KR20180135863A - The silicon-containing curing composition and the cured product thereof - Google Patents

Abstract

(B) a siloxane compound having a SiH group, (C) a silane compound represented by the following general formula (1), (D) a silane compound represented by the following general formula (1) Wherein the composition contains a filler as a component.
(Wherein 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.)

Description

The silicon-containing curing composition and the cured product thereof

The present invention relates to a silicon-containing curable composition and a cured product obtained by curing the same. The silicon-containing curable composition and the cured product thereof of the present invention are useful for a material suitable for a semiconductor, particularly for a package such as an LED and a lead frame.

Various studies have been conducted on silicon-containing compounds, and polysiloxane compounds have been used industrially to represent silicon resins. However, since the silicone resin is excellent in heat resistance and flexibility, but has many outgas components (volatile components), its use has been limited due to contamination problems in manufacturing processes of electronic components.

In recent years, in the field of electronic information, materials having high heat resistance and excellent physical and electrical properties are being exploited due to the characteristic properties of silicon because high performance is required for various materials used according to the development of technology. Among them, various techniques for producing a useful compound by applying the hydrosilylation reaction of a silicon compound have been investigated. In addition, a lithography process is widely used in a member manufacturing process in the field of electronic information, and a high resistance to basicity and solvent resistance has been demanded. For this reason, a material which satisfies both high heat resistance and crack resistance while maintaining a high resistance to alkali and solvent resistance has been demanded.

A variety of silicon-containing curable compositions have been proposed for these requirements (see, for example, Patent Documents 1 to 7, etc.).

However, although the technologies proposed for these have respective characteristics, they are not satisfactory in terms of heat resistance, light resistance, crack resistance, coloring property, and adhesion required for materials in recent electronic information fields. Among them, a problem of poor adhesion to a silver base or a copper base has been a big problem.

U.S. Patent No. 5645941 Japanese Patent Application Laid-Open No. 8-73743 Japanese Patent Application Laid-Open No. 2004-107577 Japanese Laid-Open Patent Publication No. 2005-68295 U.S. Patent Application Publication No. 2009/012256 Japanese Patent Application Laid-Open No. 2007-332259 JP-A-2009-120732

Accordingly, an object of the present invention is to provide a silicon-containing curable composition which is excellent in adhesion to silver or copper gases and which is capable of producing a cured product useful in electric and electronic materials.

The present inventors 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, they have completed the present invention.

That is,

A compound having a carbon-carbon double bond having reactivity with SiH groups as the component (A)

A siloxane compound having a SiH group as the component (B)

(C) a silane compound represented by the following general formula (1)

And a filler as a component (D).

(Wherein 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.)

The present invention also provides a method for curing the silicon-containing curable composition comprising heating the 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. The carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and examples thereof include a group represented by the following general formula (2) and a group forming an alicyclic ring represented by the following general formula (3). Use of a group capable of forming an alicyclic ring represented by the following general formula (3) is preferable because the heat resistance of the cured product becomes high.

(Wherein L ¹ represents hydrogen or a methyl group, and * represents a bond number).

(Wherein L ² represents hydrogen or a methyl group, and * represents the number of bonds).

Among the groups represented by the general formula (2), it is particularly preferable that L ¹ is hydrogen because the reactivity is good.

Of the groups forming an alicyclic ring represented by the general formula (3), it is particularly preferable that L ² is hydrogen because the reactivity is good.

Examples of the compound having a carbon-carbon double bond having reactivity with the SiH group include an organic compound having a carbon-carbon double bond (hereinafter sometimes abbreviated as (A-)) having reactivity with a SiH group, a SiH group (Hereinafter may be simply abbreviated as (A-β)) having a carbon-carbon double bond, which is reactive with a carbon-carbon double bond, can be preferably used. (A-a), only one kind of compound may be used, or plural kinds of compounds having different structures may be used. (A-beta), only one kind of compound may be used, or plural kinds of compounds having different structures may be used. Further, (A-?) And (A-?) May be mixed and used.

The above-mentioned (A-α) may be an organic compound having a carbon-carbon double bond having reactivity with SiH groups and is not particularly limited. However, it contains an element other than C, H, N, O, Is preferable. Particularly preferred examples of (A-alpha) include trimethyl isocyanurate and triallyl isocyanurate. These are commercially available as tie-and-tie products (manufactured by Nippon Kayaku Co., Ltd.), and these commercially available products can be used as (A-?) In the present invention.

The (A-β) may be any silicone compound having a carbon-carbon double bond having reactivity with a SiH group, and is not particularly limited. For example, a silicon-containing polymer containing a unit represented by the following formula (4) .

(Wherein R < ² > represents an alkenyl group having 2 to 6 carbon atoms, and * represents the number of bonds).

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 in view of reactivity.

The silicon-containing polymer containing the units represented by the general formula (4) can be obtained by, for example, hydrolyzing and condensing at least one or more organosilanes represented by the following general formula (A-1) , At least one organosilane selected from organosilanes represented by the following general formula (A-2) and organosilanes represented by the following general formula (A-3) Can be produced by hydrolysis and condensation of a mixture containing a siloxane and a siloxane.

