JPWO2017183259A1 - Silicon-containing curable composition and cured product thereof - Google Patents

Abstract

As the component (A), a compound having a carbon-carbon double bond having reactivity with the SiH group, as the component (B), a siloxane compound having an SiH group, and as the component (C), the following general formula (1) The silicon-containing curable composition characterized by containing a filler as a silane compound and (D) component represented. (In the formula, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A represents an alkanediyl group having 1 to 10 carbon atoms, and k represents a number of 2 or 3).

Description

  The present invention relates to a silicon-containing curable composition and a cured product obtained by curing the same. The silicon-containing curable composition of the present invention and the cured product thereof are useful for materials for semiconductors, particularly for packages such as LEDs and lead frames.

Various studies have been made on silicon-containing compounds, and polysiloxane compounds have been used for a long time as represented by silicone resins in industry. However, although the silicone resin is excellent in heat resistance and flexibility, its use is restricted due to contamination problems in the manufacturing process of the electronic member and the like because there are many outgas components (volatile components).
In recent years, in the field of electronic information, with the development of technology, various materials used require high performance. Therefore, taking advantage of the unique properties of silicon, it excels in heat resistance and physical and electrical characteristics. Materials have been studied. Among them, various techniques for producing useful compounds by applying hydrosilylation reaction of silicon compounds have been studied. In addition, in the member manufacturing process in the field of electronic information, a lithography process is frequently used, and high base resistance and solvent resistance have been demanded. For this reason, there has been a demand for a material that satisfies both high heat resistance and crack resistance while maintaining high base resistance and solvent resistance.
In response to these requirements, various silicon-containing curable compositions have been proposed (see, for example, Patent Documents 1 to 7).

  However, these proposed technologies have individual characteristics, but they are required for materials in the recent electronic information field in terms of heat resistance, light resistance, crack resistance, colorability, adhesiveness, etc. It was not satisfactory. Among them, a serious problem is that adhesion to a silver substrate or a copper substrate is poor.

US Pat. No. 5,645,941 JP-A-8-73743 JP 2004-107577 A JP 2005-68295 A US Patent Application Publication No. 2009/012256 JP 2007-332259 A JP 2009-120732 A

  Accordingly, an object of the present invention is to provide a silicon-containing curable composition that has excellent adhesion to a silver substrate or a copper substrate and can produce a cured product useful for an electric / electronic material.

  The inventors of the present invention have intensively studied to solve the above problems by paying attention to the structure and prepolymer of a specific silicon-containing compound, and as a result, the present invention has been completed.

That is, the present invention
As the component (A), a compound having a carbon-carbon double bond having reactivity with the SiH group,
(B) As a component, a siloxane compound having a SiH group,
As the component (C), a silane compound represented by the following general formula (1),
(D) The silicon-containing curable composition characterized by containing a filler as a component is provided.

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A represents an alkanediyl group having 1 to 10 carbon atoms, and k represents a number of 2 or 3).

  Moreover, this invention provides the method of hardening the said silicon-containing curable composition including heating the said silicon-containing curable composition.

  The present invention also provides a cured product obtained by curing the silicon-containing curable composition.

  Hereinafter, the silicon-containing curable composition of the present invention and a cured product obtained by curing the same will be described in detail.

  In the silicon-containing curable composition of the present invention, the component (A) is a compound having a carbon-carbon double bond having reactivity with a SiH group. The bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and any position in the molecule is possible. Although it does not specifically limit as a carbon-carbon double bond which has the reactivity with SiH group, For example, it represents with the group represented by following General formula (2), and following General formula (3) The group which forms an alicyclic ring can be mentioned. Use of a group that forms an alicyclic ring represented by the following general formula (3) is preferable because the heat resistance of the cured product is increased.

(In the formula, L ¹ represents hydrogen or a methyl group, and * represents a bond.)

(In the formula, L ² represents hydrogen or a methyl group, and * represents a bond.)

Among the groups represented by the general formula (2), those in which L ¹ is hydrogen are particularly preferable because of good reactivity.

Among the groups forming the alicyclic ring represented by the general formula (3), those in which L ² is hydrogen are particularly preferable because of good reactivity.

  The compound having a carbon-carbon double bond having reactivity with the SiH group is an organic compound having a carbon-carbon double bond having reactivity with the SiH group (hereinafter abbreviated as (A-α)). And a silicone compound having a carbon-carbon double bond having reactivity with the SiH group (hereinafter sometimes abbreviated as (A-β)) can be mentioned as a preferred compound. As (A-α), only one type of compound can be used, or a plurality of types of compounds having different structures can be used. As (A-β), only one type of compound can be used, or a plurality of types of compounds having different structures can be used. In addition, (A-α) and (A-β) can be used in combination.

  The (A-α) is not particularly limited as long as it is an organic compound having a carbon-carbon double bond that is reactive with a SiH group, but as constituent elements, C, H, N, O, S and Organic compounds containing no elements other than halogen are preferred. Particularly preferred (A-α) includes trimethallyl isocyanurate and triallyl isocyanurate. These are marketed as a tie and a tie derivative (manufactured by Nippon Kasei Co., Ltd.), and these commercially available products can be used as (A-α) in the present invention.

  The (A-β) is not particularly limited as long as it is a silicone compound having a carbon-carbon double bond having reactivity with the SiH group. For example, a unit represented by the following general formula (4) Examples thereof include silicon-containing polymers.

(In the formula, R ² represents an alkenyl group having 2 to 6 carbon atoms, and * represents a bond.)

Examples of the alkenyl group having 2 to 6 carbon atoms represented by R ² in the general formula (4) include a vinyl group, a 2-propenyl group, and a 3-butenyl group. R ² is preferably a vinyl group from the viewpoint of reactivity.

  The silicon-containing polymer containing a unit represented by the general formula (4) is, for example, hydrolyzing / condensing only one or more types of organosilanes represented by the following general formula (A-1), or From one or more types of organosilane represented by the following general formula (A-1), an organosilane represented by the following general formula (A-2), and an organosilane represented by the following general formula (A-3) It can be produced by hydrolyzing and condensing a mixture containing at least one selected organosilane.

(In the formula, R ³ represents an alkenyl group having 2 to 6 carbon atoms, R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a hydrocarbon group, and X ¹ represents a hydroxyl group and 1 to 1 carbon atoms. 6 represents an alkoxy group or a halogen atom.)

Examples of the alkenyl group having 2 to 6 carbon atoms represented by R ³ in the general formula (A-1) include a vinyl group, a 2-propenyl group, and a 3-butenyl group. R ³ is preferably a vinyl group from the viewpoint of reactivity.

In the general formula (A-2) and the general formula (A-3), examples of the hydrocarbon group represented by R ⁴ , R ^5, and R ⁶ include aliphatic carbon such as an alkyl group, an alkenyl group, and an alkynyl group. Examples thereof include alicyclic hydrocarbon groups such as hydrogen groups and cycloalkyl groups, and aromatic hydrocarbon groups such as aryl groups and arylalkyl groups. As the hydrocarbon group, those having 1 to 10 carbon atoms are preferable.

