JPS6312487B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a novel method for producing silicone phenolic compounds. [Prior Art] Conventionally, in the field of semiconductor products and electrical equipment, sealing materials and insulating materials have excellent adhesion and adhesion with metal inserts, crack resistance,
There is a strong demand for thermosetting type low thermal stress resins with excellent heat resistance. For these purposes, epoxy resins, urethane resins, addition type imide compounds, etc. have been mainly used. [Problems to be solved by the invention] However, all of these have problems in terms of the balance of adhesion with the metal insert, crack resistance, heat resistance, etc., and the development of a new material system is strongly desired. It was rare. The present invention was conceived in view of the above-mentioned current situation, and an object of the present invention is to improve the adhesion of metal inserts (preventing water from entering from the interface), and to improve the crack resistance (flexibility) of molded cured products. A reactive crosslinking agent (curing agent) for various new thermosetting resins that can provide material compositions with excellent heat resistance and heat resistance.
An object of the present invention is to provide a method for producing a silicone phenolic compound useful as a silicone phenolic compound. [Means for Solving the Problems] To summarize the present invention, the present invention has the following general formula:
(A)： (In the formula, R represents hydrogen or a lower alkyl group) A novolak type phenolic compound having a repeating unit represented by the following general formula (B): (In the formula, R ₁ is the same or different, H, hydroxyl group, methyl group, or phenyl group, Y is a functional group reactive with a phenolic hydroxyl group, X is a number from 0 to 1000) and heated. The following general formula [] characterized by the reaction: The present invention relates to a method for producing a silicone phenol compound containing a characteristic group represented by: In the present invention, the novolak type phenolic compound used as a raw material is, for example, phenol, o, m, p cresol, or p-
Usually obtained by reacting a mono-lower alkyl-substituted phenol such as t-butylphenol with formaldehyde in the presence of an acidic catalyst such as hydrochloric acid or oxalic acid,
What is called a phenolic novolak resin can be used. In addition, examples of the compound represented by the general formula (B) include the general formula []: [In the formula, R ₁ and Y have the same meanings as in the above general formula (B). ] There are compounds represented by dimethylsilanediol, diphenylsilanediol, dimethylsilane, diphenylsilane, etc. Also, the general formula: [In the formula, R ₁ and Y have the same meanings as in the above general formula (B),
k indicates x+1. ] There is a compound represented by
Examples include polymethylhydrosiloxane, such as tetramethyldisiloxane, hexamethyltrisiloxane, 1,5-dihydroxyhexamethyltrisiloxane, 1,3-dihydroxytetramethyldisiloxane, and 1,7-dihydroxyoctamethyltetrasiloxane. The above-mentioned siloxane compounds are commercially available from Chitsuso, Shin-Etsu Chemical, Toray Silicone, GE, etc. Examples of the group Y include well-known hydroxyl groups, lower alkoxy groups, acyloxy groups, halogens, and the like. The silicone phenol compound of the present invention can be easily obtained by simply heating each of the raw materials, but both raw material components are mixed in a solvent (methanol, ethanol, methyl ethyl ketone, benzene, toluene, xylene, acetone, etc.). ,
Cellosolve acetate, Cellosolve acetate acetate, N
- Methylpyrrolidone, dimethylformamide, dimethylacetamide, etc. may be used alone or in combination). Regarding the blending ratio of each raw material, it is preferable to carry out the reaction in the range of group (A)-containing phenolic compound/(B)=1/0.01 to 1.00. Among the obtained silicone phenol compounds, those having a molecular weight of 300 to 50,000 are useful. By the above method, at least one phenolic hydroxyl group in the phenolic compound having the group (A) reacts with (B), and a condensation reaction occurs with elimination of HY. In addition, a reaction between the methylol group in the raw material phenolic compound and (B) and a condensation reaction between (B) occur. The silicone phenolic compound obtained by the method of the present invention ranges from being liquid at room temperature to having a softening point of
It is characterized by having a temperature range of 200℃. The silicone phenolic compound obtained by the present invention can be easily cured by adding an appropriate amount of a conventionally known curing agent (including accelerator) for phenolic resin, such as hexamethylenetetramine, and has excellent electrical properties, heat resistance, and flexibility. , resulting in a cured resin with excellent moisture resistance. It is also effective as a crosslinking agent (curing agent) for thermosetting resins such as epoxy resins, addition-type imide resins, urea resins, urethane resins, and melamine resins. The blending ratio for the thermosetting resin depends on its purpose,
