JPH0565331A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition which can give a flexible cured product by mixing a specified alicyclic epoxy resin composition with a cationic polymerization initiator as essential components. CONSTITUTION:The objective composition comprises an alicyclic epoxy resin composition of formula I (wherein Z is formula II; Y<1> is formula III; Y<2> is formula IV; R<11> to R<29>, R<a> and R<b> are each H or 1-9C alkyl; (c) is 4-8; and n1 is an integer of 1 or greater) (e.g. a compound of formula V) and a cationic polymerization initiator (e.g. an initiator comprising a tris-ethylacetoacetato- aluminum as an organoaluminum compound and diphenyldimetoxy-silane as an organosilicon compound). This composition can give a tough cured product of excellent flexibility, so that the scope of application of a thermosetting epoxy resin can be extended to a field requiring flexibility. Further, when it is mixed with another thermosetting epoxy resin, the resulting mixture can give a cured product of aimed flexibility.

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.

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.

[0004]

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 a large amount of flexible epoxy resin is required. There are cases.

[0005]

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.

[0006]

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), Ra and Rb 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 Rb are all hydrogen. Also, β-methyl-
Ra and Rb are methyl groups and hydrogen when δ-valerolactone is used, and Ra and Rb are ethyl groups and hydrogen when 3-ethyl-caprolactone is used.

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 represents an integer of 1 or more and is the number of moles of the added lactone.

For example, n1 = 0 when no lactone is added and n1 = 5 when 5 mols are added.

In the composition represented by the general formula (I), n1 does not have to be a single integer, and the composition represented by the general formula (I) may be a mixture of different n1.
= 0 may be included.

Examples of the aliphatic cyclic epoxy resin represented by the general formula (I) include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate modified with caprolactone [general formula (II)]. Or 3,
4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate modified with trimethylcaprolactone [Formula (III) (II)
I) ′] or a valerolactone-modified product of 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate [the general formula (IV ) (IV) ′] and the like.

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

The composition represented by the general formula (I) can be synthesized by the synthesis method described in Japanese Patent Application No. 2-140732. Moreover, as these commercial products,
For example, Celloxide manufactured by Daicel Chemical Industries, Ltd.
2081, Celloxide 2083, Cello
xide 2085 and the like can be used. Further, the composition represented by the general formula (I) is
You may use only 1 type or 2 or more types simultaneously.

Further, the general formulas (I), (II), (III) and (II
I) ′, (IV) and (IV) ′, Y ¹ , Y ² and

[0021]

[Chemical 8]

[0022]

[Chemical 9]

Olefin before modification or modified epoxy group, for example,

[0024]

[Chemical 10]

[0025]

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 ⁻

[0027]

[Chemical 11]

[0028]

[0029]

[Chemical 12]

[0030]

[0031]

[Chemical 13]

[0032]

Sulfonium salts represented by the following general formulas (VIII), (IX) and (X):

[0034]

[Chemical 14]

[0035]

[0036]

[Chemical 15]

[0037]

[0038] 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,

[0039]

[Chemical 16]

[0040]

[0041]

[Chemical 17]

[0042]

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 amount of these cationic polymerization initiators added and compounded 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 the thermal cationic polymerization initiator.

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

[0048] [However, Hy is an OH group or a substituent that produces an OH group by hydrolysis, and R ⁴⁵ , R ⁴⁶ , and R ⁴⁷ are
They 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 and r ≦.
It represents an integer satisfying the condition of 3, 1 ≦ p + q + r ≦ 3. 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, a methoxy group, an ethoxy group, a chloromethyl group, and the like, the aryl group, for example, a phenyl group, a tolyl group, a naphthyl group, an anthranyl group, and the like, the aralkyl group, for example, a benzyl group, Examples thereof include a phenethyl group and the like, examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a phenyl group, and the like, and examples of the acyl group include an acetyl group, a benzoyl group, and the like. ~ 5 alkyl groups, aryl groups, aralkyl groups, alkenyl groups, acyl groups include halogen atoms, nitro groups, cyano groups, methoxy groups and the like. It may have a substituent.

Specific examples of such silicon compounds include, for example, triphenylmethoxysilane, diphenyldimethoxysilane, triphenylethoxysilane, diphenylmethylmethoxysilane, phenylvinylmethylmethoxysilane, diphenyldiethoxysilane, 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, And their hydrolysis products.

Organosiloxane is represented by the following formula.

[0051] [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
, An alkyl group, an aryl group, an aralkyl group, an alkenyl group, an acyl group, and an 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, a methoxy group, an ethoxy group, a chloromethyl group, and the like, the aryl group, for example, a phenyl group, a tolyl group, a naphthyl group, an anthranyl group, and the like, the aralkyl group, for example, a benzyl group, Examples thereof include a phenethyl group and the like, examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a phenyl group, and the like, and examples of the acyl group include an acetyl group, a benzoyl group, and the like. ~ 5 alkyl groups, aryl groups, aralkyl groups, alkenyl groups, acyl groups include halogen atoms, nitro groups, cyano groups, methoxy groups and the like. It may have a substituent.

