JPH0570561A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To improve flexibility by compounding a specific alicyclic epoxy resin compsn. and a cationinc polymn. initiator. CONSTITUTION:An alicyclic epoxy resin compsn. of formula I (wherein Z is a group of formula II; Y<1> is a group of formula III; Y<2> is a group of formula IV; Y<u> is a group of formula V; R is an m-valent org. 1-30C compd. residue; R<11> to R<m9> are each H or 1-9C alkyl; and R<a> and R<b> are each H or alkyl) and 0.01-20wt.% cationic polymn. initiator comprising an organosilicon compd. having a hydroxyl or hydrolyzable group directly attached to a silicon atom and an organoaluminum compd. are compounded.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aliphatic cyclic epoxy resin composition and a thermosetting resin composition containing a cationic polymerization initiator. The cured product of the conventional aliphatic cyclic epoxy resin composition is hard and brittle, while it is suitable for obtaining a cured product having flexibility.

According to the present invention, an epoxy resin cured product having excellent flexibility can be obtained, and in the field of coating resin, powder coating, hybrid baking coating, coating agent, etc. impart flexibility. It is intended to provide the excellent characteristics of.

Since the epoxy resin used in the present invention is a polyfunctional type, a tough cured product can be obtained.

The thermosetting resin composition of the present invention is an ink,
Various coating fields such as plastic coating, paper printing, film coating, metal coating, furniture coating, FRP, lining, adhesives, and insulating varnishes, insulating sheets, and laminated boards in the field of electronics. ,
It can be applied to many industrial fields such as printed circuit boards, resist inks, LED encapsulants, and semiconductor encapsulants.

[0005]

2. Description of the Related Art Epoxy resins have good workability and excellent mechanical properties of cured products, and are used in various fields. However, conventional epoxy resins have the drawback of being hard and brittle, and their applications are limited. In order to improve these drawbacks, a flexible epoxy resin or a flexibility-imparting agent has been used in the past, but many of them have a high viscosity. Therefore, those compounded with these require a low viscosity. It is not suitable for the fields in which it is used.

There is also a flexible epoxy resin such as bis (3,4-epoxycyclohexylmethyl) adipate, but when sufficient flexibility cannot be obtained, or when the flexible epoxy resin is added in a large amount. May be required.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a thermosetting resin composition containing an aliphatic cyclic epoxy resin having excellent flexibility.

[0008]

According to the present invention, there is provided a thermosetting resin composition comprising an epoxy resin composition represented by the general formula (I) and a cationic polymerization initiator.

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

In the general formula (I), R ^a and R ^b are a hydrogen atom or an alkyl group generally containing 1 to 9 carbon atoms, which depends on the starting lactone. For example, when ε-caprolactone is used as a raw material, R
^a and R ^b are all hydrogen. Also, β-methyl-
When δ-valerolactone is used, R ^a and R ^b are methyl groups and hydrogen, and when 3-ethyl-caprolactone is used, R ^a and R ^b are ethyl groups and hydrogen.

Further, c is an integer of 4 to 8, which is also determined by the starting lactone.

For example, in the case of ε-caprolactone, c =
5, c = 4 for valerolactone and c = 7 for cyclooctanone lactone.

N1 and nm represent an integer of 0 or more, which is the number of moles of the added lactone.

For example, when lactone is not added at all, n1 = 0, nm = 0, and when 5 mol is added, n1 + n2 + ...
・ = 5.

Further, in the composition represented by the general formula (I), n1 and nm do not have to be single integers, and the general formula (I)
The composition represented by may be a mixture of different n1 and nm, and may include a mixture of n1 = 0 and nm = 0.

Examples of the aliphatic cyclic epoxy resin represented by the general formula (I) when m is 2 include the epoxy resin composition represented by the general formula (II) and the epoxy represented by the general formula (IV). A resin composition etc. can be mentioned.

[0017]

[Chemical 6]

When m is 2, the composition represented by the general formula (I) can be synthesized by the synthetic method described in Japanese Patent Application No. 2-182124. Further, examples of commercially available products thereof include EPO manufactured by Daicel Chemical Industries, Ltd.
LEAD GT-300, EPOLEAD GT-30
1 and EPOLEAD GT-302, and these can be used.

When m is 4, an example of the general formula is
The epoxy resin composition represented by (III) can be mentioned. In this case, the composition represented by the general formula (I) can be synthesized by the synthesis method disclosed in Japanese Patent Application No. 2-182124. Examples of commercially available products of these include EPOLEAD GT-400, E manufactured by Daicel Chemical Industries, Ltd.
POLEAD GT-401, EPOLEAD GT-
There are 403 and the like, and these can be used. Further, the composition represented by the general formula (I) is only one kind,
Alternatively, two or more kinds may be used at the same time.