(Wherein, R ³ is a shows an alkenyl group of carbon atoms ^{2 ~ 6, R 4, R} 5 and R ⁶ independently can represent a hydrogen atom or a hydrocarbon group, X ¹ is hydroxyl group, the carbon atom to 1-6 respectively 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 in view of reactivity.

Examples of the hydrocarbon group represented by R ⁴ , R ⁵ and R ⁶ in the general formulas (A-2) and (A-3) include aliphatic hydrocarbon groups such as alkyl groups, alkenyl groups and alkynyl groups, alicyclic hydrocarbon groups such as cycloalkyl groups An aromatic hydrocarbon group such as an aromatic hydrocarbon group, an aryl group, or an arylalkyl group. The hydrocarbon group preferably has 1 to 10 carbon atoms.

Examples of the alkoxy group having 1 to 6 carbon atoms represented by X ¹ in the general formula (A-1), the general formulas (A-2) and (A-3) include a methoxy group, Propoxy group, butoxy group, and the like, and 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 in view of reactivity.

In addition, each X ¹ in the general formulas (A-1) to (A-3) may be the same or different in some cases.

Of these, 5 to 50 mol% of at least one organosilane represented by the above-mentioned general formula (A-1) (hereinafter occasionally abbreviated as (a) (Hereinafter abbreviated as "(c)") of at least one organosilane represented by the following general formula (A-5) in an amount of 0 to 50 mol% And 0 to 50 mol% of at least one organosilane represented by the following general formula (A-6) (hereinafter sometimes abbreviated as (d) (B) and an organosilane (c) in an amount of 0 to 40 mol% of at least one organosilane represented by the following formula (A-7) It is particularly preferable to use a silicon-containing polymer obtained by hydrolysis / condensation of an organosilane mixture having a sum of 5 to 60 mol%.

(Wherein R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 2 to 6 carbon atoms Alkenyl group or an alkyl group having 1 to 6 carbon atoms, at least one of R ⁷ , R ⁸ and R ⁹ is a methyl group, R ¹⁰ is an alkyl group having 1 to 6 carbon atoms , R ¹¹ represents an epoxy group having 2 to 10 carbon atoms, and X ² represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.)

The alkyl group having 1 to 6 carbon atoms represented by R ⁷ in the general formula (A-4) can be any of straight chain, branched and cyclic groups. Specific examples thereof include methyl, ethyl, propyl, isopropyl, 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 in view of reactivity.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁸ and R ⁹ in the general formula (A-5) and the alkyl group having 1 to 6 carbon atoms, which may be substituted with a phenyl group represented by R ⁸ and R ⁹ , Include the same ones as those listed above as R < ⁷ >. Examples of the alkenyl group having 2 to 6 carbon atoms represented by R ⁸ and R ⁹ include the same groups as those listed for R ³ above. R ⁸ and R ⁹ are preferably a methyl group or an unsubstituted phenyl group in terms of industrial availability and particularly preferably a methyl group.

Examples of the alkyl group having 1 to 6 carbon atoms which may be substituted for the phenyl group represented by R ¹⁰ in the above general formula (A-6) include the same groups as those listed for R ⁷ above. R ¹⁰ is preferably a phenyl group which is not substituted in terms 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 cyclic ether of a 3-membered ring, and examples thereof include epoxyethyl group, glycidyl group, 2,3- , 3,4-epoxybutyl group, epoxyethylphenyl group, 4-epoxyethylphenylethyl group, 3,4-epoxycyclohexyl group, 2- (3,4-epoxycyclohexyl) And the like. R ¹¹ is preferably a glycidyl group, a 3,4-epoxycyclohexyl group or a 2- (3,4-epoxycyclohexyl) ethyl group in view of imparting adhesion to a heterogeneous material.

The Examples of the formula (A-4) ~ alkoxy group (A-7) the number of carbon atoms represented by X ² between 1 and 6, there may be mentioned a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc., X ² Include a chlorine atom, a bromine atom and an iodine atom. X ² is preferably a methoxy group or an ethoxy group in view of reactivity. The X ¹ in the general formula (A-1) and the respective X ² in the general formulas (A-4) to (A-7) may be the same or different from each other.

As the five components, X ¹ and When X < ^{2 >} is an alkoxy group (alkoxy silane) having a total of 1 to 6 carbon atoms, hydrolysis and condensation of alkoxysilane may be carried out by the so-called sol-gel reaction, In the presence of a catalyst such as an acid or a base in a solvent or a solvent. The solvent to be used here is not particularly limited and specific examples include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, And toluene. These may be used alone or in admixture of two or more.

The hydrolysis / condensation reaction of the alkoxysilane proceeds by hydrolysis of the alkoxysilane with water to produce a silanol group (Si-OH), and the resulting silanol groups or silanol groups and alkoxy groups are condensed. To proceed with this reaction, it is preferable to add an appropriate amount of water, and water may be added to the solvent, or the catalyst may be added in water. The hydrolysis / condensation reaction also proceeds by moisture in the air or a trace amount of water contained in the solvent.

