JP3090351B2 - Thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

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

[0003] The thermosetting resin composition of the present invention comprises an ink,
Various coating fields such as plastic paints, paper printing, film coating, metal coating, furniture coating, FRP, lining, adhesives, and insulating varnishes, insulating sheets, laminates in the electronics field ,
It can be applied to many industrial fields such as print base, resist ink, LED encapsulant, and semiconductor encapsulant.

[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 disadvantage of being hard and brittle, and their applications are limited. Conventionally, a flexible epoxy resin or a flexibility-imparting agent has been used to improve these drawbacks. However, many of these resins have a high viscosity. It is not suitable for the field where it is done. 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 the 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 has as its object 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-
When δ-valerolactone is used, Ra and Rb are methyl groups and hydrogen, and when 3-ethyl-caprolactone is used, Ra and Rb are ethyl groups and hydrogen.

Also, 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 is an integer of 1 to 20 and is the number of moles of the added lactone. n1 is preferably 1 to 5.

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

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

Examples of the aliphatic cyclic epoxy resin represented by the general formula (I) include, for example, caprolactone-modified 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate [general formula (II)] And 3,
Trimethylcaprolactone modified product of 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate [general formula (III) (II
I) '] or a valerolactone-modified 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate [formula (IV) ) (IV) ′].

[0015]

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[0016]

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[0017]

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[0018]

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The composition represented by the general formula (I) can be synthesized by a synthesis method described in Japanese Patent Application No. 2-140732 (Japanese Patent Application Laid-Open No. 4-36263).
In addition, examples of these commercially available products include Celloxide 2081 and Celloide manufactured by Daicel Chemical Industries, Ltd.
There are xide 2083, Celloxide 2085, and the like, and these can be used. Further, the composition represented by the general formula (I) is only one type, or
Two or more types may be used simultaneously.

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

[0021]

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[0022]

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Unmodified olefin or modified epoxy group, for example,

[0024]

[Formula 10]

[0025]

The cationic polymerization initiator which is another essential component of the present invention includes the following boron trifluoride complex: C ₆ H ₅ NH ₂ · BF ₃ (CH ₃ ) ₂ CH ₂ NH ₂ · BF ₃ (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]

[Formula 11]

[0028]

[0029]

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[0030]

[0031]

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[0032]

A sulfonium salt represented by the following general formulas (VIII), (IX) and (X):

[0034]

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[0035]

[0036]

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[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]

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[0040]

[0041]

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[0042]

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

The amount of the cationic polymerization initiator added is from 0.01 to 20% by weight, preferably from 0.1 to 5% by weight, based on the epoxy resin.

If the compounding 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. Products are not preferred because they can be problematic.

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

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

[0048] [Where Hy is an OH group or a substituent that generates an OH group by hydrolysis, and R ⁴⁵ , R ⁴⁶ , and R ⁴⁷ are
They may be the same or different and represent an alkyl group having 1 to 5 carbon atoms, an aryl group, an aralkyl group, an alkenyl group, an acyl group, etc., wherein p, q and r are 0 ≦ p, q, r ≦
3, represents an integer satisfying the condition of 1 ≦ p + q + r ≦ 3. 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, an n-propyl group, an n-butyl group, a t-butyl group, a sec-butyl group, and an n-pentyl. Groups, methoxy group, ethoxy group, chloromethyl group and the like, and the aryl group includes, for example, a phenyl group, a tolyl group, a naphthyl group, an anthranyl group, and the like, and the aralkyl group includes, for example, a benzyl group, Phenethyl group and the like; alkenyl group includes, for example, vinyl group, allyl group, propenyl group and phthenyl group; and acyl group includes, for example, acetyl group, benzoyl group and the like. And alkyl groups, aryl groups, aralkyl groups, alkenyl groups, and acyl groups, such as halogen atoms, nitro groups, cyano groups, and methoxy groups. 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-phenyldiphenylmethoxysilane, di (2-pentenyl) phenylethoxysilane, phenyldipropylmethoxysilane, tri (paramethoxyphenyl) ethoxysilane, paramethylbenzyl Trimethoxysilane, trifluoroacetyltrimethoxysilane, di (parachlorophenyl) diethoxysilane, triethylmethoxysilane, trimethylmethoxysilane, tripropylmethoxysilane, tributylethoxysilane, tributylacetoxysilane, And their hydrolysis products.

The 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 simultaneously changed to each group, and include an OH group, a hydrolyzable group,
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
At least one of a group and a hydrolyzable group. N2 is an integer of 0 or more. 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, an n-propyl group, an n-butyl group, a t-butyl group, a sec-butyl group, and an n-pentyl. Groups, methoxy group, ethoxy group, chloromethyl group and the like, and the aryl group includes, for example, a phenyl group, a tolyl group, a naphthyl group, an anthranyl group, and the like, and the aralkyl group includes, for example, a benzyl group, Phenethyl group and the like; alkenyl group includes, for example, vinyl group, allyl group, propenyl group and phthenyl group; and acyl group includes, for example, acetyl group, benzoyl group and the like. And alkyl groups, aryl groups, aralkyl groups, alkenyl groups, and acyl groups, such as halogen atoms, nitro groups, cyano groups, and methoxy groups. It may have a substituent.

