JP2000344895A - Production of curable resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin which gives a cured item excellent in softness and resistances to heat and moisture by subjecting a compound having (meth)allyl groups and a silicone compound having Si-H groups to addition reaction. SOLUTION: Because of the good compatibility with and the smoothness in addition reaction with a silicone compound (B) having Si-H groups, tris(2- propenyl) isocyanurate is preferable as the compound (A) having (meth)allyl groups. A silicone compound having Si-H groups at the silicone chain terminals is preferable as compound B, since such a compound has a good reactivity with compound A; compound B having Si-H groups at both the molecular terminals, e.g. a compound represented by the formula, is preferable, since a cured item having especially good properties is obtained. In the formula, R2 and R3 are each (cyclo)alkyl or aryl; R1 and R4 are each R2, alkoxy, or aryloxy; and n is 0-100. This resin is excellent in compatibility and copolymerizability with a maleimide compound and gives a low-permittivity cured item.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a curable resin having a silicone chain. The curable resin obtained by the production method of the present invention has good curability and gives a cured product having excellent heat resistance, moisture resistance, and flexibility, and thus is useful as a material for printed wiring boards, semiconductor packages, and the like.

[0002]

2. Description of the Related Art As a curable resin having a silicone chain, a compound having two or more acryloyl groups or methacryloyl groups (hereinafter, both of which are referred to as (meth) acryloyl groups) (hereinafter, polyfunctional (meth) acrylate). ) And a silicone compound having two or more Si-H groups are known to be produced (JP-A-10-158404). However, a curable resin synthesized by the production method described in the above publication, that is, a silicone resin having a (meth) acryloyl group,
Heat resistance, moisture resistance, gives a cured product excellent in flexibility, but depending on the conditions may not be able to obtain a preferred cured product,
The use is restricted depending on the application. For example, a compound having a maleimide group (hereinafter, referred to as a maleimide compound) has heat resistance and a low dielectric constant, so that it is used as a material for a printed wiring board, a semiconductor package, or the like, but has poor flexibility. Even if the silicone resin having the (meth) acryloyl group is mixed and cured for the purpose of improving flexibility while maintaining heat resistance,
The features of both may not be exhibited well.

[0003]

An object of the present invention is to provide a method for producing a curable resin having a silicone chain, which has good copolymerizability with a maleimide compound.

[0004]

