the compound represented by Formula (1), and / or the compound represented by Formula (2). Therefore, it can contain an additive further.

Examples of the additive include curing agents, fillers (fillers), reactive diluents, plasticizers, thixotropy-imparting agents, pigments, dyes, antioxidants, antioxidants, antistatic agents, and flame retardants other than the aromatic polyamine compound (B). (Iii), an adhesive imparting agent, a dispersing agent, and a solvent are mentioned.

As a thermosetting epoxy resin composition of this invention, a one-component thermosetting epoxy resin composition and a two-component thermosetting epoxy resin composition are mentioned, for example. In the present invention, "one-component thermosetting epoxy resin composition" may be described as "one-component", and "two-component thermosetting epoxy resin composition" may be described as "two-component".

The composition of the present invention is not particularly limited with respect to its preparation. For example, the epoxy resin (A), the aromatic polyamine compound (B), and the compound represented by the formula (I) and additives are sufficiently kneaded using a stirring apparatus such as a mixing mixer under reduced pressure or under a nitrogen atmosphere. By uniformly dispersing, the composition of the present invention can be prepared as a one-component composition.

For example, an epoxy resin (A), an aromatic polyamine compound (B), the compound represented by Formula (1), and / or the compound represented by Formula (2), and the additive which can be used as needed are made under pressure reduction. Alternatively, the composition of the present invention can be prepared as a one-part composition by sufficiently kneading and uniformly dispersing using a stirring apparatus such as a mixing mixer under a nitrogen atmosphere.

The composition of the present invention is not particularly limited with respect to the preparation even when the compound represented by the formula (I) and / or the curing agent are contained by the microcapsules. When the microcapsules contain a compound represented by formula (I), for example, an epoxy resin, a microcapsule containing a compound represented by formula (I), a curing agent and an additive which can be used as needed may be used under reduced pressure or Under nitrogen atmosphere, the composition of the present invention can be prepared as a one-component composition by sufficiently mixing using a stirring apparatus such as a mixing mixer. In addition, when a microcapsule contains a hardening | curing agent, for example, an epoxy resin, the compound represented by Formula (I), the microcapsule containing a hardening | curing agent, and the additive which can be used as needed under reduced pressure or nitrogen atmosphere, By mixing sufficiently using a stirring apparatus, such as a mixing mixer, the composition of this invention can be manufactured as a one-component composition.

When the composition of this invention and the compound represented by Formula (I) and / or a hardening | curing agent are contained by a microcapsule, it is 24 hours under the conditions of 25 degreeC with respect to initial viscosity from a viewpoint that it is excellent in storage stability. Since the increase rate of the viscosity after annealing can be 10% or less, it is more preferable. Viscosity shall be measured at 25 degreeC using the E-type viscosity meter VISCONIC EHD type (made by Toki-Sankyo Co., Ltd.).

When the composition of this invention and the compound represented by Formula (I) and / or a hardening | curing agent are contained by a microcapsule, it is excellent in storage stability and can be preserve | saved for a long time at room temperature (20-30 degreeC).

When the composition of the present invention is a one-part type, it is excellent in workability in the field.

When the composition of the present invention is two-component, there is no particular limitation regarding the preparation thereof. For example, it has a 1st liquid (main agent) containing an epoxy resin (A), and the 2nd liquid (curing agent) containing an aromatic polyamine compound (B) and the compound represented by Formula (I). It can be prepared as a two-component composition. The additive may be added to the first liquid and / or the second liquid. Each of the first liquid and the second liquid can be prepared by kneading sufficiently under a reduced pressure or a nitrogen atmosphere by using a stirring apparatus such as a mixing mixer and dispersing uniformly.