Although it varies depending on the application and is not particularly limited, it is preferable that the reactive functional group of the target thermosetting resin and the hydroxyl group of the silicone phenol compound vary over a considerable range around the stoichiometric ratio. Can be used. These products can be used in a wide range of applications, including varnishes, paints, prepregs, laminates for printed circuit boards, and molding materials including encapsulating materials for coils and semiconductor products (IC, LSI, etc.). By adding a known epoxy compound to the silicone phenol compound of the present invention, a cured product with excellent heat resistance and moldability can be obtained. Examples of the epoxy compound used in the present invention include glycidyl ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexanecarboxylate, vinylcyclohexene dioxide, 4,4'- Di(1,2-epoxyethyl)
Diphenyl ether, 2,2-bis(3,4-epoxycyclohexyl)propane, glycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis-(2,3-epoxycyclopentyl) ether , 2-(3,4-epoxy)
Cyclohexane-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, bis-
(3,4-epoxy-6-methylcyclohexyl)
Adipate, N,N'-m-phenylenebis (4,
Difunctional epoxy compounds such as 5-epoxy-1,2-cyclohexanedicarboximide, p-
Triglycidyl derivative of aminophenol, polyallyl glycidyl ether, 1,3,5-tri(1,2-epoxyethyl)benzene, 2,2',
Tri- or higher functional epoxy compounds such as 4,4'-tetraglycidoxybenzophenone, polyglycidyl ether of phenol formaldehyde novolac resin, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, and brominated epoxy A halogenated epoxy compound such as or a hydantoin epoxy compound is used. Furthermore, the silicone phenol compound of the present invention has the following formula: [In the formula, R ₂ represents H or CH ₃ , and R ₃ represents a divalent organic group. It can also be used in combination with a known bismaleimide compound represented by the following formula, and a cured product with excellent heat resistance can be obtained. As the bismaleimide compound, for example, N,N′-
Ethylene dilemaleimide, N,N'-ethylenebis[2-methylmaleimide], N,N'-trimethylene dimaleimide, N,N'-tetramethylene dimaleimide, N,N'-hexamethylene dimaleimide, N, N'-hexamethylenebis[2-methylmaleimide], N,N'-dodecamethylene dimaleimide, N,N'-m-phenylene dimaleimide,
N,N'---p-phenylene dimaleimide, N,
N'-(oxy-p-phenylene) dimaleimide,
N,N'-(methylene-di-p-phenylene) dimaleimide, N,N'-(methylene-di-p-phenylene)bis[2-methylmaleimide], N,
N-2,4-tolylene dimaleimide, N,N'-
2,6-tolylene dimaleimide, N,N'-m-
Xylylene dimaleimide, N,N'-p-xylylene dimaleimide, N,N'-oxypropylene dimaleimide, N,N'-ethylene bis(oxypropylene maleimide), N,N'-oxydiethylene dimaleimide, etc. , used alone or in combination of two or more. The silicone phenol compound of the present invention can be made into a cured product with excellent heat resistance and moldability by adding a known polyfunctional isocyanate compound. In the present invention, methane diisocyanate, butane-1,
1-diisocyanate, ethane-1,2-diisocyanate, butane-1,2-diisocyanate, transvinylene diisocyanate, propane-1,3-diisocyanate, butane-1,4
-Diisocyanate, 2-butene-1,4-diisocyanate, pentane-1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-1,7-diisocyanate, octane-
1,8-diisocyanate, nonane-1,9-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, ω,ω′-1,3
-dimethylbenzene diisocyanate, ω,
ω'-1,4-dimethylbenzene diisocyanate, ω,ω'-1,3-dimethylcyclohexane diisocyanate, ω,ω'-1,4-dimethylcyclohexane diisocyanate, ω,ω'-1,
4-dimethylnaphthalene diisocyanate, ω,
ω'-1,5-dimethylnaphthalene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate Nylene diisocyanate, 1-
Methylbenzene-2,4-diisocyanate, 1
-Methylbenzene-2,5-diisocyanate,
1-methylbenzene-2,6-diisocyanate, 1-methylbenzene-3,5-diisocyanate, diphenyl ether-4,4'-diisocyanate, diphenyl ether-2,4'-diisocyanate, naphthalene-1,4- Diisocyanate, naphthalene-1,5-diisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-
Dimethylbiphenyl-4,4'-diisocyanate, 2,3'-dimethoxybiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4' -diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate and other bifunctional isocyanate compounds, Tri- or higher functional isocyanate compounds such as polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, tris(4-isocyanate phenyl) thiophosphate, 3,3',4,4'-diphenylmethane tetraisocyanate used. Furthermore, dimers and trimers of these isocyanate compounds can also be used. Various catalysts that are important for improving curability can be added to these resin compositions. Examples of such catalysts include tertiary amines such as tetramethylbutanediamine, tetramethylhexanediamine, triethylenediamine, and dimethylaniline, oxyalkylamines such as dimethylaminoethanol, triethanolamine, and dimethylaminopentanol, and tris(dimethyl There are amines such as (aminomethyl)phenol and N-methylmorpholine. Also, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride,