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

Specific examples of such an organosiloxane include, for example, 1,3-dimethoxy-1,3-dimethyl-1,3-diphenyldisiloxane, 1,5-diethoxy-1,3,5-trimethyl-siloxane. 1,3,5-triphenyltrisiloxane, 1,7-dimethoxy-1,3,3
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]

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[0055]

[0056] And hydrolysis products thereof.
3037 (Methoxy group content 18% by weight, Toshiba Silicon-
Silicone resin available under trade names such as SH6018 (OH equivalent about 400, Toray Silicone Co., Ltd.).

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

Specific examples of the aluminum compound used simultaneously with these silicon compounds include trismethoxyaluminum, trisethoxyethoxyaluminum, trisisopropoxyaluminum, trisphenoxyaluminum, trisparamethylphenoxyaluminum,
Isopropoxydiethoxyaluminum, Trisstopoxyaluminum, Trisacetoxyaluminum, Tristearatealuminum, Trisbutyratealuminum, Trispropionatealuminum, Trisisopropionatealuminum, Trisacetylacetonatealuminum, Tristrifluoroacetylacetate Sodium aluminum, trishexafluoroacetylacetonatoaluminum, trisethylacetoacetatealuminum, trissalicylaldehyde aluminum, trisdiethylmalolatoaluminum, trispropylacetoacetatealuminum, tris Butyl acetoacetate aluminum, aluminum trisdipivaloyl methanate, diacetylacetonato todipivaloyl methanate Aluminum,

[0059]

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[0060]

[0061]

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[0062]

[0063]

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[0064]

[0065]

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[0066]

[0067]

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[0068]

[0069]

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[0070]

[0071]

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[0072]

[0073]

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[0074]

[0075]

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[0076]

[0077]

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[0078]

And the like.

These aluminum compounds may be used in one kind or in a mixture of two or more kinds. The compounding amount thereof is 0.001 to 100% by weight to the epoxy resin.
%, Preferably in the range of 1 to 10%.

If the amount is less than 0.001% by weight, sufficient curing characteristics of the film cannot be obtained.
Exceeding 0% by weight not only increases the cost, but also
It is not preferable because the moisture resistance tends to decrease.

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

The curing temperature in this case is 30 to 200.
° C.

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

[0085] As the aluminum compound used simultaneously with the silicon compound, the aluminum compound used simultaneously with the silicon compound which generates a silanol group by heating as described above can be used as it is.

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

The curing temperature in this case is 0 to 200 ° C.
Is fine.

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

In the resin composition of the present invention, other epoxy resins such as an epoxy resin such as an epi-bis type epoxy resin, limonene diepoxide, vinylcyclohexene diepoxide, and vinylcyclohexene monoepoxide may be used as long as their properties are not impaired. An alicyclic epoxy may be used as a mixture.

[0090]

The thermosetting resin composition of the present invention is a tough cured product having excellent flexibility. By utilizing this feature, the application range of the thermosetting epoxy resin can be extended to fields requiring flexibility. In addition, by using a mixture with another 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 An epoxy resin composition of the general formula II
And n1 = 1 (average) epoxy resin (hereinafter referred to as epoxy resin [A]), n1 = 3 (average) epoxy resin in general formula II (hereinafter expressed as epoxy resin [B]), and general formula An epoxy resin of 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) organosilicon compounds, diphenylsilanediol, diphenyldimethoxysilane) and aniline / boron trifluoride complex were used in the proportions shown in Table 1 to form a cured plate having a thickness of 3 mm. It was made and physical properties were measured. The results are shown in Table 1.

[0093]

Comparative Examples 1-2 As an epoxy resin composition, general formula II
And a complex of a silicon compound and an aluminum compound (as an organoaluminum compound, trisethylacetoacetatoaluminum (TE)
AACA) diphenyldimethylsilane as the organosilicon compound) and an aniline / boron trifluoride complex were blended in the proportions shown in Table 1 to prepare a 3 mm-thick cured plate and to measure its physical properties. The results are shown in Table 1. <Evaluation Method> Curing physical properties were measured at 20 ° C. and 65% RH. The measurement of tensile strength and tensile elongation is JIS
Performed according to K 6911. Tg is a high-performance differential scanning calorimeter (DSC 8230B manufactured by Rigaku Corporation).
It measured using.

Table 1 Example 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 Diphenylsilane di- 1.0 Diphenyldimethoxysilane 0.1 0.1 Aniline / boron trifluoride complex 0.05 0.05 Curing condition Curing temperature (° C) 140 100 25 140 100 Curing time (hour) 5 10 160 5 10 Tg (° C / DSC) 110 10 -20 160 140 140 Tensile strength (kgf / mm ² ) 6.4 1.7 0.3 4.0 4.9 Tensile elongation (%) 10 40 150 23

Claims (3)

(57) [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) [wherein, in the formula (I), Z has the following structure: Embedded image Y ¹ has the following structure Y ² has the following structure R ¹¹ -R ²⁹ , R ^a , and R ^b can be simultaneously replaced with hydrogen or an alkyl group generally containing 1 to 9 carbon atoms, respectively. c represents an integer of 4 to 8, and n1 represents an integer of 1 to 20 . ] 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). Embedded image [N1 represents an integer of 1 to 20; ] 3. The thermosetting resin composition according to claim 1, wherein the cationic polymerization initiator comprises an organosilicon compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom and an organoaluminum compound.