Moreover, for example, the 1st liquid (the subject) containing an epoxy resin (A), an aromatic polyamine compound (B), the compound represented by Formula (1), and / or the compound represented by Formula (2) are included. The composition of the present invention can be prepared as a two-component composition having a second liquid (curing agent). The additive may be added to the first liquid and / or the second liquid. Each of the first liquid and the second liquid can be prepared by kneading sufficiently under a reduced pressure or a nitrogen atmosphere by using a stirring apparatus such as a mixing mixer and dispersing uniformly.

When the composition of this invention is a two-component type, it is preferable from a viewpoint of being excellent in storage stability.

In the present invention, the gelation time (gel time) of the thermosetting epoxy resin composition is within 3 minutes (180 seconds) at 150 ° C. The gelling time is preferably within 60 seconds at 150 ° C., more preferably within 50 seconds.

In this invention, gelation time (gel time) was measured by the method according to JIS C2161: 1997, or the method using a Yasuda type gel time tester.

The composition of the present invention can be used, for example, for adhesives, for coating, for civil construction, for electricity, for transportation, for medical, for packaging, for textiles, for sports and for leisure.

As a to-be-adhered body which can apply the composition of this invention, a metal, glass, a plastic, mortar, concrete, rubber, wood, leather, cloth, paper are mentioned, for example.

The method of applying the composition of the present invention to the adherend is not particularly limited. For example, a conventionally well-known thing is mentioned.

It is preferable that it is 100-250 degreeC from a viewpoint that the temperature at the time of hardening the composition of this invention is more excellent in curability, and the glass transition temperature of hardened | cured material is high, and it is more preferable that it is 120-200 degreeC.

<Examples>

An Example is shown to the following and this invention is concretely demonstrated to it. However, this invention is not limited to these.

1. Evaluation

The gel time and glass transition temperature were evaluated by the method shown below about the epoxy resin composition obtained as follows. The results are shown in the first and second tables.

(1) gel time

Evaluation of curability measured the gel time at 150 degreeC using the Yasuda type gel time tester (made by Yasuda Seiki Seisakusho, No.153 gel time tester).

The Yasuda gel time tester rotates the rotor in a test tube containing a sample in an oil bath, and when the gelation proceeds and a constant torque is applied, the rotor is pulled out by a magnetic coupling mechanism. The timer stops.

(2) glass transition temperature

The epoxy resin composition obtained in the following manner was cured in an oven at 150 ° C for 1 hour, and the dynamic viscoelasticity measurement (Dynamic Mechanical Analysis) was distorted with respect to the cured product. In the temperature range from room temperature to 200 ° C., forced elongation excitation was performed to measure storage modulus (G ′).

2. Preparation of Epoxy Resin Composition

The components shown in the following 1st table | surface and the 2nd table | surface were mixed by the quantity (mass part) shown by the said table | surface, and the epoxy resin composition was manufactured.

The detail of each component shown to a 1st table | surface and a 2nd table | surface is as follows.

Epoxy resin (A): EP4100E (made by ADEKA) Bisphenol A type epoxy resin, epoxy equivalent 188 g / mol

Aromatic polyamine compound (B) 1: The compound represented by the following formula, made by Tokyo Kasei Kogyo Co., Ltd.

Aromatic polyamine compound (B) 3: It is made from bis (amino phenyl) fluorene and JFE Chemical Corporation (JFE Chemical Corporation) represented by the following formula.

Aromatic polyamine compound (B) 4: methylene bis (2-ethyl-6-methylaniline) (brand name Kayhahaddo MED) represented by the following formula, IHARA CHEMICAL INDUSTRY CO ., LTD.)

Compound 1 represented by formula (I): A compound represented by the following formula (1), produced by Hogkyo Kagaku Kogyo Co., Ltd.

Compound 2 represented by formula (I): Compound represented by formula (2) below, made by Hokkaido Kagaku Kogyo Co., Ltd.

TTP: Made by Tokyo Kasei Kogyo Co., Ltd. and used as a curing accelerator.

Aliphatic amines: Compounds represented by the following formula, trade name DMP-30, manufactured by Tokyo Kasei Kogyo Co., Ltd.