In the general formula (A-1), the general formula (A-2), and the general formula (A-3), the alkoxy group having 1 to 6 carbon atoms represented by X ¹ is a methoxy group. , An ethoxy group, a propoxy group, a butoxy group, and the like. Examples of the halogen atom represented by X ¹ include a chlorine atom, a bromine atom, and an iodine atom. X ¹ is preferably a methoxy group or an ethoxy group from the viewpoint of reactivity.
Incidentally, each of ^{X 1} in formula (A-1) ~ (A -3) can sometimes be identical to each other, it may be different.

  Among these, 1 to 5 mol% of organosilanes represented by the above general formula (A-1) (hereinafter sometimes abbreviated as (a)), and the following general formula (A-4) One or more types of organosilanes represented by the following formula (A-5) (hereinafter abbreviated as (c)) 1) or more of 0 to 40 mol%, organosilane represented by the following general formula (A-6) (hereinafter sometimes abbreviated as (d)) of 0 to 50 mol% and It consists of one or more kinds of organosilanes represented by the general formula (A-7) (hereinafter sometimes abbreviated as (e)) in an amount of 0 to 40 mol%, and consists of organosilane (b) and organosilane (c). It is obtained by hydrolyzing and condensing an organosilane mixture whose sum is 5 to 60 mol%. It is particularly preferable to use a silicon-containing polymer.

(Wherein R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 2 to 2 carbon atoms. 6 alkenyl group, or an also phenyl group when substituted with an alkyl group having 1 to 6 carbon atoms, at least one of R ^7, R ⁸ and R ⁹ are methyl groups, R ¹⁰ Represents a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, R ¹¹ represents an epoxy group having 2 to 10 carbon atoms, X ² represents a hydroxyl group, and 1 to 1 carbon atoms. 6 represents an alkoxy group or a halogen atom.)

In the general formula (A-4), the alkyl group having 1 to 6 carbon atoms represented by R ⁷ can be linear, branched or cyclic, and specific examples thereof include a methyl group and an ethyl group. Propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, t-amyl group, hexyl group, cyclohexyl group and the like. R ⁷ is preferably a methyl group from the viewpoint of reactivity.

In formula (A-5), an alkyl group having 1 to 6 carbon atoms represented by R ⁸ and R ^9, as well as the number of carbon atoms, sometimes substituted phenyl group represented by R ⁸ and R ⁹ Examples of the alkyl group of 1 to 6 include the same groups as those described above for R ⁷ . Examples of the alkenyl group having 2 to 6 carbon atoms represented by R ⁸ and R ⁹ include the same alkenyl groups as those represented by R ³ above. R ⁸ and R ⁹ are preferably a methyl group or an unsubstituted phenyl group, and particularly preferably a methyl group, from the viewpoint of industrial availability.
In the general formula (A-6), the alkyl group having 1 to 6 carbon atoms that may substitute the phenyl group represented by R ¹⁰ is the same as those exemplified as those represented by R ^7. Can be mentioned. R ¹⁰ is preferably an unsubstituted phenyl group from the viewpoint of industrial availability.

In the general formula (A-7), the epoxy group having 2 to 10 carbon atoms represented by R ¹¹ is a substituent having a three-membered cyclic ether, such as an epoxyethyl group, a glycidyl group, 2 , 3-epoxybutyl group, 3,4-epoxybutyl group, epoxyethylphenyl group, 4-epoxyethylphenylethyl group, 3,4-epoxycyclohexyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 2 , 3-epoxynorbornylethyl group and the like. R ¹¹ is preferably a glycidyl group, a 3,4-epoxycyclohexyl group, or a 2- (3,4-epoxycyclohexyl) ethyl group from the viewpoint of imparting adhesion to different materials.

In the general formulas (A-4) to (A-7), examples of the alkoxy group having 1 to 6 carbon atoms represented by X ² include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen atom represented by X ² include a chlorine atom, a bromine atom, and an iodine atom. X ² is preferably a methoxy group or an ethoxy group from the viewpoint of reactivity. Incidentally, ^{X 1} and the general formula in formula (A-1) (A- 4) ~ each ^{X 2} in (A-7) may, in some cases the same as each other or may be different.

When X ¹ and X ² are all alkoxy groups having 1 to 6 carbon atoms (alkoxysilane) as the above five components, the hydrolysis / condensation reaction of alkoxysilane is carried out by performing a so-called sol-gel reaction. Often, the sol-gel reaction includes a method of performing a hydrolysis / condensation reaction with a catalyst such as an acid or a base in the absence of a solvent or in a solvent. The solvent used here is not particularly limited. Specifically, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, toluene and the like can be used. 1 type of these can be used, and 2 or more types can also be mixed and used.

  The hydrolysis / condensation reaction of the alkoxysilane proceeds when the alkoxysilane generates silanol groups (Si—OH) by hydrolysis with water, and the generated silanol groups or silanol groups and alkoxy groups condense. In order to advance this reaction, it is preferable to add an appropriate amount of water, which can be added to the solvent, or the catalyst can be added by dissolving it in water. The hydrolysis / condensation reaction proceeds even with moisture in the air or a trace amount of moisture contained in the solvent.

  The catalyst such as acid and base used in the hydrolysis / condensation reaction is not particularly limited as long as it promotes the hydrolysis / condensation reaction, and specifically, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid; Organic acids such as acetic acid, oxalic acid, p-toluenesulfonic acid, monoisopropyl phosphate; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia; trimethylamine, triethylamine, monoethanolamine, diethanolamine, etc. Amine compounds; titanium esters such as tetraisopropyl titanate and tetrabutyl titanate; tin carboxylates such as dibutyltin laurate and tin octylate; boron compounds such as trifluoroboron; metals such as iron, cobalt, manganese and zinc Metal carboxylates such as chlorides, naphthenates or octylates Aluminum compounds such as aluminum tris acetylacetonate and the like, also the use of these one may be used in combination of two or more.

  A preferred example of the hydrolysis / condensation reaction of the alkoxysilane is a method in which a base catalyst is added and a polycondensation reaction is performed under basic conditions (pH 7 or more). In addition, hydrolysis and dehydration polycondensation can be performed under the acidic condition (pH 7 or less) by adding an acid catalyst.

  In addition, when performing the said hydrolysis and condensation reaction, it is preferable to stir a reaction system, and reaction can be accelerated | stimulated by heating at 40-150 degreeC.

The order of the hydrolysis / condensation reaction is not particularly limited. For example, an alkoxysilane having an alkenyl group (R ³ Si (X ¹ ) ₃ ) and another alkoxysilane (R ⁷ Si (X ² ) ₃ , R ⁸ R ⁹ Si (X ² ) ₂ , R ¹⁰ Si (X ² ) ₃ , R ¹¹ Si (X ² ) ₃ ) can be mixed together to carry out a hydrolysis / condensation reaction. It is also possible to carry out hydrolysis / condensation reaction to some extent by using one kind of alkoxysilane alone, and further adding other alkoxysilane to carry out hydrolysis / condensation reaction.

As the 5 components, as X ¹ or X ² is a hydroxyl group, X ¹ or X ² can be used in combination as an alkoxy group, in this case, hydrolysis is one X ¹ and X ² is a hydroxyl group It can be used without decomposition.