Means for Solving the Problems The present inventors have developed a curable resin produced by an addition reaction of a compound having two or more allyl groups or methallyl groups and a silicone compound having two or more Si—H groups. The inventors have found that the above problems can be solved and completed the present invention.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In addition, in this specification, allyl and / or methallyl are represented as (meth) allyl. As the compound having two or more (meth) allyl groups in the present invention (hereinafter, referred to as a polyfunctional (meth) allyl compound), 1,1,1,3,3,3
3-hexafluoro-2,2-bis [4- (2-propenyloxy) phenyl] propane, 1,1,1,3
3,3-hexafluoro-2,2-bis [4- (2-methyl-2-propenyloxy) phenyl] propane,
1,1,1-tris [4- (2-propenyloxy) phenyl] ethane, 1,1,1-tris [4- (2-methyl-2-propenyloxy) phenyl] ethane, 1,1
-Bis [4- (2-propenyloxy) phenyl] ethylbenzene, 1,1-bis [4- (2-propenyloxy) phenyl] cyclohexane, 1,1-bis [4-
(2-methyl-2-propenyloxy) phenyl] ethylbenzene, 1,1-bis [4- (2-methyl-2-propenyloxy) phenyl] cyclohexane, 1,2,2
4-tris (2-propenyloxy) benzene, 1,
2,4-tris (2-methyl-2-propenyloxy)
Benzene, 1,2-bis (2-propenyloxy) anthraquinone, 1,2-bis (2-propenyloxy) naphthalene, 1,2-bis (2-methyl-2-propenyloxy) anthraquinone, 1,2-bis (2-methyl-
2-propenyloxy) naphthalene, 1,4-bis (2
-Propenyloxy) anthraquinone, 1,4-bis (2-propenyloxy) naphthalene, 1,4-bis (2-propenyloxy) benzene, 1,4-bis (2
-Methyl-2-propenyloxy) anthraquinone,
1,4-bis (2-methyl-2-propenyloxy) naphthalene, 1,4-bis (2-methyl-2-propenyloxy) benzene, 1,5-bis (2-propenyloxy) anthraquinone, 1,5 -Bis (2-propenyloxy) naphthalene, 1,5-bis (2-methyl-2-propenyloxy) anthraquinone, 1,5-bis (2-
Methyl-2-propenyloxy) naphthalene, 1,6-
Bis (2-propenyloxy) naphthalene, 1,6-bis (2-methyl-2-propenyloxy) naphthalene,
1,8-bis (2-propenyloxy) anthraquinone, 1,8-bis (2-methyl-2-propenyloxy) anthraquinone, 1- [1-methyl-1- (4-
(2-methyl-2-propenyloxy) phenyl) ethyl] -4- [1,1-bis (4- (2-methyl-2-propenyloxy) phenyl) ethyl] benzene, 2,
2'-bis (2-propenyloxy) azobenzene.
2,2'-bis (2-methyl-2-propenyloxy)
Azobenzene. 2,2′-bis [4- (2-propenyloxy) phenyl] propane, 2,2′-bis [4-
(2-methyl-2-propenyloxy) phenyl] propane, 2,2-bis [3-methyl-4- (2-propenyloxy) phenyl] propane, 2,2-bis [3-methyl-4- (2 -Methyl-2-propenyloxy) phenyl] propane, 2,2′-bis (2-propenyloxy) biphenyl, 2,2′-bis (2-methyl-2-propenyloxy) biphenyl, 2,2′-bis [4-
(2-propenyloxy) phenyl] propane, 2,
2′-bis [4- (2-methyl-2-propenyloxy) phenyl] propane, 2,3-bis (2-propenyloxy) naphthalene, 2,3-bis (2-propenyloxy) benzaldehyde, 2,3 -Bis (2-methyl-2-propenyloxy) naphthalene, 2,3-bis (2-methyl-2-propenyloxy) benzaldehyde, 2,4-bis (2-propenyloxy) acetophenone, 2,4-bis ( 2-propenyloxy) benzaldehyde, 2,4-bis (2-methyl-2-propenyloxy) acetophenone, 2,4-bis (2-methyl-
2-propenyloxy) benzaldehyde, 2,5-bis (2-propenyloxy) acetophenone, 2,5-
Bis (2-propenyloxy) benzaldehyde, 2,
5-bis (2-methyl-2-propenyloxy) acetophenone, 2,5-bis (2-methyl-2-propenyloxy) benzaldehyde, 2,6-bis (2-propenyloxy) acetophenone, 2,6-bis (2-propenyloxy) naphthalene, 2,6-bis (2-methyl-2-propenyloxy) acetophenone, 2,6-bis (2-methyl-2-propenyloxy) naphthalene,
2,7-bis (2-propenyloxy) naphthalene,
2,7-bis (2-methyl-2-propenyloxy) naphthalene, 2- (2-propenyloxy) phenyl 4
-(2-propenyloxy) phenyl ketone, 2-
(2-methyl-2-propenyloxy) phenyl 4-
(2-methyl-2-propenyloxy) phenyl ketone, 3,3-bis [4- (2-propenyloxy) phenyl] phthalide, 3,3-bis [4- (2-methyl-2)
-Propenyloxy) phenyl] phthalide, 3,4-bis (2-propenyloxy) benzaldehyde, 3,4
-Bis (2-methyl-2-propenyloxy) benzaldehyde, 3,5-bis (2-propenyloxy) acetophenone, 3,5-bis (2-methyl-2-propenyloxy) acetophenone, 4,4'-bis (2-propenyloxy) biphenyl, 4,4′-bis (2-methyl-2-propenyloxy) biphenyl, 9,9-bis [4- (2-propenyloxy) phenyl] fluorene, 9,9-bis [ 4- (2-methyl-2-propenyloxy) phenyl] fluorene, tris (2-propenyl) isocyanurate, tris (2-methyl-2-propenyl) isocyanurate, tris (2-propenyl)
Cyanurate, tris (2-methyl-2-propenyl)
Cyanurate, tris [4- (2-propenyloxy)
Phenyl] methane, tris [4- (2-methyl-2-propenyloxy) phenyl] methane, bis [2- (2-
Propenyloxy) phenyl] ketone, bis [2- (2
-Propenyloxy) phenyl] methane, bis [2-
(2-methyl-2-propenyloxy) phenyl] ketone, bis [2- (2-methyl-2-propenyloxy)
Phenyl] methane, bis [4- (2-propenyloxy) phenyl] ether, bis [4- (2-propenyloxy) phenyl] ketone, bis [4- (2-propenyloxy) phenyl] sulfide, bis [4- (2-propenyloxy) phenyl] sulfoxide, bis [4-
(2-propenyloxy) phenyl] sulfone, bis [4- (2-propenyloxy) phenyl] methane, bis [4- (2-methyl-2-propenyloxy) phenyl] ether, bis [4- (2-methyl) -2-propenyloxy) phenyl] ketone, bis [4- (2-methyl-2-propenyloxy) phenyl] sulfide, bis [4- (2-methyl-2-propenyloxy) phenyl] sulfoxide, bis [4- (2-methyl-2-propenyloxy) phenyl] sulfone, bis [4- (2-
Methyl-2-propenyloxy) phenyl] methane and the like. In addition to these, a (meth) allyl group is
Any compound having at least one compound can be used without any particular limitation, but a compound having no hydroxyl group in the molecule is a preferable compound because the obtained curable resin has good stability.