Amine latent curing agent: PN23J (made by Ajinomoto Fine-Techno co., Inc.)

Phenolic novolac resin hardener: MEH-8000H (made by Meiwa Kasei Co., Ltd.)

Phenolic aralkyl resin curing agent: MEH-7800S (made by Meiwa Kasei Co., Ltd.)

Acid anhydride curing agent: Rikashido MT-500 (manufactured by Shin-Nihon Rika Co., Ltd.)

As is clear from the results shown in the first and second tables, Comparative Example I-1, which does not contain the compound represented by the formula (I), has a poor gel curability at 150 ° C. over 3 minutes and is poor in curability. The transition temperature was low. In Comparative Example I-5 which did not contain the compound represented by Formula (I), the gel time in 150 degreeC exceeded 3 minutes, and was curable. In addition, Comparative Examples I-2 to 4 which do not contain the compound represented by formula (I) and contain other curing accelerators (TPP, aliphatic amines, amine latent curing agents) have a gel time of 150 minutes at 150 ° C. The curability was bad beyond and the glass transition temperature was low. In Comparative Examples I-6 to 8, which do not contain the compound represented by formula (I) and contain other curing accelerators (TPP, aliphatic amines, amine latent curing agents), the gel time at 150 ° C exceeds 3 minutes. Curability was bad. In Comparative Example I-9 using triphenylphosphine as a curing agent for epoxy resins, the gel time at 150 ° C. exceeded 3 minutes and was poor in curability. Furthermore, Comparative Examples I-10 to 11 containing a compound represented by the formula (I) but containing a curing agent of a phenolic resin (combination of the compound represented by the formula (I) with a phenolic resin) and an acid anhydride type In Comparative Example I-12 containing a curing agent, the gel time at 150 ° C exceeded 3 minutes in the same manner as in Comparative Example I-9, and the curability was bad.

On the other hand, in Examples I-1 to 13, the gel time in 150 degreeC was 120 second or less, was excellent in sclerosis | hardenability, and the glass transition temperature of the hardened | cured material obtained was high. In detail, Examples I-1 to 13 can harden | cure under 120-200 degreeC conditions, although it contains an aromatic polyamine, Furthermore, hardening time is short. That is, the thermosetting epoxy resin composition of this invention is excellent in low temperature curability compared with the conventional epoxy resin composition containing an epoxy resin and an aromatic polyamine.

3. Evaluation

About the composition obtained as follows, the gel time, the viscosity, and the rate of viscosity increase were evaluated by the following method. The results are shown in Tables 3-7.

(1) gel time (fast curing)

Evaluation of curability was measured on a hot plate gel time at 150 ℃ according to JIS C2161: 1997. Specifically, 0.1 g of the epoxy resin composition obtained in the following manner is placed on a hot plate, and the metal rods are agitated and mixed at a rate of 60 ± 5 times / minute, and when the composition becomes a gel phase from the start of evaluation (the whole cannot be stirred by stirring or The time until the end of the needle is not adhered to the needle) was defined as gelation time (gel time).

(2) viscosity

About the composition obtained as follows, the initial viscosity was measured according to using the E-type viscosity meter VISCONIC EHD type (made by Toki Sangyo Co., Ltd.) on 25 degreeC conditions.

In addition, after the composition obtained as follows was preserve | saved for 24 hours in 25 degreeC conditions in the thermostat, the viscosity (viscosity after storage) of the composition was measured similarly to initial stage viscosity.

(3) viscosity increase rate (storage stability)

The viscosity increase rate was computed by applying the value of the obtained initial viscosity and the viscosity after storage to the following formula.

% Viscosity increase = (viscosity after preservation-initial viscosity) / initial viscosity x 100

As evaluation criteria of a viscosity increase rate, when it was within 10%, it was made possible to use it as a one-component thermosetting epoxy resin composition.