When using halogenosilanes such as chlorosilane (wherein the above five components X ¹ and X ² are halogen atoms), hydrolysis / condensation reaction can be carried out in the same manner as in the case of alkoxysilane.

  In order to obtain the produced silicon-containing polymer from the reaction system in which the hydrolysis / condensation reaction is completed, the reaction solvent, water, and catalyst may be removed. For example, after solvent extraction by adding a solvent such as toluene, The extraction solvent may be distilled off under reduced pressure under a nitrogen stream.

In the organosilane mixture, the organosilane (a) is preferably 10 to 40 mol% from the viewpoint of controlling the crosslinking density during curing.
As long as the sum of organosilane (b) and organosilane (c) is 5 to 60 mol%, either one of the components can be used as organosilane (b) and (c). The organosilane (b) is preferably 20 to 40 mol% from the viewpoint of controlling the crosslinking density at the time of curing, and the organosilane (c) is preferably 10 to 25 from the viewpoint of imparting flexibility to the resin. It is preferable that it is mol%.
The organosilane (d) can be omitted, but is preferably 5 to 45 mol% from the viewpoint of controlling the resin melting temperature. The organosilane (e) may be not used, but is preferably 5 to 25 mol% from the viewpoint of imparting adhesion to different materials.
Moreover, it is preferable that the sum of organosilane (b) and organosilane (c) is 25-55 mol% from the point of control of the crosslinking density at the time of hardening.
The organosilane contained in the organosilane mixture is composed of only five components of organosilanes (a), (b), (c), (d) and (e) from the viewpoint of controlling the molecular weight of the silicon-containing polymer. Preferably there is.

In the silicon-containing polymer containing the unit represented by the general formula (4), for example, it is derived from each of the organosilanes (a), (b), (c), (d) and (e) (R ³ SiO _3/2 ), (R ⁷ SiO _3/2 ), (R ⁸ R ⁹ SiO), (R ¹⁰ SiO _3/2 ) and (R ¹¹ SiO _3/2 ) Are connected in two dimensions or three dimensions at random, and each terminal is an OH group, X ¹ or X ² . X ¹ and X ² are groups derived from organosilane (a), (b), (c), (d) or (e).
The (R ³ SiO _3/2 ) includes (R ³ SiX′O _2/2 ), and the (R ⁷ SiO _3/2 ) includes (R ⁷ SiX′O _2/2 ). (R ¹⁰ SiO _3/2 ) includes (R ¹⁰ SiX′O _2/2 ), and (R ¹¹ SiO _3/2 ) includes (R ¹¹ SiX′O _2/2 ). Shall be. X ′ is the same as X ¹ and X ² contained in each of the organosilanes (a), (b), (d) and (e), or represents an OH group.

  Among the silicon-containing polymers containing the unit represented by the general formula (4), the proportion of phenyl groups in all organic components (components excluding silicon) is 50% by mass or less, particularly 40% by mass or less. Some are preferable, and those having a methyl group ratio of 85% by mass or less, particularly 70% by mass or less are preferable. When the proportion of the phenyl group is large, the melting point of the silicon-containing polymer becomes high and it is difficult to melt at the molding temperature, and it becomes difficult to increase the molecular weight of the cured product (polymer) at the time of molding. Therefore, it is preferable that the ratio of the phenyl group is small and the ratio of the methyl group is large, and the ratio of the ratio of the phenyl group to the ratio of the methyl group (the former: the latter) is more preferably 30:50 to 30:80. .

  Among the silicon-containing polymers containing the unit represented by the general formula (4), a silicon-containing polymer having a weight average molecular weight of 300 to 100,000 in terms of polystyrene is preferable, and a weight average molecular weight is more preferable. Is in the range of 800 to 50,000. Here, if the weight average molecular weight of the silicon-containing polymer is smaller than 300, the thermal stability may be deteriorated. If it is larger than 100,000, the silicon-containing polymer may not melt at the processing temperature in transfer molding, or may melt. However, the viscosity of the resin is low and the fluidity of the resin is low, and the moldability may be reduced.

  The silicon-containing polymer containing the unit represented by the general formula (4) can be modified and used. The modification applied to the silicon-containing polymer is not particularly limited, and various modifications that can be performed to make the silicone resin a reactive silicone resin are possible. More specifically, amino modification, epoxy modification, Carboxyl modification, carbinol modification, methacryl modification, mercapto modification, phenol modification and the like can be carried out by conventional methods.

  The silicon-containing polymer containing the unit represented by the general formula (4) described in detail above can be used alone or as a mixture of two or more.

  Moreover, as a silicone compound which can be preferably used as said (A- (beta)), the siloxane compound which contains one or more carbon-carbon double bonds which have reactivity with Si-H group in 1 molecule is mentioned, for example. Can be mentioned. The siloxane compound is not particularly limited as long as it is a siloxane compound containing at least one carbon-carbon double bond having reactivity with the Si-H group in one molecule. Various types such as linear, cyclic, branched, and those having a partial network can be used. Among these, a siloxane compound containing two or more carbon-carbon double bonds having reactivity with Si—H groups in one molecule is preferable, and carbon-carbon two having reactivity with Si—H groups is preferable. A linear siloxane compound containing two or more heavy bonds in one molecule or a cyclic siloxane compound containing two or more carbon-carbon double bonds having reactivity with Si-H groups was used. In this case, a silicon-containing curable composition having higher adhesion is particularly preferable.

The linear siloxane compound containing two or more carbon-carbon double bonds having reactivity with the Si-H group in one molecule is a carbon-carbon double bond having reactivity with the Si-H group. Is a linear siloxane copolymer containing 2 or more per molecule. The linear siloxane copolymer may be a random copolymer or a block copolymer. 2-10 are preferable and, as for the number of the carbon-carbon double bond which has reactivity with Si-H group, 2-6 are more preferable from the point of the crosslinking density of hardened | cured material. Examples of the carbon-carbon double bond include alkenyl groups such as a vinyl group, 2-propenyl group, and 3-butenyl group. Since the reactivity is good, a vinyl group bonded to a silicon atom (Si is preferably -CH = a CH ₂ group).
Among linear siloxane copolymers containing 2 or more carbon-carbon double bonds having reactivity with Si-H groups in one molecule, the following general ones are particularly preferable from the viewpoint of physical properties of the cured product. A linear siloxane copolymer represented by the formula (A-8) can be given.

(Wherein R ¹² and R ³¹ each independently represents an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an epoxy group having 2 to 10 carbon atoms, or a trimethylsilyl group, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²⁰ , R ²⁴ , R ²⁸ , R ²⁹ and R ³⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹⁷ , R ¹⁸ and R ¹⁹ each represent a phenyl group, R ²¹ , R ²² and R ²³ each independently represent an alkenyl group having 2 to 6 carbon atoms, and R ²⁵ , R ²⁶ and R ²⁷ each independently represent Represents an epoxy group having 2 to 10 carbon atoms, and when R ¹² and R ³¹ are alkyl groups having 1 to 6 carbon atoms, v ≧ 1 or v + w ≧ 2, and R ¹³ , R ¹⁴ , R ^{15, R} 16, ^{R 20, 24,} when at least one of ^{R 28, R 29} and ^{R 30} are hydrogen atoms, v is ≧ 1 or w ≧ 1, the p number of ^{R 15} and ^{R 16} there may also respectively identical differ , Q R ¹⁷ and R ¹⁸ , r R ¹⁹ and R ²⁰ , v R ^{21 and} R ²² , w R ^{23 and} R ²⁴ , x R ^{25 and} R ²⁶ , y R ^{27 and} R ²⁸ may be the same as or different from each other, p, q, r, v, w, x and y each independently represent a number from 0 to 3000, and p + q + r + v + w + x + y ≧ 1.