Further, the general formulas (I), (II), (III) and (IV)
Where Y ¹ , Y ^m and

[0021]

[Chemical 7]

Further, as the cationic polymerization initiator which is another essential component of the present invention, the following boron trifluoride complex, C ₆ H ₅ NH ₂ .BF ₃ (CH ₃ ) ₂ CH ₂ NH ₂ .BF _{3 is used. (C 6 H 5) 3 P} · BF 3 CH 3 CH 2 NH 2 · BF 3 CH 3 CH 2 NH 3 + · BF 4 - (sec-Bu) 2 NH · BF 3 (sec-Bu) 2 NH 2 + ^{_{· BF 4 - CH 3 NH 2}} · BF 3 CH 3 NH 3 + · BF 4 - below the metal fluoride ^{_{complexes, C 6 H 5 NH 3 +}} · AsF 6 - C 6 H 5 NH 3 + · BF 4 - C 6 H ₅ NH ₃ ⁺ · PF ₆ ⁻ Sulfonium salt represented by the following general formulas (VIII), (IX) and (X),

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

[0026]

[0027] Yo as represented by the following general formula (XI) - Doniumu ^{salt, R 40 -I + -R 41 ·} MX n - ····· (XI) following general formula (XII), in (XIII) A metal compound, as shown,

[0028]

[Chemical 11]

[0029]

General formulas (VIII), (IX), (X), (XI), (XII)
In, MX _n ⁻ is SbF ₆ ⁻ , AsF ₆ ⁻ , PF
₆ ^-, BF ₄ ^- is at least one selected from the.

The addition amount of these cationic polymerization initiators is in the range of 0.01 to 20% by weight, preferably 0.1 to 5% by weight, based on the epoxy resin.

If the blending amount is less than 0.01% by weight, sufficient curing characteristics cannot be obtained, and it is possible to use more than 20% by weight, but the cost is high and the decomposition of the catalyst component is degraded. The product may be a problem and is not preferred.

Further, a mixture such as a complex of a silicon compound which produces a silanol group by heating and an aluminum compound can be used as a thermal cationic polymerization initiator.

Examples of such silicon compounds include organosilane and organosiloxane. Such an organosilane is represented by the following formula.

[0035] [Wherein Hy is an OH group or a substituent that produces an OH group by hydrolysis, and R ⁴⁵ , R ⁴⁶ , and R
⁴⁷ may be the same or different and each represents an alkyl group having 1 to 5 carbon atoms, an aryl group, an aralkyl group, an alkenyl group, an acyl group or the like, and p, q and r are 0 ≦ p,
q, r ≦ 3, 1 ≦ p + q + r ≦ 3 represents an integer satisfying the condition] In the above formula, examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an isopropyl group, and n.
-Propyl group, n-butyl group, t-butyl group, sec-
Butyl group, n-pentyl group, methoxy group, ethoxy group,
Examples of the chloromethyl group and the like, as the aryl group,
Examples thereof include a phenyl group, a tolyl group, a naphthyl group, an anthranyl group, and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkenyl group include a vinyl group, an allyl group, and a propenyl group. Examples of the acyl group include an acetyl group and a benzoyl group, and an alkyl group having 1 to 5 carbon atoms, an aryl group, an aralkyl group, an alkenyl group, and an acyl group are halogen groups. It may have a substituent such as an atom, a nitro group, a cyano group or a methoxy group.

Specific examples of such silicon compounds include, for example, triphenylmethoxysilane, diphenyldimethoxysilane, triphenylethoxysilane, diphenylmethylmethoxysilane, phenylvinylmethylmethoxysilane, diphenyldiethoxysilane and tri (para). (Methoxyphenyl) methoxysilane, triacetylmethoxysilane, diphenylethylethoxysilane, diphenylpropylethoxysilane, diphenylmethylacetoxysilane, diphenyldipropionyloxysilane, diphenylmethyltriphenylacetoxysilane,
Tri (paranitrophenyl) methoxysilane, phenyldivinylpropoxysilane, 2-futenyldiphenylmethoxysilane, di (2-pentenyl) phenylethoxysilane, phenyldipropylmethoxysilane, tri (paramethoxyphenyl) ethoxysilane, paramethylbenzyl Trimethoxysilane, trifluoroacetyltrimethoxysilane, di (parachlorophenyl) diethoxysilane, triethylmethoxysilane, trimethylmethoxysilane, tripropylmethoxysilane, tributylethoxysilane, tributylacetoxysilane, [B is a benzene nucleus] And their hydrolysis products.

Organosiloxane is represented by the following formula.