4. Microencapsulation of a Compound Represented by Formula (I) (Preparation of Microcapsules Using a Compound Represented by Formula (I) as a Core)

Microencapsulation was carried out by a spray drying method using a spray dryer GS310 made by Yamato Kagaku Co., Ltd. (YAMATO SCIENTIFIC CO., LTD.).

(1) microcapsules having a thickness equivalent to 10 mass% of the weight of the core

TPP-S (10g, melting point 205 ° C, made in Hokkaido Kagaku Kogyo Co., Ltd., as follows) (or TPTP-S: 10g, melting point 171 ° C, made in Hokkyo Kagaku Co. 50 g of a curing accelerator solution suspended in solvent: ethyl acetate (40 g) and a solvent: thermoplastic resin solution (1 g of thermoplastic resin in solvent) dissolved in ethyl acetate (9 g) were mixed using the spray drying apparatus. Spray drying was performed to obtain powder (microcapsules having a thickness of 10% by mass).

(2) microcapsules having a thickness equivalent to 20% by weight of the weight of the core

50 g of a curing accelerator solution in which TPP-S (10 g) (or TPTP-S: 10 g) is suspended in solvent: ethyl acetate (40 g), and a thermoplastic resin solution (2 g of thermoplastic resin in solvent) dissolved in solvent: ethyl acetate (18 g). ) Was mixed and spray-dried using the said spray drying apparatus, and powder (microcapsules of 20 mass% thickness) was obtained.

(1) TPP-S @ MC1

Shell: Urethane resin Desmocoll (Desmocoll) 500 (made by Bayer Holding Ltd., as follows) is 10% by mass with respect to the core (TPP-S). Microencapsulation was performed to make thickness. The obtained microcapsules are referred to as TPP-S @ MC1. The average particle of TPP-S @ MC1 was 10 μm.

(2) TPP-S @ MC2

Shell: The microencapsulation was performed so that urethane resin desmocol 500 might be 20 mass% of thickness with respect to the core (TPP-S). The obtained microcapsules are referred to as TPP-S @ MC2. The average particle of TPP-S @ MC2 was 11 µm.

(3) TPP-S @ MC3

Shell agent: Styrene butadiene elastomer Tufprene 912 (made by Asahi Kasei Corporation, block copolymer, the same) is 10% by mass relative to the core (TPP-S) Microencapsulation was performed to make thickness. The obtained microcapsules are referred to as TPP-S @ MC3. The average particle of TPP-S @ MC3 was 10 μm.

(4) TPP-S @ MC4

Shell: Polyvinyl acetal resin KS10 (made by Sekisui Kagaku Kogyo Co., Ltd., weight average molecular weight 56,000, hydroxyl group 18 mol%, acetalization degree 80 mol%, the same applies below.) Microencapsulation was performed so as to have a thickness of 10% by mass with respect to TPP-S). Let the obtained microcapsule be TPP-S @ MC4. The average particle of TPP-S @ MC4 was 10 μm.

(5) TPP-S @ MC5

Shell: Phenoxy Resin YP-50 (made by Toto Kasei Co., Ltd., having a weight average molecular weight of 60,000 to 80,000, is the same below) at a thickness of 10% by mass with respect to the core (TPP-S). Microencapsulation was carried out as much as possible. Let the obtained microcapsule be TPP-S @ MC5. The average particle of TPP-S @ MC5 was 10 μm.

(6) TPP-S @ MC6

Shell: The microencapsulation was performed so that polyvinyl alcohol (brand name NH-18, made by Nippon Kosei Kagaku Co., Ltd.) was 10 mass% with respect to the core (TPP-S). The obtained microcapsules are referred to as TPP-S @ MC6. The average particle of TPP-S @ MC6 was 10 μm.