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 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,

[0054]

[Chemical 18]

[0055]

[0056] 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 either individually or in combination of two or more.

Specific examples of aluminum compounds used together with these silicon compounds include trismethoxyaluminum, trisethoxyaluminum, 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,

[0059]

[Chemical 19]

[0060]

[0061]

[Chemical 20]

[0062]

[0063]

[Chemical 21]

[0064]

[0065]

[Chemical 22]

[0066]

[0067]

[Chemical 23]

[0068]

[0069]

[Chemical 24]

[0070]

[0071]

[Chemical 25]

[0072]

[0073]

[Chemical 26]

[0074]

[0075]

[Chemical 27]

[0076]

[0077]

[Chemical 28]

[0078]

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 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 is 30 to 200.
℃ is good.

Further, 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.

[0085] 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 addition of these cationic polymerization initiators is 0.001 to 20% by weight, preferably 0.001 to 20% 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 0 to 200 ° C.
Good.

In the present invention, a filler such as silica, a pigment, a dye or the like may be added if necessary.

In the resin composition of the present invention, other epoxy resins, such as epi-bis type epoxy resin, limonene diepoxide, vinylcyclohexene diepoxide, vinylcyclohexene monoepoxide, etc., can be used as long as the characteristics are not impaired. You may mix and use alicyclic epoxy etc.

[0090]

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.

[0092]

[Examples 1 to 3] As an epoxy resin composition, a compound represented by the general formula II
And n1 = 1 (average) epoxy resin (hereinafter referred to as epoxy resin [A]), n1 = 3 (average) epoxy resin (hereinafter referred to as epoxy resin [B]) in general formula II, and general formula An epoxy resin having n1 = 5 (average) in II (hereinafter referred to as epoxy resin [C]) is further used as a thermal cationic polymerization initiator, and a complex of a silicon compound and an aluminum compound (trisethylacetoacetate as an organic aluminum compound). Aluminum (TEAACA) as the organosilicon compound, diphenylsilanediol, diphenyldimethoxysilane), and aniline / boron trifluoride complex were used in the proportions shown in Table-1 to form a 3 mm thick cured plate. It was created and the physical properties were measured. The results are shown in Table-1.

[0093]

[Comparative Examples 1 and 2] As an epoxy resin composition, a compound represented by the general formula II
And an epoxy resin of n1 = 0 (hereinafter referred to as epoxy resin [D]) is used as a thermal cationic polymerization initiator and a complex of a silicon compound and an aluminum compound (trisethylacetoacetatoaluminum (TE) as an organoaluminum compound).
AACA) Diphenyldimethylsilane) was used as the organosilicon compound, and aniline / boron trifluoride complex was 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. <Evaluation method> The cured physical properties were measured under the conditions of 20 ° C. and 65% RH. JIS measurement of tensile strength and tensile elongation
It carried out according to K 6911. In addition, Tg is a high-performance differential scanning calorimeter (DSC 8230B manufactured by Rigaku Denki Co., Ltd.)
Was measured.

Table-1 Examples 1 2 3 Comparative Example 1 Comparative Example 2 Epoxy resin [A] 100 Epoxy resin [B] 100 Epoxy resin [C] 100 Epoxy resin [D] 100 100 TEAACA 0.05 0.5 0.05 Diphenylsilanedio- Le 1.0 Diphenyldimethoxysilane 0.1 0.1 Aniline / boron trifluoride complex 0.05 0.05 Curing conditions Curing temperature (° C) 140 100 25 25 140 100 Curing time (hours) 5 10 160 5 10 Tg (° C / DSC) 110 10-20 20 160 140 Tensile strength (kgf / mm ² ) 6.4 1.7 0.3 4.0 4.9 Tensile elongation (%) 10 40 150 2 3

Claims (3)

[Claims] 1. A thermosetting resin composition Y comprising (a) an aliphatic cyclic epoxy resin composition represented by the following general formula (I) and (b) a cationic polymerization initiator as essential components. ^{_{1 -CO- [Z] n1 -OCH 2}} -Y 2 ····· (I) [where in formula (I), Z is the following structure Y ¹ has the following structure: Y ² has the following structure: R ^{11 to} R ²⁹ , R ^a , and R ^b can be simultaneously replaced by hydrogen or an alkyl group, typically containing 1 to 9 carbon atoms, for each group. c is an integer from 4 to 8, n1
Represents an integer of 1 or more. ] 2. The thermosetting resin composition according to claim 1, wherein a part or all of the composition represented by the general formula (I) is a composition represented by the general formula (II). [Chemical 3] 3. 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.