In the general formula (A-8), the alkenyl group having 2 to 6 carbon atoms represented by R ¹² and R ³¹ , R ²¹ , R ²² , and R ²³ is represented by R ³ above. The thing similar to what was mentioned is mentioned.
Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹² and R ³¹ , and R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²⁰ , R ²⁴ , R ²⁸ , R ²⁹ and R ³⁰ include It includes the same groups as represented by R ^7.
Examples of the epoxy group having 2 to 10 carbon atoms represented by R ¹² and R ³¹ , R ²⁵ , R ^26, and R ²⁷ include the same as those exemplified as those represented by R ¹¹ above. .

In the general formula (A-8), R ¹² and R ³¹ are preferably a vinyl group or a 2-propenyl group from the viewpoint of reactivity, and R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²⁰ , R ²⁴ are preferable. , R ²⁸ , R ²⁹ and R ³⁰ are preferably a methyl group or an ethyl group from the viewpoint of industrial availability, and R ²¹ , R ²² and R ²³ are preferably a vinyl group or 2- A propenyl group is preferred.
Among these, preferable specific examples of the linear siloxane copolymer containing two or more carbon-carbon double bonds having reactivity with Si-H group in one molecule include the following formula (A The linear siloxane compound shown by -9)-(A-17) is mentioned.

(In the formula, p, q and r have the same meanings as in the general formula (A-8).)

(In the formula, r and q have the same meaning as in the general formula (A-8).)

(In the formula, p has the same meaning as the above general formula (A-8).)

(In the formula, p and q are as defined in the general formula (A-8).)

(In the formula, p and w are as defined in the general formula (A-8).)

(In the formula, p, r and w have the same meanings as in the general formula (A-8).)

(In the formula, p, r and w have the same meanings as in the general formula (A-8).)

(In the formula, p, r and w have the same meanings as in the general formula (A-8).)

In the cyclic siloxane compound containing two or more carbon-carbon double bonds having reactivity with the Si-H group in one molecule, the number of carbon-carbon double bonds is preferably 2 to 10. 2 to 6 is more preferable because the crosslink density of the cured product is increased. Examples of the carbon-carbon double bond include alkenyl groups such as a vinyl group, 2-propenyl group, and 3-butenyl group. Since the reactivity is good, a vinyl group bonded to a silicon atom (Si is preferably -CH = a CH ₂ group).
Among the cyclic siloxane compounds containing two or more carbon-carbon double bonds having reactivity with Si-H group in one molecule, the following general formula (A- The cyclic siloxane compound represented by 18) can be mentioned.

(In the formula, R ³² , R ³³ and R ³⁴ each represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and n R ³² may be the same or different, and m R ³³ and m R ³⁴ may be the same as or different from each other, n represents a number of 2 to 10, m represents a number of 0 to 8, and m + n ≧ 2.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ³² , R ³³ and R ³⁴ are the same as those exemplified as those represented by R ⁷ . In the general formula (A-18), R ³² , R ³³ and R ³⁴ are preferably a methyl group or a phenyl group from the viewpoint of industrial availability. n is preferably 2 to 4 because the crosslink density is good, and m is preferably 1 to 3 from the viewpoint of viscosity.
Among these, preferred specific examples of the cyclic siloxane copolymer containing two or more carbon-carbon double bonds having reactivity with Si—H group in one molecule include the following formula (A-19): ) To (A-21).

  In addition, a compound having a carbon-carbon double bond that is reactive with a SiH group may also have a SiH group (for example, a compound represented by the above formula (A-17)). It is handled as the component (A), not the component (B). The component (B) does not have a carbon-carbon double bond having reactivity with the SiH group.

  The component (B) in the silicon-containing curable composition of the present invention is a siloxane compound having a SiH group. The component (B) is not particularly limited as long as it is a siloxane compound having one or more SiH groups in one molecule, but a siloxane compound having two or more SiH groups in one molecule is preferably used. Can do.

  The content of the component (B) in the silicon-containing curable composition of the present invention is preferably in the range of 0.1 to 100 parts by mass, and 1 to 60 parts by mass with respect to 100 parts by mass of the component (A). Is more preferable, and a range of 5 to 40 parts by mass is more preferable.

  Among the siloxane compounds having two or more SiH groups in one molecule, one or more selected from cyclic siloxane compounds represented by the following general formula (B-1), the following general formula (B-2), and the following A siloxane compound having two or more SiH groups in one molecule, obtained by hydrosilylation reaction of one or more selected from compounds represented by formula (B-3) or the following general formula (B-4) Hereinafter, (B-α) may be preferably used.

(Wherein R ³⁵ , R ³⁶ and R ³⁷ each independently represent a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms, f R ³⁵ may be the same or different, and g R ³⁶ and g R ³⁷ may be the same or different, respectively, and f represents a number of 2 to 10 and g Represents a number from 0 to 8,
f + g ≧ 2. )

(In the formula, R ³⁸ represents an alkenyl group having 2 to 10 carbon atoms, and R ³⁹ and R ⁴⁰ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or Represents an epoxy group having 2 to 10 carbon atoms, and h represents 1 or 2.)

In the general formula (B-1), the alkyl group having 1 to 6 carbon atoms represented by R ³⁵ , R ³⁶ and R ³⁷ can be linear, branched or cyclic. Methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, t-amyl group, hexyl group, cyclohexyl group, etc. Can be mentioned.

In the general formula (B-1), R ³⁵ is preferably a methyl group, and R ³⁶ and R ³⁷ are preferably a methyl group or a phenyl group. f is preferably from 4 to 6, and g is preferably from 0 to 1 from the viewpoint of the crosslinking density of the curing reaction. When both a methyl group and a phenyl group are included, the ratio of the number of methyl groups to the number of phenyl groups (the former: the latter) is 4: 1 to 1: 4 in the total number of substituents R ^{35 to} R ³⁷ . The range is preferable because the molecular weight can be controlled stably.

In the general formula (B-4), examples of the alkenyl group having 2 to 10 carbon atoms represented by R ³⁸ , R ^39, and R ⁴⁰ include a vinyl group, a 2-propenyl group, and a 3-butenyl group. .

In the general formula (B-4), the alkyl group having 1 to 10 carbon atoms represented by R ³⁹ and R ⁴⁰ may be linear, branched or cyclic, and specific examples include a methyl group. , Ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, t-amyl group, hexyl group, cyclohexyl group, heptyl group, octyl Group, nonyl group, decyl group, ethylhexyl group and the like.