Among the above polyfunctional (meth) allyl compounds,
Tris (2-propenyl) isocyanurate is Si-
It is particularly preferable because it has good compatibility with the silicone compound having two or more H groups and can smoothly carry out the addition reaction. The silicone compound having two or more Si-H groups in the present invention (hereinafter, simply referred to as a silicone compound) has two or more Si-H groups in the middle or at the end of the silicone chain, but has at the terminal. Is preferred because of its good reactivity with the polyfunctional (meth) allyl compound. Silicone compounds having Si-H groups at both ends of the silicone chain are more preferred because the properties of the resulting cured product are particularly good. Examples of preferred silicone compounds having Si-H groups at both ends of the silicone chain in the present invention are shown in Formula 1 below.

[0007]

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In formula 1, R ¹ and R ⁴ are each an alkoxy group, aryloxy group, alkyl group, cycloalkyl group or aryl group, and R ² and R ³ are each an alkyl group, cycloalkyl group or aryl group. ,
n is a positive number from 0 to 100. R ¹ and R ^{4 in the} above formula 1
Examples of the alkoxy group in are methoxy, ethoxy, n- and i-propoxy, n-, i- and t-
Examples include a butoxy group, and examples of the aryloxy group include a phenoxy group. Examples of the alkyl group include a methyl group, an ethyl group, n- and i-propyl groups, n-, i- and t-butyl groups, and examples of the cycloalkyl group include a cyclohexyl group and the like. Examples include a phenyl group. R ¹ and R ⁴ may be the same group or different groups. Further, the silicone compound represented by the structural formula shown in Formula 1 has two R ¹ and R ⁴ in one molecule, and these may be the same group or different groups.

The alkyl group, cycloalkyl group and aryl group in R ² and R ³ in the above formula 1 are the same as those exemplified in the description of R ¹ and R ⁴ , respectively. R ² and R ³ may be the same group or different groups. Also be a n-number of R ² is also different for two or more be all the same radical groups contained in one molecule is the same for R ^3.

The silicone compound represented by the above formula 1 is
When R ¹ or R ⁴ is an alkoxy group or an aryloxy group, it is preferable because the curable resin produced from the silicone compound tends to have good compatibility with the (meth) allyl compound described later. is there. A silicone compound in which both R ¹ and R ⁴ are an alkoxy group or an aryloxy group is more preferable because the compatibility of the curable resin becomes particularly good. Further, a silicone compound in which two R ¹ and two R ⁴ present in one molecule are the same group is preferable because of easy synthesis, and a silicone compound in which R ¹ and R ⁴ are all the same group is more preferable for the same reason. . Incidentally, silicone compounds in which R ¹ and R ⁴ are ethoxy groups are particularly preferred because of their low toxicity.