[0038] [However, R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ , R ⁵² , and R ⁵³
May be the same or different and can be changed to each group at the same time, and an OH group, a hydrolyzable group, and a carbon number of 1 to 5
Alkyl group, aryl group, aralkyl group, alkenyl group, acyl group, and organosiloxane residue represented by the following formula And so on. In particular, at least one of the structural units is OH
It contains at least one of a group and a hydrolyzable group. Further, n2 is an integer of 0 or more. In the above formula, examples of the alkyl group having 1 to 5 carbon atoms include, for example, methyl group, ethyl group, iropropyl group, n-propyl group, n-butyl group, t-butyl group, sec-butyl group, n-pentyl group. Group, methoxy group, ethoxy group, chloromethyl group and the like, and as the aryl group, for example, phenyl group, tolyl group, naphthyl group, anthranyl group and the like,
Examples of the aralkyl group include a benzyl group and a phenethyl group, and examples of the alkenyl group include:
Examples thereof include a vinyl group, an allyl group, a propenyl group, and a phenyl group. Examples of the acyl group include an acetyl group and a benzoyl group. An alkyl group having 1 to 5 carbon atoms, an aryl group, an aralkyl group, The alkenyl group and the acyl group may have a substituent such as a halogen atom, a nitro group, a cyano group and a methoxy group.

Among the above-mentioned organosiloxanes, the degree of polymerization is 50 or less and the OH group equivalent or hydrolyzable group equivalent is 10
Those having a OH group equivalent of 5 or less are suitable for the present invention.
Those of 0 to 500 are preferable.

Specific examples of such an organosiloxane include, for example, 1,3-dimethoxy-1,3-dimethyl-1,3-diphenyldisiloxane and 1,5-diethoxy-1,3,5-trimethyl- 1,3,5-triphenyltrisiloxane, 1,7-dimethoxy-1,3
5,7-Tetramethyl-1,3,5,7-tetraphenyltetrasiloxane, 1,3-dimethoxytetraphenyldisiloxane, 1,5-dimethoxy-3,3-dimethyl-1,1,5,5- Tetraphenyltrisiloxane,
1,3,5-trimethoxypentaphenyltrisiloxane, 1,5-dimethoxyhexa (p-methoxyphenyl) trisiloxane,

[0041]

[Chemical 12]

[0042]

[0043] [B is a benzene nucleus] And hydrolysis products thereof, and Q1-
3037 (Methoxy group content 18% by weight, Toshiba Silicon
Silicone resin), SH6018 (OH equivalent of about 400, Toray Silicone Co., Ltd.) and the like, which are available under the trade names are also applicable.

The above-mentioned organosilane and organopolysiloxane compounds may be used alone or in combination of two or more.

Specific examples of aluminum compounds used together with these silicon compounds include trismethoxyaluminum, tris-ethoxyaluminum, trisisopropoxyaluminum, trisphenoxyaluminum, trisparamethylphenoxyaluminum,
Isopropoxydiethoxyaluminum, trisptoxyaluminum, trisacetoxyaluminum, trisstearate aluminum, trisbutyrate aluminum, trispropionate aluminum, trisisopropionate aluminum, trisacetylacetonate aluminum, tristrifluoroacetylacetate Sodium aluminum, tris hexafluoroacetyl acetonate aluminum, tris ethyl acetoacetate aluminum, tris salicyl aldehyde aluminum, tris diethyl malolato aluminum, tris propyl acetoacetate aluminum, tris Butyl acetoacetate aluminum, tris dipivaloyl methanate aluminum, diacetyl acetonate dipivaloyl methana Aluminum,

[0046]

[Chemical 13]

[0047]

[0048]

[Chemical 14]

[0049]

[0050]

[Chemical 15]

[0051]

[0052]

[Chemical 16]

[0053]

[0054]

[Chemical 17]

[0055]

[0056]

[Chemical 18]

[0057]

[0058]

[Chemical 19]

[0059]

[0060]

[Chemical 20]

[0061]

[0062]

[Chemical 21]

[0063]

[0064]

[Chemical 22]

[0065]

And the like.

These aluminum compounds may be used alone or in a mixture of two or more, and the addition amount thereof is 0.001 to 100 by weight ratio with respect to the epoxy resin.
%, Preferably 1 to 10%.

If the blending amount is less than 0.001% by weight, sufficient curing characteristics of the coating cannot be obtained, and 10
If it exceeds 0% by weight, not only the cost will increase, but also
Moisture resistance tends to decrease, which is not preferable.

The amount of these cationic polymerization initiators added and compounded is 0.001 to 20% by weight, preferably 0.1% by weight, based on the epoxy resin, of both the silicon compound and the aluminum compound.
It is in the range of 005 to 10% by weight.

The curing temperature in this case is 30 to 200.
℃ is good.

Furthermore, a mixture such as a complex of a silicon compound having a silanol group represented by the following formula and an aluminum compound can be used as the thermal cationic polymerization initiator. A silicon compound having such a silanol group is represented by the following formula.