In the general formula (B-4), the epoxy group having 2 to 10 carbon atoms represented by R ³⁹ and R ⁴⁰ is a substituent having a three-membered cyclic ether, such as an epoxyethyl group or glycidyl. Group, 2,3-epoxybutyl group, 3,4-epoxybutyl group, epoxyethylphenyl group, 4-epoxyethylphenylethyl group, 3,4-epoxycyclohexyl group, 2- (3,4-epoxycyclohexyl) ethyl Group, a 2,3-epoxynorbornylethyl group, and the like.

  Examples of the cyclic siloxane compound represented by the general formula (B-1) include 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, Examples include 1,3,5,7,9,11-hexamethylcyclohexasiloxane, and 1,3,5,7-tetramethylcyclotetrasiloxane is preferred. The cyclic siloxane compound represented by the general formula (B-1) can be used alone or in combination of two or more.

  The compound represented by the general formula (B-2) represents divinylbenzene when h is 1, and can be any of o-divinylbenzene, m-divinylbenzene or p-divinylbenzene, h Is 2, it indicates trivinylbenzene, and any of 1,2,3-trivinylbenzene, 1,2,4-trivinylbenzene and 1,3,5-trivinylbenzene is possible. In the compound represented by the general formula (B-2), a functional group other than a vinyl group (for example, an alkyl group such as a methyl group) may be bonded to a benzene ring or a mixture thereof. .

  Of the compounds represented by the above general formula (B-2), the above formula (B-3) and the above general formula (B-4), divinylbenzene is preferable. The compounds represented by the above general formula (B-2), the above formula (B-3) and the above general formula (B-4) can be used alone or in combination of two or more. it can.

  The (B-α) is one or more selected from the cyclic siloxane compounds represented by the general formula (B-1) and the general formula (B-2), the formula (B-3), or the general formula. It can be obtained by hydrosilylating one or more selected from the compounds represented by (B-4). One or more selected from the cyclic siloxane compounds represented by the above general formula (B-1) and the above general formula (B-2), the above formula (B-3) or the above general formula (B-4). The compounding ratio of one or more selected from the compounds to be selected is not particularly limited as long as it has two or more SiH groups in one molecule. Preferably, the number of SiH groups contained in one or more selected from the cyclic siloxane compound represented by the general formula (B-1), the general formula (B-2), the formula (B-3), or The ratio (the former: the latter) to the number of carbon-carbon double bonds having reactivity with SiH groups contained in one or more selected from the compounds represented by the general formula (B-4) is 10: It is the range of 1-2: 1, More preferably, it is the range of 4: 1-2: 1.

  The concentration of the (B-α) SiH group is preferably 0.0001 mmol / g to 100 mmol / g, and more preferably 0.01 mmol / g to 20 mmol / g, since the curability is improved.

  The (B-α) preferably has a weight average molecular weight of 500 to 500,000, and more preferably 1000 to 300,000, because of good heat resistance. The weight average molecular weight may be measured using GPC, and may be determined by polystyrene conversion.

  The hydrosilylation reaction may be performed using a platinum-based catalyst. As the platinum-based catalyst, a known catalyst containing one or more metals of platinum, palladium and rhodium that promote the hydrosilylation reaction can be used. These platinum-based catalysts used as hydrosilylation catalysts include platinum-carbonyl vinylmethyl complexes, platinum-divinyltetramethyldisiloxane complexes, platinum-cyclovinylmethylsiloxane complexes, platinum-octylaldehyde complexes, etc. In addition to the catalyst, compounds containing platinum-based metals such as palladium and rhodium can be used instead of platinum. One of these can be used alone, or two or more can be used in combination. In particular, those containing platinum are preferable from the viewpoint of curability, and specifically, platinum-divinyltetramethyldisiloxane complex (Karsttedt catalyst) and platinum-carbonylvinylmethyl complex (Ossko catalyst) are preferable. In addition, a so-called Wilkinson catalyst containing the above platinum-based metal such as chlorotristriphenylphosphine rhodium (I) is also included in the platinum-based catalyst in the present invention. The amount of the platinum-based catalyst used is one or more selected from cyclic siloxane compounds represented by the above general formula (B-1), the above general formula (B-2), the above formula ( 5-3 mass% or less of the total amount of 1 or more types chosen from the compound represented by B-3) or the said general formula (B-4) is preferable, and 0.0001-1.0 mass% is more preferable. The hydrosilylation reaction conditions are not particularly limited, and may be carried out under the conditions known in the art using the above catalyst. From the viewpoint of curing speed, it is preferably carried out at room temperature to 130 ° C. During the reaction, toluene, xylene, hexane Conventionally known solvents such as MIBK (methyl isobutyl ketone), cyclopentanone, and PGMEA (propylene glycol monomethyl ether acetate) can also be used. The catalyst can be removed after the hydrosilylation reaction, and can be used as it is in the silicon-containing curable composition without being removed.

  (C) component in the silicon-containing curable composition of this invention is a silane compound represented by the said General formula (1). A silicon-containing cured product having excellent adhesion to a silver substrate or a copper substrate is produced by using the component (C) in combination with the component (A), the component (B) and the component (D). A silicon-containing curable composition that can be obtained can be obtained. It is preferable that content of (C) component in the silicon-containing curable composition of this invention is 0.001-0.1 mass part with respect to 100 mass parts of said (A) component. When the amount is less than 0.001 part by mass, the effect of addition is hardly exhibited. Moreover, even if it adds more than 0.1 mass part, a mixing effect will hardly improve.

In the general formula (1), examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, and a third group. A butyl group can be mentioned. Among these, a methyl group or an ethyl group is preferable because the obtained cured product has a high effect of having excellent adhesion to a silver substrate or a copper substrate.

  In the general formula (1), examples of the alkanediyl group having 1 to 10 carbon atoms represented by A include, for example, a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, a pentylene group, a hexylene group, and a heptylene. Group, octylene group and the like. Since the obtained hardened | cured material has the high effect which has the outstanding adhesiveness with respect to a silver base or a copper base, a C1-C5 alkanediyl group is more preferable, and a propylene group is especially preferable.

  In the general formula (1), k represents a number of 2 or 3. Since the obtained cured product has a high effect of having excellent adhesion to a silver substrate or a copper substrate, k is preferably 3.

  Preferable specific examples of the compound represented by the general formula (1) include the following chemical formula No. 1-No. The compound represented by 20 is mentioned. In addition, the following chemical formula No. 1-No. In 20, “Me” represents a methyl group, and “Et” represents an ethyl group.

  The component (D) in the silicon-containing curable composition of the present invention is a filler. By using the component (D) in combination with the components (A) to (C), the obtained cured product can be colored in a desired color, and the hardness of the obtained cured product can be increased. As the filler, a transparent filler, a white pigment and an inorganic filler are preferable. The content of the component (D) in the silicon-containing curable composition of the present invention is preferably 100 to 1500 parts by mass, more preferably 100 to 1400 parts by mass with respect to 100 parts by mass of the component (A). 300 to 1350 parts by mass is more preferable. In the silicon-containing curable composition of the present invention, it is also preferable to use the white pigment and the inorganic filler in combination as the component (D).