dodecyltrimethylammonium iodide,
There are quaternary ammonium salts such as trimethyldodecyl ammonium chloride, benzyldimethyltetradecylammonium chloride, benzyldimethylpalmitylammonium chloride, allyldodecyltrimethylammonium bromide, benzyldimethylstearylammonium bromide, stearyltrimethylammonium chloride, and benzyldimethyltetradecylammonium acetate. . 2-ethylimidazole, 2-
Undecylimidazole, 2-heptadecylimidazole, 2-methyl-4-ethylimidazole, 1-butylimidazole, 1-propyl-2
-Methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine-2-methylimidazole , imidazoles such as 1-azine-2-undecylimidazole, triphenylphosphine tetraphenylborate, tetraphenylphosphonium tetraphenylborate, triethylaminetetraphenylborate, N-methylmorpholinetetraphenylborate, pyridine tetraphenylborate enylborate, 2-ethyl-4-methylimidazoletetraphenylborate, 2-ethyl-
Tetraphenylboron salts such as 1,4-dimethylimidazole tetraphenylborate are also useful. In addition, depending on the purpose and use mentioned above,
Various known additives can also be added. For example, inorganic fillers include zircon, silica, fused silica glass, alumina, aluminum hydroxide, glass, calcium silicate, gypsum, calcium carbonate, magnesite, clay, talc, mica, asbestos, lead oxide, and zinc oxide. , titanium white, and molybdenum disulfide. In addition, if necessary, mold release agents such as higher fatty acids and waxes, and coupling agents such as epoxysilane, vinylsilane borane compounds, and alkoxy titanate compounds can be used. Furthermore, flame retardant materials made of antimony, phosphorus compounds, etc. can be used. [Example] The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto. In addition, confirmation of the characteristic group represented by the above general formula is
This was done using an IR spectrum (near 1260 cm ^-1 ). Examples 1 to 5 As a phenolic compound, 100 parts by weight of a novolac-type condensate of phenol and formaldehyde (average molecular weight, 375) was added to a hydroxyl group-terminated polydiphenylsiloxane compound (PS-080: manufactured by Chitsuso Corporation) as a siloxane compound. 5, 10, 20, 30,
Add 40 parts by weight separately to 120℃~180℃
Heat reaction for 2 to 3 hours [(a) in Table 1~
(e)] Five types of silicone phenol compounds were obtained. These IR spectra had a characteristic absorption at 1260 cm ^-1 . Examples 6 to 10 As a phenol compound, 100 parts by weight of a condensate of novolac type phenol and formaldehyde (average molecular weight: 410) was added as a siloxane compound, a methylol group-terminated polydimethylsiloxane compound (PS-197: manufactured by Chitsuso Corporation) 10, 20, 30, 40, 50
Add each part by weight separately and heat at 120 to 180℃ for 1
The reaction was carried out for ~2 hours to obtain five types of silicone phenol compounds (F) to (N) listed in Table 1. These IR spectra had a characteristic absorption at 1258 cm ^-1 . Examples 11-12 100 parts by weight of a condensate of novolac-type orthocresol and formaldehyde (average molecular weight: 450) as a phenolic compound, and polymethylhydrosiloxane (PS-120:
10 and 20 parts by weight (manufactured by Chitsuso Co., Ltd.) were added separately and reacted by heating at 130 to 200°C for 1 to 2 hours.
Two types of silicone phenol compounds (L) and (E) described above were obtained. These IR spectra had a characteristic absorption at 1260 cm ^-1 . Examples 13 to 16 100 parts by weight of a condensate of novolac-type phenol and formaldehyde (average molecular weight: 450) as a phenolic compound, and dimethylpolysiloxane-based silicone oil KF-96 (Shin-Etsu) as a siloxane compound. (manufactured by Kagakusha), KF-54
(manufactured by Shin-Etsu Chemical Co., Ltd.) and heated to react at 130 to 200°C for about 1 to 2 hours to form four types of silicone phenol compounds (W) to (T) listed in Table 1. I got it. A characteristic absorption was slightly observed at 1257 cm ^-1 in these IR spectra.

[Table] Example 17 (Application example) To 100 parts by weight of each of the silicone phenol compounds (A) to (E) obtained in Examples 1 to 5, 7 parts by weight of hexamethylenetetramine and stearin as a mold release agent were added. 1 part by weight of zinc oxide, 180 parts by weight of silica powder, 90 parts by weight of clay powder as a filler, 1 part by weight of epoxy silane KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, and 1 part by weight of carbon black as a coloring agent. After blending, the mixture was roll-kneaded at 80 to 95°C for 10 minutes and then cooled to obtain a molding material composition. Next, transfer molding was performed at 150 to 160°C for 2 minutes to prepare specimens for measuring each characteristic. The bending strength of the above cured product is 1000-1200Kg/at room temperature.