(7) TPTP-S @ MC1

Shell: Microencapsulation was performed so that the phenoxy resin YP-50 had a thickness of 10% by mass relative to the core (TPTP-S). Let the obtained microcapsules be TPTP-S @ MC1. The average particle of TPTP-S @ MC1 was 10 mu m.

5. Microencapsulation of Curing Agents (Preparation of Microcapsules with Curing Agent as Core)

(1) Hardener (1) @ MC1

Shell agent: It is micro so that urethane resin desmochol 500 may have thickness of 10 mass% with respect to a core [hardening agent (1): the compound represented by following formula, melting point 89 degreeC, made in Tokyo Kasei Kogyo Co., Ltd., the following.] Encapsulation was done. Let obtained microcapsule be a hardening | curing agent (1) @ MC1. The average particle of the curing agent (1) @ MC1 was 10 μm.

(2) curing agent (1) @ MC2

Shell agent: The microencapsulation was performed so that urethane resin desmochol 500 might be 20 mass% of thickness with respect to the core [curing agent (1)]. Let the obtained microcapsule be a hardening | curing agent (1) @ MC2. The average particle of the curing agent (1) @ MC2 was 10 μm.

(3) curing agent (1) @ MC3

Shell agent: Microencapsulation was performed so that styrene-butadiene elastomer-tuffrene 912 became 10 mass% of thickness with respect to the core [curing agent (1)]. Let the obtained microcapsule be a hardening | curing agent (1) @ MC3. The average particle of the curing agent (1) @ MC3 was 10 μm.

(4) Hardener (1) @ MC4

Shell agent: The microencapsulation was performed so that polyvinyl acetal resin KS10 may be 10 mass% of thickness with respect to the core [curing agent (1)]. Let the obtained microcapsule be a hardening | curing agent (1) @ MC4. The average particle of the curing agent (1) @ MC4 was 10 μm.

(5) Hardener (1) @ MC5

Shell agent: The microencapsulation was performed so that phenoxy resin YP-50 might be 10 mass% of thickness with respect to the core [curing agent (1)]. Let the obtained microcapsule be a hardening | curing agent (1) @ MC5. The average particle of the curing agent (1) @ MC5 was 10 μm.

(6) curing agent (2) @ MC1

Shell agent: The phenoxy resin YP-50 is 10 mass% with respect to a core [hardening agent (2): bis (amino phenyl, melting point 237 degreeC) fluorene represented by the following formula, made from JFE Chemiru Kabushiki Kaisha]. Microencapsulation was carried out as much as possible.

Let the obtained microcapsule be a hardening | curing agent (2) @ MC1. The average particle of the hardening | curing agent (2) @ MC1 was 10 micrometers.

6. Preparation of Composition

The composition shown in Table 3-Table 7 was used for the quantity (mass part) shown by the table, and they were mixed with the reduced pressure stirrer and the composition was produced.

In addition, in 3rd table | surface, 4th table | surface, and 6th table | surface, the numerical value which has "eq" as a unit with respect to the quantity of a hardening | curing agent is the equivalent number (active hydrogen / epoxy group) of active hydrogen of the hardening | curing agent with respect to an epoxy group.

In 3rd table | surface and 4th table | surface, the quantity (mass part) as a microcapsule is shown about the microcapsule which contains the compound represented by Formula (I).

In the 5th table, about the microcapsule which contains a hardening | curing agent, the quantity (mass part) as a microcapsule is shown.

Each component shown in 3rd table-7th table | surface is as follows.

Epoxy resin: same as the first table

Curing agent (1): same as the aromatic polyamine compound (B) 1 of the 1st table

Curing agent (2): same as the aromatic polyamine compound (B) 3 of the 1st table

Curing agent (3): TMTG represented by the following formula: made from trimethylolpropane tris (thioglycolate) and Yodo Kagakusha Co., Ltd.

Curing agent (4): mercaptosilane condensate represented by the following formula (manufactured by Z6362H, Dow Corning Toray co., Ltd.)

In formula, n is 6-8.