The white pigment is blended to increase whiteness as a white colorant. For example, titanium oxide is preferably used, and the unit cell of the titanium oxide may be any of rutile type, anatase type, and brookite type. However, in consideration of light resistance, a rutile type is preferably used. Moreover, although an average particle diameter and a shape are not limited, an average particle diameter is 0.05-5.0 micrometers normally. The titanium oxide can be surface-treated in advance with a hydrous oxide such as Al or Si in order to enhance compatibility and dispersibility with a resin or an inorganic filler.
The average particle size can be determined as a mass average value D ₅₀ in the particle size distribution measurement by laser diffraction method (or median diameter).

  In addition to titanium oxide, potassium titanate, zircon oxide, zinc sulfide, alumina, zinc oxide, magnesium oxide, beryllium oxide, barium sulfate, and the like can be used as the white pigment. Among these, magnesium oxide and zinc oxide are preferable. These white pigments can be used alone or in combination with titanium oxide.

The said inorganic filler can use what is normally mix | blended with sealing materials, such as a silicone resin composition and an epoxy resin composition. For example, silicas such as fused silica, fused spherical silica, crystalline silica, colloidal silica, fumed silica, and silica gel; metal oxides such as alumina, iron oxide, titanium oxide, and antimony trioxide; silicon nitride, aluminum nitride, and nitride Ceramics such as boron and silicon carbide; Minerals such as mica and montmorillonite; Metal hydroxides such as aluminum hydroxide and magnesium hydroxide or those modified by organic modification treatment; calcium carbonate, calcium silicate, magnesium carbonate , Metal carbonates such as barium carbonate or the like modified by organic modification treatment; pigments such as metal borate and carbon black; carbon fiber, graphite, whisker, kaolin, talc, glass fiber, glass beads, glass Microsphere, silica glass, layered clay ore , Clay, silicon carbide, quartz, aluminum, zinc, and the like. As the filler (D), organic fillers such as acrylic beads, polymer fine particles, transparent resin beads, wood powder, pulp, and cotton chips can also be used.
Although the average particle diameter and shape of these inorganic fillers and organic fillers are not particularly limited, the average particle diameter is usually 0.1 to 80 μm. The average particle size can be determined as a mass average value D ₅₀ in the particle size distribution measurement by laser diffraction method (or median diameter).

As the inorganic filler, from the viewpoint of resin moldability and strength, silicas, metal oxides, metal carbonates that may be modified, and pigments are preferable, and in particular, fused silica, fused spherical silica, crystals Silica, silicone beads, colloidal silica, aluminum oxide, titanium oxide, calcium carbonate, magnesium carbonate, carbon black, kaolin and glass fiber are preferred.
As the inorganic filler, in particular, fused silica, fused spherical silica, a composite of titanium oxide and calcium carbonate is preferably used from the viewpoint of moldability of the resin. The particle size is not particularly limited, but is preferably 4 to 40 μm, particularly preferably 7 to 35 μm from the viewpoint of moldability and fluidity. Further, in order to obtain high fluidity, it is desirable to use a combination of a fine region of 3 μm or less, a medium particle size region of 4 to 8 μm, and a coarse region of 10 to 40 μm.

  Further, the silicon-containing curable composition of the present invention includes an organic peroxide, a metal catalyst, an adhesion aid, a free radical scavenger, various known resins, and a mold release as long as the target performance of the present invention is not impaired. Optional components such as agents and additives can also be blended. The amount of each optional component used is not particularly limited, but is 10% by mass or less in the silicon-containing curable composition of the present invention so as not to impair the effects of the present invention. It is preferably 5% by mass or less.

  As said organic peroxide, what is generally used when hardening a silicone rubber composition can be used, for example, For example, benzoyl peroxide, o-methylbenzoyl peroxide, p-methylbenzoyl Peroxide, o-monochlorobenzoyl peroxide, p-monochlorobenzoyl peroxide, bis-2,4-dichlorobenzoyl peroxide, 2,4-dicumylbenzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl Benzoate, t-butylcumylbenzoyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexane, 1,6-bis (t-butylperoxy) Carboxy) hexane, dichromyl peroxide, dimyristyl peroxycarbonate, t-butylperoxy 2-ethylhexyl carbonate, dicyclododecyl peroxydicarbonate, compounds represented by the following general formula (5) or (5 ′) Etc. Among these, benzoyl peroxide compounds are preferable from the viewpoint of reactivity and workability, and benzoyl peroxide and 2,4-dicumylbenzoyl peroxide are particularly preferable.

(In the formula, R and R ′ are each independently a hydrocarbon group having 3 to 10 carbon atoms.)

  Examples of the hydrocarbon group having 3 to 10 carbon atoms represented by R in the general formulas (5) and (5 ′) and R ′ in the general formula (5 ′) include propyl, isopropyl, butyl, Dibutyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, cyclohexylmethyl, 2-cyclohexylethyl, heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl Alkyl groups such as nonyl, isononyl, decyl, vinyl, 1-methylethenyl, 2-methylethenyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, alkenyl groups such as 1-phenylpropen-3-yl, Phenyl, 2-methylphenyl, 3-methylphenol 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 2,3-dimethylphenyl, 2,4- Alkylaryl groups such as dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-ditertiarybutylphenyl, benzyl, 2- Arylalkyl groups such as phenylpropan-2-yl, styryl, cinnamyl, etc., which are interrupted by an ether bond or a thioether bond, such as 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxy Ethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3 Examples include methoxybutyl, 2-phenoxyethyl, 3-phenoxypropyl, 2-methylthioethyl, 2-phenylthioethyl, and these groups are substituted with alkoxy groups, alkenyl groups, nitro groups, cyano groups, halogen atoms, and the like. Sometimes it is.

  0.0001-10 mass parts is preferable with respect to 100 mass parts of said (A) component, and, when using the said organic peroxide, 0.01-5 mass parts is more preferable.

Examples of the metal catalyst include platinum-based catalysts, tris (2,4-pentanedionato) aluminum, triisopropoxide aluminum, Al (ClO ₄ ) ₃ , tetraisopropoxide titanium, tetraisobutoxide titanium, dibutyl bis (2, Examples thereof include Al-based, Ti-based and Sn-based metal catalysts such as 4-pentanedionate) tin and Bu ₂ Sn (C ₇ H ₁₅ COO) ₂ .
Of these, platinum-based catalysts and Al-based catalysts are preferable from the viewpoint of reactivity and colorability, and in particular, platinum-carbonylvinylmethyl complexes (Ossko catalysts), platinum-divinyltetramethyldisiloxane complexes (Karstedt complexes), tris. (2,4-Pentandionato) aluminum is preferred.

When using the metal catalyst, the content is preferably 1 × 10 ^{−4 to} 0.5 parts by mass with respect to 100 parts by mass of the component (A), and preferably 1 × 10 ^{−3 to} 0.2 parts by mass. More preferably, it is contained.