The silicone compound in which R ² and R ³ are a methyl group or an ethyl group can be produced from inexpensive raw materials, and the cured product described below has particularly good releasability, surface lubricity and water / oil repellency. And a silicone compound in which R ² and R ³ are all methyl groups is more preferable for the same reason.

In the above formula 1, n is an integer from 0 to 100. When n exceeds 100, the reaction does not proceed smoothly due to insufficient compatibility of the silicone compound with the polyfunctional (meth) allyl compound. The compatibility with the compound may be low. Silicone compounds having n of 50 or less are preferred because of the good compatibility described above, and silicone compounds of 30 or less are more preferred. Further, n is preferably 1 or more, and the obtained cured product is particularly preferable because of its excellent releasability, surface lubricity and water / oil repellency, and more preferably 3 or more silicone compounds.

In the present invention, the silicone compound and the polyfunctional (meth) allyl compound are preferably reacted in a molar ratio of 1: 1 to 5, and preferably in a molar ratio of 1: 1.5 to 4.5. Is more preferred. The reason for this is that if the amount of the polyfunctional (meth) allyl compound is too small, gelation tends to occur, and if the amount is too large, the curable resin after the reaction tends to undergo layer separation.

In the addition reaction of the present invention, a method using a Group VIII metal compound as a catalyst is a preferable method because the reaction proceeds smoothly. Examples of Group 8 metal compounds include simple substances of Group 8 metals such as cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum;
Examples include an organic metal complex, a metal salt, and a metal oxide.
Of these, simple platinum metals, organometallic complexes, metal salts and metal oxides are preferred, and organic platinum complexes are particularly preferred, for reasons such as high catalytic activity and ease of handling. This catalyst is preferably used in an amount of 5 to 1000 ppm by weight, more preferably 15 to 500 ppm by weight, based on the total amount of the silicone compound and the unsaturated compound. The reason is that if the amount of the catalyst used is too small, the reaction is not completed, and the curable resin may have insufficient curability.If the amount is too large, the storage stability of the obtained curable resin may be insufficient. This is because it may be sufficient.

Illustrating other reaction conditions of the present invention,
The preferred reaction temperature is 20-90 ° C, and the preferred reaction time is 2-60 hours. An addition reaction is performed using a compound having three allyl groups as a polyfunctional (meth) allyl compound and using a silicone compound represented by the structural formula shown in the above formula 1 as a silicone compound having two or more Si-H groups. Structural formulas of the main components of the curable resin which are considered to be formed in the above case are schematically illustrated in the following formulas 2 and 3.

[0016]

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R ¹ , R ² , R ³ , R ⁴ in the formulas 2 and 3
And n each have the same meaning as described in Formula 1, and Z is a trivalent organic group. The curable resins represented by the schematic structural formulas shown in Formulas 2 and 3 have one and two skeletons derived from a silicone compound as a structural unit, respectively. In some cases, there can be three or more. The curable resin obtained by the production method of the present invention, in particular, the curable resin having one or more (meth) allyl groups at both ends can be easily cured by heat, ultraviolet rays, electron beams and the like. The curable resin of the present invention provides a cured product having excellent releasability, surface lubricity, water repellency and oil repellency. Further, the curable resin of the present invention has good compatibility and copolymerizability with a maleimide compound, and a cured product obtained by curing a mixture of both has heat resistance, a low dielectric constant,
Moreover, it had flexibility.

The curable resin may be subjected to curing as a curable resin composition in which a compound having a (meth) allyl group other than the curable resin is mixed according to the purpose. As the compound having a (meth) allyl group other than the curable resin, the same as the above-mentioned (meth) allyl compound can be used. Of these, only one kind may be used, or two or more kinds may be used in combination.

The method for curing the curable resin composition comprising the curable resin produced according to the present invention is not particularly limited, and known means such as heat curing, ultraviolet curing and electron beam curing may be applied. Can be. The curable resin composition provided a cured product having excellent releasability, surface lubricity, and water / oil repellency. Further, the curable resin composition has good compatibility and copolymerizability with a maleimide compound, and a cured product obtained by curing a mixture of both has heat resistance, low dielectric constant, and flexibility. I had one.