Curing agent (5): trade name PN, phenol novolak (made by Nippon Kayaku Co., Ltd.)

Curing agent (6): trade name XYLOK-4L, xylene glycol / phenol condensate (made by Mitsui Chemicals, Inc.)

Curing agent (7): methylene bis (2-ethyl-6-methylaniline) represented by the following formula (trade name: Kayahado MED, manufactured by Ihara Chemical Co., Ltd.)

TTP-S @ MC1 to TPP-S @ MC6, TPTP-S @ MC1: microcapsules containing the compound represented by formula (I) prepared as above.

Curing agent (1) @ MC1-hardening | curing agent (1) @ MC5, hardening | curing agent (2) @ MC1: The microcapsule containing the hardening | curing agent manufactured as mentioned above.

TTP-S: similar to compound 1 represented by formula (I) in the first table.

TPTP-S: similar to compound 2 represented by formula (I) in the first table.

Phenolic novolac resin curing agent: same as in the second table

Phenolic aralkyl resin curing agent: same as in the second table

Acid anhydride hardener: same as in the second table

TTP: Like the second table

Aliphatic amines: the same as in the second table

Amine latent curing agents: the same as in the second table

As apparent from the results shown in Tables 3 to 7, the epoxy resin, the compound represented by formula (I), and the aromatic polyamine represented by formula (II) as a curing agent are contained, and are represented by formula (I). Examples IV-1 to 6, in which the compound and the curing agent were not contained by the thermoplastic resin, were excellent in fast curing properties. Comparative Examples III-5 and 6, which do not contain the aromatic polyamine represented by the formula (II) and instead contain a phenol resin or a condensate of a phenol resin, were inferior in fast curing properties.

Moreover, Comparative Examples IV-1-8 which do not contain the compound represented by Formula (I) were inferior to fast hardening property. Comparative Example IV-9 containing phenol resin as curing agent and TPP as curing accelerator, no aromatic polyamine represented by formula (II) as curing agent, instead containing phenol resin and containing TPP-S as curing accelerator Comparative Examples IV-10 to 12 were inferior to fast curing properties.

On the other hand, in Examples II-1 to 15 and Examples III-1 to 12, the viscosity increase rate was less than 10%, and the storage stability was excellent, and excellent fast hardenability was maintained.

Claims (5)

In the thermosetting epoxy resin composition containing an epoxy resin (A), an aromatic polyamine compound (B), and a compound represented by the following formula (I), the gelation time is within 3 minutes at 150 ° C, characterized in that the thermosetting epoxy resin Composition.
[Formula 1]

(In formula, R <^1> , R <^2> represents a hydrogen atom and an alkyl group, respectively.) The method of claim 1,
The thermosetting epoxy resin composition containing the compound represented by following formula (1) and / or the compound represented by following formula (2) as a compound represented by said Formula (I).
(2)

(In formula, Ph represents a phenyl group or a phenylene group.) The method according to claim 1 or 2,
The thermosetting epoxy resin composition in which the said aromatic polyamine compound (B) is represented by following formula (II).
(3)

[In formula (II), R <^3> , R <^4> is an alkyl group, respectively, R <^5> is at least 1 sort (s) chosen from the group which consists of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group, and a sulfide group. M and n are each an integer of 0 to 4.] 4. The method according to any one of claims 1 to 3,
The thermosetting epoxy resin composition in which any one or both of the compound represented by the said Formula (I) and the said aromatic polyamine compound (B) is contained as a microcapsule contained by a thermoplastic resin. The method according to any one of claims 1 to 4,
The equivalent number of active hydrogens which the aromatic polyamine compound (B) has is 0.5-2.5 equivalents with respect to the epoxy group which the said epoxy resin (A) has,
The thermosetting epoxy resin composition whose quantity of the compound represented by said Formula (I) is 1-30 mass parts with respect to 100 mass parts of said epoxy resins (A).