  As the adhesion assistant, for example, a compound having a cyanuric acid structure can be used. Examples of the compound having a cyanuric acid structure include isocyanuric acid, triallyl cyanuric acid, 1,3,5-triglycidyl isocyanuric acid, tris (2-hydroxyethyl) isocyanuric acid, and tris (2,3-dihydroxypropyl). Isocyanuric acid, tris (2,3-epoxypropyl) isocyanuric acid, Japanese Patent No. 2768426, Japanese Patent Laid-Open No. 3-261769, Japanese Patent Laid-Open No. 4-139911, Japanese Patent Laid-Open No. 4-139174, and Japanese Patent Laid-Open No. 10-333330 Can be used. In addition, these compounds may be subjected to various modification treatments such as silicone modification, ethylene oxide modification, propylene oxide modification and the like by ordinary methods. When using the compound which has a cyanuric acid structure, 0.0001-10 mass% is preferable, and, as for content of this compound in the silicon-containing curable composition of this invention, 0.01-1.0 mass% is further. preferable.

  As said free radical scavenger, antioxidant substances, such as antioxidant and a stabilizer, can be mentioned, for example. For example, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], dibutylhydroxytoluene (BHT), 2,6-di-t-butyl-paracresol (DBPC). ) And the like. When using a free radical scavenger, 0.1 to 10% by mass is preferable in the silicon-containing curable composition of the present invention in terms of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling, 1-5 mass% is more preferable.

  Examples of the various resins include polybutadiene resins and modified products thereof, modified products of acrylonitrile copolymers, polystyrene resins, polyethylene resins, fluororesins, polyimide resins, polyethylene glycol, polyphenylene ether, polypropylene glycol and other polyether resins, polyurethane Resins, epoxy resins, phenol resins, polyester resins, melamine resins, polyamide resins, polyphenylene sulfide resins and the like can be mentioned.

  Examples of the mold release agent include carnauba wax, fatty acid ester, glyceric acid ester, stearic acid, montanic acid, behenic acid and its metal salt, alkali metal compound, organic titanium, organic zirconia, organic tin compound, imidazole compound, carboxyl Group-containing polyolefins, polyethylene-polyoxyethylene resins, carnauba and the like can be used.

  Examples of the additive that can be optionally blended include brighteners, waxes, ultraviolet absorbers, antistatic agents, antioxidants, deterioration inhibitors, modifiers, silane coupling agents, defoaming agents, dyes, maleimide compounds , Cyanate ester compounds, silicone gels, silicone oils and the like.

  Since the silicon-containing curable composition of the present invention is solid at room temperature (25 ° C.), it has excellent handling properties. The silicon-containing curable composition of the present invention can be in the form of powder, granules, tablets, etc., and can also be used by dissolving in a solvent. The silicon-containing curable composition of the present invention preferably has a melting point of 50 ° C. or higher and 150 ° C. or lower, and more preferably 50 ° C. or higher and 120 ° C. or lower. The silicon-containing curable composition of the present invention is preferably melted at 50 ° C. to 150 ° C. and then cured by heat. Moreover, the hardened | cured material which consists of a silicon-containing curable composition of this invention is excellent in the adhesiveness to a silver base | substrate and a copper base | substrate, and also excellent in heat resistance and adhesiveness. As for the heat resistance, specifically, a cured product having a temperature causing a weight loss of 5% by mass of the cured product is preferably 400 ° C. or higher, more preferably 500 ° C. or higher. Moreover, the hardened | cured material with few crack generation is suitably obtained from the silicon-containing curable composition of this invention.

  The silicon-containing curable composition of the present invention can be made uniform and transparent, and in that case, the light-transmitting light such as ultraviolet rays is good, and by adding a photoreactive catalyst, photocuring can be achieved. Is possible. Of course, a photoreactive monomer or resin can be further blended, and any one or more of each component in the silicon-containing curable composition can have a photoreactive group. Furthermore, from the silicon-containing curable composition of the present invention, weather resistance, hardness, stain resistance, flame resistance, moisture resistance, gas barrier properties, flexibility, elongation and strength, electrical insulation, low dielectric constant properties A material having excellent mechanical properties such as mechanical properties, optical properties, electrical properties, and the like can be obtained.

Next, the cured product of the present invention will be described.
The silicon-containing curable composition of the present invention can be cured by heating to obtain a cured product. This curing reaction can be performed by a method of mixing and heating the compounding components of the silicon-containing curable composition of the present invention immediately before use, and a method of heating when performing the curing reaction by mixing all the compounding components in advance. Can also be done.
The heating temperature for curing is preferably equal to or higher than the temperature at which the resin melts, for example, 35 to 350 ° C, and more preferably 50 to 250 ° C. The curing time is preferably 2 to 60 minutes, more preferably 2 to 10 minutes. Further, after curing, it can be annealed or molded. The annealing time varies depending on the temperature, but it is preferably about 5 to 60 minutes at 150 ° C. By performing a curing reaction under these curing reaction conditions, a cured product having performances excellent in heat resistance, durability, adhesion, and the like can be obtained from the silicon-containing curable composition of the present invention. As the molding method, known methods such as transfer molding, compression molding, and cast molding can be used, and transfer molding is preferable from the viewpoint of workability and dimensional stability.

The transfer molding is preferably performed using a transfer molding machine at a molding pressure of 5 to 20 N / mm ² and a molding temperature of 120 to 190 ° C. for 30 to 500 seconds, particularly 150 to 185 ° C. for 30 to 180 seconds. The compression molding method is preferably performed using a compression molding machine at a molding temperature of 120 to 190 ° C. for 30 to 600 seconds, particularly at 130 to 160 ° C. for 120 to 300 seconds. In any molding method, it can be cured at 150 to 185 ° C. for 2 to 20 hours.
Moreover, when hardening the silicon-containing curable composition of this invention, film-forming methods, such as spin casting, potting, and dipping, can be applied suitably.

  The silicon-containing curable composition of the present invention has excellent physical properties such as heat resistance, light resistance, crack resistance, and colorability in addition to the excellent adhesion of the cured product to the silver base and the copper base. It can be used as an excellent curable composition. The silicon-containing curable composition and cured product of the present invention are used for sealing materials such as display materials, optical materials, recording materials, printed circuit boards, semiconductors, and solar cells in the field of electric and electronic materials; high-voltage insulating materials, insulating and preventing materials It can be used as various materials for the purpose of vibration, waterproofing and moisture prevention. Applications include prototype molds for plastic parts, coating materials, interlayer insulation films, prepregs, insulating packings, heat-shrinkable rubber tubes, O-rings, sealants and protective materials for display devices, optical waveguides, optical fiber protective materials , Optical lenses, adhesives for optical equipment, high heat resistant adhesives, elastic adhesives, adhesives, die bonding agents, high heat dissipation materials, high heat resistant sealing materials, solar cell / fuel cell members, solid electrolytes for batteries, It can also be applied to insulation coating materials, photosensitive drums for copying machines, and gas separation membranes. It can also be applied to concrete protection materials, linings, soil injecting agents, sealing agents, cold storage materials, glass coatings, foams, paints, etc. in the civil engineering / building materials field, and also in the medical materials field, tubes and seals. It can be applied to materials, coating materials, printed circuit board applications, sealing materials for sterilization equipment, contact lenses, oxygen-enriched films, etc. In addition, it can be applied to films, gaskets, casting materials, various molding materials, sealants for rust prevention and waterproofing of netted glass, automobile parts, various machine parts, and the like.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further, this invention is not limited by these Examples. In the examples, “parts” and “%” are based on mass.

