JPH0460143B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel and useful highly heat-resistant resin composition, and more particularly, the present invention relates to a resin composition containing a specific ladder-type polysiloxane, a silanol compound, and a curing catalyst as essential components. In particular, the object of the present invention is to use a ladder type polysiloxane having an aryl group and not having a so-called hydrolyzable group such as an alkoxysilyl group and a silanol group.
Suitable for use as a coating liquid for coating film forming,
In particular, it is an object of the present invention to provide a resin composition for obtaining a coating film with good adhesion to a substrate. Among this kind of ladder-type polysiloxanes having acyl groups (see the following formula), ladder-type polysiloxanes containing especially phenyl groups as organic groups have already been described in U.S. Pat.

[However, in the formula, R ¹ represents a C ₁ to _{C 18} alkyl group, aryl group, alkenyl group, or alkynyl group, and X represents a C ₁ to _{C 4} alkoxy group or a halogen atom. ]

and/or the general formula Si(OR ² ) ₄ [] [However, R ² in the formula represents an alkyl group consisting of C ₁ to _{C 4} . ] It refers to a hydrolyzed product of the silane compound shown by the above formula, which has a molecular weight that is soluble in a solvent. Among the silanol compounds (B), preferred ones are those represented by the above formula [], A compound in which R ¹ directly bonded to a silicon atom (Si) is a C ₁ to C ₄ alkyl group, and particularly preferred is a compound in which R ¹ is a C 1 to C 4 alkyl group.
is a compound with a methyl group. The silanol compound (B) is, for example, R ¹ SiX ₃
or Si(OR ² ) ₄ in an organic solvent in the presence of an acid or a base. The mixing ratio of the aryl group-containing ladder type polysiloxane (A) and the silanol compound (B) can be appropriately selected depending on the purpose and use. If the proportion of the silanol compound (B) increases, for example when used as a coating liquid composition, the adhesion between the coating film and the substrate will increase, but the heat resistance will deteriorate; When the proportion of (B) decreases, heat resistance becomes good, but the adhesion between the coating film and the substrate inevitably deteriorates. Therefore, the mixing ratio of both components (A) and (B) should be determined by considering the balance between adhesion, heat resistance, and both properties. A particularly preferred mixing ratio of component (A) to component (B) is within the range of 8:2 to 3:7 by weight. Furthermore, typical curing catalysts (C) include 1,8-diazabicyclo-[5,4,0]
-7-undecene, 1,4-diazabicyclo-
[2,2,2]-octane, triethylamine, ethylenediamine, triethanolamine, n-butylamine, di-n-butylamine or n-
Various amines such as hexylamine; iron, lead,
various metal organic carboxylates such as tin, antimony, cadmium, titanium, calcium, bismuth, zirconium, sodium, potassium, cesium or magnesium; various metal hydroxides such as lithium, sodium or potassium; benzyltrimethylammonium hydroxide or Various quaternary ammonium salts such as tetramethylammonium hydroxide; dibutyltin diacetate, dibutyltin dioctate,
Various metal-containing compounds such as dibutyltin dilaurate, dibutyltin arate or...butyltin oxide; or various acidic compounds such as p-toluenesulfonic acid, trichloroacetic acid or phosphoric acid. The amount of the curing catalyst (C) used is as follows:
Based on the total weight of and silanol compound (B)
A range of 0.001 to 10% is appropriate; if it is less than this range, it will be difficult to obtain a coating film with good adhesion when used as a coating liquid composition, and conversely, if it is less than this range, it will be difficult to obtain a coating film with good adhesion. If the amount is too large, the coating film becomes too hard and cracks are more likely to occur, which is undesirable. Particularly preferably, it is within a range of 0.01 to 5% based on the total weight of both components (A) and (B). In particular, when using a basic curing catalyst, it is effective to add acetic acid as a curing inhibitor, but the amount of such curing inhibitor used is 1 part by weight of this type of basic curing catalyst. A suitable proportion is 100 parts by weight, preferably 5 to 50 parts by weight. In addition, the solvent used in preparing the composition of the present invention, for example, for preparing a coating composition, can dissolve both the aryl group-containing ladder hard polysiloxane (A) and the silanol compound (B). Any solvent may be used as long as it can be used, and various known and commonly used solvents such as alcohols, esters, ketones, ethers, aromatic hydrocarbons, halogenated hydrocarbons, and non-aqueous polar solvents can be used as is. These may be used alone or in combination of two or more. The thus obtained composition of the present invention not only has improved adhesion to substrates such as glass and metal, compared to coating films obtained only from conventional aryl group-containing ladder-type polysiloxanes. It also has the characteristics of improved solvent resistance and excellent heat resistance. Therefore, the composition of the present invention can be used as a heat-resistant insulating film for electronic devices such as a heat-resistant interlayer dielectric film such as an IC or LSI, and when a coating film is formed from the composition of the present invention, it can be used as a colorless and transparent film. It can be used for various purposes such as coating on glass substrates, forming coatings on transparent electrode substrates of liquid crystal assemblies, and forming coatings to protect the surfaces of solar system equipment and equipment. be sent. In particular, when the composition of the present invention is used as a coating liquid composition, the coating film curing temperature is 50 to 200°C.
It is appropriate that the curing time be within the range shown in FIG. Particularly preferably, the temperature is within the range of 80 to 150°C. Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following, all parts and percentages are based on weight unless otherwise specified. Example 1 1 part of a phenyl group-containing ladder polysiloxane with w of 5.5×10 ⁵ , 0.5 part of a hydrolysis product of methyltriethoxysilane with w of 2000, 1,
0.015 parts of 8-diazabicyclo-[5,4,0]-7-undecene, 0.12 parts of acetic acid, and 11 parts of tetrahydrofuran were mixed to obtain the desired resin composition. Next, this resin composition was applied as a coating solution onto a glass substrate using a bar coater, and after evaporating the solvent tetrahydrofuran, it was applied using a hot air dryer.
The mixture was heated at 150° C. for 1 hour to obtain a colorless and transparent cured coating film with a thickness of 5 μm. Thereafter, the adhesion (checkerboard test), solvent resistance (rubbing test), and thermal decomposition initiation temperature in a nitrogen atmosphere were investigated for this coating film, and the results are summarized in Table 1. Examples 2 to 4 Target resin compositions were obtained in the same manner as in Example 1, except that the composition ratios were changed to those shown in Table 1, and then each resin composition was used as a coating liquid. A colorless and transparent cured coating film having a film thickness of 5 μm was obtained. The performance of each coating film was then evaluated and the results are summarized in the same table. Example 5 Part of a phenyl group-containing ladder-type polysiloxane with a w of 5.5×10 ⁵ and a hydrolysis product of tetraethyl silicate with a w of 1000, respectively.
The target resin composition was obtained in the same manner as in Example 1, except that 0.3 parts of the resin was used. Next, a colorless and transparent cured coating film having a thickness of 5 μm was obtained in the same manner as in Example 1 except that this resin composition was used as a coating solution. Table 1 summarizes the locations where the performance of this coating film was evaluated. Example 6 1,8-diazabicyclo- as a curing catalyst
A target resin composition was obtained in the same manner as in Example 5, except that the same amount of triethylamine was used instead of [5,4,0]-7-undecene.
Next, a colorless and transparent cured coating film having a film thickness of 5 μm was obtained in the same manner as in Example 1, except that the resin composition thus obtained was used as a coating liquid. Table 1 summarizes the areas where the performance of this coating film was evaluated. Comparative Example 1 Only a 10% tetrahydrofuran solution of phenyl group-containing ladder type polysiloxane with w of 5.5×10 ⁵ was used, and heating conditions using a hot air dryer were changed.
A control resin composition was obtained in the same manner as in Example 1, except that the temperature was 150°C for 30 minutes, and then the film thickness was determined in the same manner as in Example 1, except that this resin composition was used as a coating solution. A colorless and transparent control coating film was obtained by adjusting the thickness to 5 μm. Thereafter, the performance of this coating film was also evaluated, and the results are shown in Table 1. Comparative Example 2 Except that no silanol compound was used and the amount of tetrahydrofuran used was 9 parts,
A control resin composition was obtained in the same manner as in Example 1. Next, a colorless and transparent coating film having a thickness of 5 μm was obtained in the same manner as in Example 1, except that this resin composition was used as a coating liquid. Thereafter, the performance of this control coating was also evaluated. The results are summarized in Table 1. Examples 7 to 9 Target resin compositions were obtained in the same manner as in Example 1, except that the composition ratios were changed as shown in Table 1, and then each resin composition was used as a coating liquid. A colorless and transparent cured coating film having a film thickness of 5 μm was obtained. The performance of each coating film was then evaluated and is summarized in the same table.