^cm2 , the retention rate of bending strength after 30 days at 180°C was 90 to 100% in all cases. In addition, the water absorption rate of the cured product is 0.5 to 0.5 when soaked in water for 24 hours.
It was 0.6%. Example 18 (Application example) Silicone phenol compounds (F) to (F) obtained in Examples 6 to 16 were added to 70 parts by weight of novolac type epoxy DEN-438 as an epoxy resin.
(manufactured by Dow Chemical Company) 100 parts by weight, 1 part by weight of Hoechstwax E as a mold release agent, 290 parts by weight of quartz powder as a filler, 250 parts by weight of fused silica glass powder,
2 parts by weight of triethylamine tetraphenylborate as a curing accelerator, 2 parts by weight of epoxysilane KBM303 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, and 1 part by weight of carbon black as a coloring agent were mixed, and the mixture was rolled at 60 to 70°C for 10 minutes. After kneading, the mixture was cooled and pulverized to obtain a molding material composition. Next, using these molding powders, (a) the glass transition point and Young's modulus of the molded product (after curing), (b) heat cycle test,
(c) A clamping stress measurement test, and (d) a high temperature volume resistivity test of the molded product (after curing). However, the molding conditions were 180°C for 2 minutes, followed by post-curing at 180°C for 6 hours. Heat cycle test was performed on 5x5mm MOS type LSI
Mounted products (20 pieces each) were prepared and repeatedly subjected to a thermal shock test in which they were immersed in an oil bath at 150°C for 2 minutes and then immediately immersed in liquid nitrogen at -196°C for 2 minutes. Tightening stress was measured by modeling the stress generated when transfer molding was performed using the molding material. The model was made by pasting a strain gauge on the inside of a steel cylinder (outside diameter 10φ, thickness 0.3mm, height 20mm) and molding the outside with resin. The thickness of the resin is 10mm. After molding, the stress generated in the circumferential direction was determined from the amount of deformation of the steel. In addition, the glass transition temperature, which is a criterion for determining heat resistance, is ASTM D-
Measured according to 696. The results are shown in Table 2 together with comparative examples.

[Table] Examples 19 to 21 (Application examples) Silicone phenol compounds obtained in Examples
For 70 parts by weight of each of (c), (g), and (f), 100 parts by weight of tolylene diisocyanate (TDI manufactured by Sumitomo Bayer) as an isocyanate compound, 1 part by weight of stearic acid as a mold release agent, and 1 part by weight of stearic acid as a filler. quartz powder
290 parts by weight, 250 parts by weight of fused silica glass powder, 3 parts by weight of hexamethylenetetramine as a hardening accelerator,
Epoxysilane KBM as a coupling agent
303 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 1 part by weight of carbon black as a coloring agent were blended and kneaded with rolls at 60 to 70°C for 10 minutes to obtain a molding material composition. Next, using these molding materials, various cured products (test pieces) were created in the same manner as in Example 18 by molding at 170° C. for 3 minutes. The results are listed in Table 3. Examples 22 to 24 (Application examples) Silicone phenol compounds obtained in Examples
(C), (G), and (F) are added to 70 parts by weight each as an addition type polyimide resin.
100 parts by weight of dimaleimide (phenylene), 1 part by weight of stearic acid as a mold release agent, 290 parts by weight of quartz powder as a filler, 250 parts by weight of fused silica powder, 3 parts by weight of hexamethylenetetramine as a hardening accelerator, and epoxy as a coupling agent. Silane KBM
-303 (manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by weight and 1 part by weight of carbon black as a coloring agent were blended, Examples 19 to 21
The mixture was kneaded under the same conditions as above to prepare specimens for various property tests. The results are listed in Table 3.

〔Effect of the invention〕

As is clear from the above examples, the use of the silicone phenol compound of the present invention has the remarkable effect of providing a cured resin product with excellent heat resistance and crack resistance.

Claims (1)

[Claims] 1 The following general formula (A): (In the formula, R represents hydrogen or a lower alkyl group) A novolak type phenolic compound having a repeating unit represented by the following general formula (B): (In the formula, R ₁ is the same or different, H, hydroxyl group, methyl group, or phenyl group, Y is a functional group reactive with a phenolic hydroxyl group, X is a number from 0 to 1000) and heated. The following general formula [] characterized by the reaction: A method for producing a silicone phenol compound containing a characteristic group represented by the formula [wherein X, R and R ₁ have the same meanings as in formulas (A) and (B) above].