[Production Example 1] Synthesis of A-1 In a 2000 ml four-necked flask equipped with a cooling tube and a stirrer, 0.5 mol of vinyltrimethoxysilane as component (a) and 0.5 mol of methyltrimethoxysilane as component (b) , Dimethyldimethoxysilane 0.25 mol as component (c), 1.0 mol phenyltrimethoxysilane as component (d), and 650 g of toluene were added, and 31.4 g of 0.5% aqueous sodium hydroxide solution was added for 30 minutes with stirring. The solution was added dropwise and subjected to a dehydration polymerization reaction at 60 to 65 ° C. for 3 hours. After cooling to room temperature, 600 g of toluene and 1500 g of ion-exchanged water are added, the oil layer is extracted, washed with water until neutrality, the solvent is removed, and the silicon-containing polymer A-1 as component (A) is obtained. 232.6 g was obtained (white powder). When the weight average molecular weight (Mw) of the silicon-containing polymer A-1 was analyzed by GPC under the following conditions, it was Mw = 15000 (polystyrene conversion).
(GPC measurement conditions)
Column: SuperMultiporeHZ-M
Developing solvent: Tetrahydrofuran

[Production Example 2] Synthesis of B-1 100 parts of 1,3,5,7-tetramethylcyclotetrasiloxane, 100 parts of divinylbenzene, 60 parts of toluene and 0.0005 part of platinum-carbonylvinylmethyl complex (Ossko catalyst) In addition, the mixture was refluxed for 5 hours with stirring. The solvent was distilled off from the reaction solution under reduced pressure at 70 ° C. to obtain a prepolymer B-1 as component (B).
When analyzed by GPC under the above conditions, the weight average molecular weight of the prepolymer B-1 is Mw = 140,000 (polystyrene conversion), and the content of hydrosilyl group (Si—H group) is from ¹ H-NMR. It was 5.3 mmol / g.

[Example 1] Production of silicon-containing curable composition Using the compounds shown in Table 1, Example Composition No. 1-28 were produced.

[Comparative Example 1] Production of Comparative Silicon-containing Curable Composition Comparative Examples Compositions 1 to 30 were produced with the compositions shown in Table 3 using the compounds shown in Table 1 and the following Comparative Compounds 1 to 3.

[Example 2] Production 1 of cured product
Example Composition No. 1-No. 28 was poured into a mold placed on a silver substrate (length 50 mm × width 55 mm × thickness 0.25 mm), 170 ° C. for 180 seconds (molding step), and then 150 ° C. for 2 hours (after-baking step) By heating under the conditions, the pudding cup-shaped example cured product No. 3.5 mm in diameter x 4 mm in height was used. 1-28 were molded.

[Comparative Example 2] Production of comparative cured product 1
Comparative Example Composition No. 1-No. 30 was poured into a mold placed on a silver substrate (length 50 mm × width 55 mm × thickness 0.25 mm), 170 ° C. for 180 seconds (molding step), and then 150 ° C. for 2 hours (after-baking step) By heating under these conditions, pudding cup-shaped comparative cured products 1 to 30 having a diameter of 3.5 mm and a height of 4 mm were formed.

[Evaluation Example 1] Pudding cup test 1 (silver substrate)
Example cured product No. About 1-28 and comparative example hardened | cured material 1-30, the pudding cup test was done as follows. That is, the adhesion force between the silver substrate and the molding resin is measured using a bond tester, and the case where the adhesion force is higher than 20 kg / cm ² is defined as ++, the case where the adhesion force is in the range of 5-20 kg / cm ² is defined as +, and 5 kg. / cm ² less than a is a case - to evaluate the adhesion as. When the evaluation result is +, it means that excellent adhesion is shown, and when it is ++, it means that particularly excellent adhesion is shown. The results are shown in Tables 3-1 to 3-4.

  As is clear from Tables 3-1 to 3-4, the cured products of Comparative Examples 1 to 30 had poor adhesion. On the other hand, Example cured product No. using the silicon-containing curable composition of the present invention. Nos. 1 to 28 all had good adhesion to the silver substrate. Among these, the cured product No. of Example. 1-18 had very high adhesiveness.

[Example 3] Production 2 of cured product
Example Composition No. 1-No. 28 was poured into a mold placed on a copper substrate (length 50 mm × width 55 mm × thickness 0.25 mm), 170 ° C. for 180 seconds (molding step), and then 150 ° C. for 2 hours (after-baking step) By heating under the conditions, the pudding cup-shaped example cured product No. 3.5 mm in diameter x 4 mm in height was used. 29-56 were molded.

[Comparative Example 3] Production of comparative cured product 2
Comparative Example Composition No. 1-No. 30 was poured into a mold placed on a copper substrate (length 50 mm × width 55 mm × thickness 0.25 mm), 170 ° C. for 180 seconds (molding step), and then 150 ° C. for 2 hours (after-baking step) By heating under these conditions, pudding cup-shaped comparative example cured products 31 to 60 having a diameter of 3.5 mm and a height of 4 mm were formed.

[Evaluation Example 2] Pudding cup test 2 (copper substrate)
Example cured product No. About the 29-56 and comparative example hardened | cured material 31-60, the pudding cup test was done as follows. That is, the adhesion strength between the copper substrate and the molding resin is measured using a bond tester, and the case where the adhesion strength is higher than 20 kg / cm ² is defined as ++, the case where it is in the range of 5-20 kg / cm ² is defined as +, and 5 kg. / cm ² less than a is a case - to evaluate the adhesion as. When the evaluation result is +, it means that excellent adhesion is shown, and when it is ++, it means that particularly excellent adhesion is shown. The results are shown in Tables 4-1 to 4-4.

  As is clear from Tables 4-1 to 4-4, the comparative cured products 31 to 60 had poor adhesion. On the other hand, Example cured product No. using the silicon-containing curable composition of the present invention. All of Nos. 29 to 56 had good adhesion to a copper substrate.

ADVANTAGE OF THE INVENTION According to this invention, the silicon containing curable composition which can manufacture the hardened | cured material which is excellent in the adhesiveness to a silver base | substrate and a copper base | substrate, and is useful for an electrical / electronic material etc. can be provided. The silicon-containing curable composition has a good curability and can be molded by a mold such as transfer molding and injection molding, and the cured product has excellent heat resistance, crack resistance and mechanical strength. Therefore, it can be suitably used as a semiconductor sealing material, an LED sealing material, a molding material for a white LED package, and the like.

Claims (3)

As the component (A), a compound having a carbon-carbon double bond having reactivity with the SiH group,
(B) As a component, a siloxane compound having a SiH group,
As the component (C), a silane compound represented by the following general formula (1),
(D) The silicon-containing curable composition characterized by containing a filler as a component.
(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A represents an alkanediyl group having 1 to 10 carbon atoms, and k represents a number of 2 or 3).   A method of curing the silicon-containing curable composition comprising heating the silicon-containing curable composition according to claim 1. A cured product obtained by curing the silicon-containing curable composition according to claim 1.