[0020]

The present invention will now be described more specifically with reference to examples and comparative examples. In this specification, the molecular weight is GPC
(Gel Permeation Chromatograph) means the number average molecular weight in terms of polystyrene. In addition,
The present invention is not limited by the following examples.

(Synthesis Example) This synthesis example is an example of producing a silicone compound which is a raw material of a curable resin. Α, ω-dihydroxypolydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,840) 25 in a 500 ml four-necked flask equipped with a stirrer, thermometer and cooler
After charging 2.12 g (0.14 mol) and degassing in vacuo, the inside of the system was replaced with nitrogen. While heating the content to 60 ° C, 56.57 g (0.34 mol) of triethoxysilane (trade name “TRIS” manufactured by Toagosei Co., Ltd.) was added, and the mixture was stirred and reacted while maintaining the system at 60 ° C. Proceeded. The progress of the reaction was followed by gas chromatography. After 6 hours, it was confirmed that the composition ratio of the raw material triethoxysilane and the by-produced ethanol had not changed, and the reaction was terminated. Excess triethoxysilane and by-produced ethanol were removed from the resulting reaction solution under heating and reduced pressure (60 to 70 ° C, 2 to 3 mmHg) to obtain a colorless and transparent viscous liquid. The obtained substance was identified as 2,20 in the IR chart.
It had a peak near 0 cm ^-1 indicating the presence of a hydrogen atom bonded to the terminal silicon. This substance also
3.8 ppm peak in the NMR chart (derived from a hydrogen atom (Si—OCH ₂ —) bonded to a carbon atom adjacent to oxygen of an ethoxy group bonded to the terminal silicon)
And the peak area ratio of the 4.7 ppm peak (derived from the hydrogen atom (Si-H) bonded to the terminal silicon),
It was found that the ratio of the number of ethoxy groups bonded to the terminal silicon to the number of hydrogen atoms was 2: 1. Based on the above considerations,
In the silicone compound obtained in this synthesis example, both R ¹ and R ⁴ in the above formula 1 are ethoxy groups, both R ² and R ³ are methyl groups, n is about 25, It was found that the compound had Si-H groups at both ends.

Example 1 A curable resin was produced by reacting the silicone compound obtained in the synthesis example with tris (2-propenyl) isocyanurate. 104 g (50 mmol) of the silicone compound obtained in the synthesis example and 20 g (80 mmol) of tris (2-propenyl) isocyanurate were charged into a 300-ml reactor equipped with a stirrer, a thermometer, and a cooler. Was replaced with nitrogen. After the temperature of the system was raised to 65 ° C., 150 μl of a 0.067 M ethanol solution of chloroplatinic acid was charged, and the mixture was stirred and reacted for 30 hours while maintaining the system at 65 ° C. to obtain a yellow transparent product. From the results of GPC analysis, it was found that the silicone resin containing an allyl group and unreacted tris (2-propenyl) isocyanurate were contained at a weight ratio of 89:11, respectively. The main reaction which seems to be occurring in Example 1 is represented by the following formula 4.

[0023]

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[0024]

The curable resin having a silicone chain obtained by the production method of the present invention gives a cured product excellent in heat resistance, moisture resistance, flexibility and the like. Further, the curable resin has a good curability when mixed with a maleimide compound, and the cured product has particularly excellent heat resistance, moisture resistance, flexibility and the like. The curable resin of the present invention having the above-mentioned features is useful as a printed wiring board, a semiconductor package material and the like.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kaoru Kimura 1-1, Funami-cho, Minato-ku, Nagoya-shi, Aichi F-term in Nagoya Research Institute, Toagosei Co., Ltd. 4J035 BA02 CA021 CA13M CA22M FB01 LA03 LB02 LB03

Claims (1)

[Claims] 1. A method for producing a curable resin, comprising producing an addition-reacted compound having two or more allyl groups or methallyl groups and a silicone compound having two or more Si—H groups.