[0072] As the aluminum compound used together with the silicon compound, the aluminum compound used together with the silicon compound which produces a silanol group by the above heating can be used as it is.

The amount of these cationic polymerization initiators added and added is 0.001 to 20% by weight, preferably 0.
It is in the range of 005 to 10% by weight. The curing temperature in this case may be 0 to 200 ° C. In the present invention, a filler such as silica, a pigment, a dye or the like may be added if necessary. Further, in the resin composition of the present invention, other epoxy resins such as epi-bis type epoxy resin, limonene diepoxide, vinylcyclohexene diepoxide, vinylcyclohexene monoepoxide and the like, as long as the characteristics are not impaired. Etc. may be mixed and used.

[0074]

The thermosetting resin composition of the present invention is a tough cured product having excellent flexibility. Utilizing this feature, the range of application of the thermosetting epoxy resin can be expanded to fields requiring flexibility. In addition, by mixing with other thermosetting epoxy resin, it is possible to impart flexibility according to the purpose.

Next, the present invention will be described with reference to examples.

[0076]

Examples 1 to 4 As an epoxy resin composition, a compound represented by the general formula II
Where n1 = n2 = 0 (hereinafter referred to as epoxy resin [A]), general formula II n1 + n2 = 2 (average) epoxy resin (hereinafter referred to as epoxy resin [B]), general formula
An epoxy resin of n1 = n2 = n3 = 0 in III (hereinafter referred to as epoxy resin [C]), and an epoxy resin of n1 + n2 + n3 = 3 (average) in general formula III (hereinafter referred to as epoxy resin [D]) Further, as a thermal cationic polymerization initiator, a complex of a silicon compound and an aluminum compound (trisethylacetoacetoaluminum (TEAACA as an organic aluminum compound) diphenylsilanediol, diphenyldimethoxysilane as an organic silicon compound), and aniline. The boron trifluoride complex was used and compounded in the proportions shown in Table-1, and a cured plate having a thickness of 3 mm was prepared and measured for physical properties. The results are shown in Table-1.

Table-1 Example 1 2 3 4 Comparative Example 1 Epoxy resin [A] 100 Epoxy resin [B] 100 Epoxy resin [C] 100 Epoxy resin [D] 100 Epoxy resin [E] 100 TEAACA 0.05 0.5 0.05 0.05 Diphenylsilanediol 1.0 Diphenyldimethoxysilane 0.1 0.1 0.1 Aniline / boron trifluoride 0.05 Complex curing conditions Curing temperature (° C) 140 140 140 140 140 140 Curing time (hours) 5 5 5 5 5 Tg (° C / DSC) 170 120 170 125 160 Tensile strength (kgf / mm ² ) 5.0 6.1 5.2 4.9 4.0 Tensile elongation (%) 2 6 2 4 2

[0078]

Comparative Example 1 An epoxy resin represented by the general formula XIV (hereinafter referred to as epoxy resin [E]) was used as an epoxy resin composition, and a complex of a silicon compound and an aluminum compound (organoaluminum) was used as a thermal cationic polymerization initiator. Trisethyl acetoacetate aluminum (TEA as a compound
(ACA) Diphenyldimethoxysilane) was used as the organosilicon compound and mixed in the proportions shown in Table 1 to prepare a 3 mm-thick cured plate, and its physical properties were measured. The results are shown in Table-1.

[0079]

[Chemical 23]

[0080]

<Evaluation Method> Cured physical properties were measured at 20 ° C.
It was measured under the condition of 65% RH. The tensile strength and tensile elongation were measured according to JIS K6911. Also, Tg
Is a high performance differential scanning calorimeter (DSC manufactured by Rigaku Denki Co., Ltd.)
8230B).

Claims (4)

[Claims] 1. A thermosetting resin composition comprising (a) an aliphatic cyclic epoxy resin composition represented by the following general formula (I) and (b) a cationic polymerization initiator as essential components. [However, in the formula (I), Z is the following structure Y ¹ has the following structure: Y ² has the following structure: Y ^m has the following structure: Represents. R is an alkyl group having 1 to 30 carbon atoms, a m-valent organic compound residue, R ^{11 to} R ^m9 are hydrogen, and generally 1 to
An alkyl group containing 9 carbon atoms can be converted to each group at the same time. n1 and nm are integers of 0 or more, m is 2
Represents the above integers. ] 2. The curable resin composition according to claim 1, wherein a part or all of the aliphatic cyclic epoxy resin composition represented by the general formula (I) is a composition represented by the general formula (II). [Chemical 4] 3. The curable resin composition according to claim 1, wherein a part or all of the aliphatic cyclic epoxy resin composition represented by the general formula (I) is a composition represented by the general formula (III). [Chemical 5] 4. The thermosetting resin composition according to claim 1, wherein the cationic polymerization initiator comprises an organic silicon compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom and an organic aluminum compound.