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Claims (1)

[Claims] 1. Contains (A) an aryl group as an essential component,
A highly heat-resistant resin composition, further comprising a ladder-type polysiloxane having neither a hydrolyzable group nor a silanol group, (B) a silanol compound, and (C) a curing catalyst. 2 The silanol compound (B) described above has the general formula R ¹ SiX ₃ [] [However, R ¹ in the formula is an alkyl group, an aryl group, an alkenyl group, or an alkynyl group having 1 to 18 carbon atoms, X represents an alkoxyl group having 1 to 4 carbon atoms or a halogen atom. ] The composition according to claim 1, which is a hydrolysis product of a compound represented by the following. 3 The above-mentioned silanol compound (B) has the general formula Si(OR ² ) ₄ [] [However, R ² in the formula represents an alkyl group having 1 to 4 carbon atoms. ] The composition according to claim 1, which is a hydrolysis product of a compound represented by the following. 4 The above-mentioned silanol compound (B) has the general formula R ¹ SiX ³ [] [However, R ¹ in the formula is an alkyl group, an aryl group, an alkenyl group, or an alkynyl group having 1 to 18 carbon atoms, X represents an alkoxyl group having 1 to 4 carbon atoms or a halogen atom. ] A hydrolysis product of a compound represented by the general formula Si(OR ² ) ₄ [] [However, R ² in the formula represents an alkyl group having 1 to 4 carbon atoms. ] The composition according to claim 1, which is a mixture of a compound represented by the above with a hydrolysis product.