The catalysts such as acids and bases used in the hydrolysis-condensation reaction are not particularly limited as long as they promote the hydrolysis and condensation reaction. Specific examples thereof include inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid; Organic acids such as acetic acid, oxalic acid, p-toluenesulfonic acid and monoisopropyl phosphate; Inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; Amine compounds such as trimethylamine, triethylamine, monoethanolamine and diethanolamine; Titanium esters such as tetraisopropyl titanate and tetrabutyl titanate; Tin carboxylates such as dibutyltin dilaurate and tin octylate; Boron compounds such as trifluoroboron; Metal carboxylates such as chlorides, naphthenates or octylates of metals such as iron, cobalt, manganese and zinc; And aluminum compounds such as aluminum trisacetylacetate. These compounds may be used alone or in combination of two or more.

As the hydrolysis-condensation reaction of the alkoxysilane, a method of adding a base catalyst and carrying out a polycondensation reaction under a basic condition (pH 7 or more) is a preferred example. It is also possible to carry out hydrolysis and dehydration polycondensation under acidic conditions (pH 7 or less) by adding an acid catalyst.

When the hydrolysis-condensation reaction is carried out, the reaction system is preferably stirred, and the reaction can be promoted by heating at 40 to 150 ° C.

The order of the hydrolysis-condensation reaction is not particularly limited. For example, the alkoxysilane (R ³ Si (X ¹ ) ₃ ) and alkoxysilane (R ⁷ Si (X ² ) ₃ , R ⁸ R ⁹ Si (X ² ) ₂ , R ¹⁰ Si (X ² ) ₃ and R ¹¹ Si (X ² ) ₃ ) can be quantitatively mixed to carry out the hydrolysis and condensation reaction. One of these five alkoxy A hydrolysis / condensation reaction may be carried out by adding another alkoxysilane to the hydrolysis / condensation reaction.

As the above-mentioned five components, X ¹ or X ² may be a hydroxyl group and X ¹ or X ² may be an alkoxy group. In this case, X ¹ and X ² may be hydroxyl groups without hydrolysis .

Halogenosilanes such as chlorosilane (X ¹ of the five components and And X < ² > is a halogen atom), a hydrolysis-condensation reaction can be carried out in the same manner as in the case of alkoxysilane.

In order to obtain the resulting silicon-containing polymer from the reaction system in which the hydrolysis-condensation reaction has been completed, the reaction solvent, water and catalyst may be removed. For example, a solvent such as toluene is added to extract the solvent, It may be distilled off under reduced pressure in an air stream.

In the organosilane mixture, the organosilane (a) is preferably 10 to 40 mol% from the viewpoint of controlling the crosslinking density at the time of curing.

As long as the sum of the organosilane (b) and the organosilane (c) is 5 to 60 mol%, the organosilane (b) and the organosilane (c) The silane (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 mol% from the viewpoint of imparting flexibility to the resin .

The organosilane (d) may not be used but is preferably 5 to 45 mol% from the viewpoint of controlling the melting temperature of the resin. The organosilane (e) may not be used, but it is preferably 5 to 25 mol% from the viewpoint of imparting adhesion to different materials.

The sum of the organosilane (b) and the organosilane (c) is preferably 25 to 55 mol% from the viewpoint of controlling the crosslinking density at the time of curing.

Further, the organosilane contained in the organosilane mixture is only the five components of the organosilanes (a), (b), (c), (d) and (e) .

In the silicon-containing polymer containing a unit represented by the above-mentioned general formula (4), for example, it is possible to use an organopolysiloxane derived from each of organosilanes (a), (b), (c), (d) 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 randomly connected two-dimensionally and three-dimensionally, and the respective terminals are OH groups, X ¹ and X < ^{2 &} gt ;. X ¹ and X ² is a group derived from an organosilane (a), (b), (c), (d) or (e)

The (R ³ SiO _3/2 ) also includes (R ³ SiX'O _2/2 ), and the (R ⁷ SiO _3/2 ) also includes (R ⁷ SiX'O _2/2 ) and to be the (R ¹⁰ SiO _3/2), the (R ¹⁰ SiX'O _2/2) is (R ¹¹ SiX'O _2/2) also to be included, and wherein (R ¹¹ SiO _3/2) Are also included. X 'is at least one of X ¹ and X ² contained in each of the organosilanes (a), (b), (d) and (e) X ² , or an OH group.

Among the silicon-containing polymers containing a unit represented by the general formula (4), the proportion of phenyl groups in the entire organic component (excluding silicon) is preferably 50 mass% or less, particularly preferably 40 mass% or less, By mass or less, particularly preferably 70% by mass or less. When the proportion of the phenyl group is high, the melting point of the silicon-containing polymer is increased, so that it is difficult to melt at the temperature at the time of molding, 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 proportion of the phenyl group is small and the proportion of the methyl group is large, and it is more preferable that the ratio of the phenyl group to the methyl group (electron: latter) is 30:50 to 30:80.

Among silicon-containing polymers containing a unit represented by the general formula (4), silicon-containing polymers having a weight average molecular weight of 300 to 100,000 in terms of polystyrene are preferable, and a weight average molecular weight is more preferably in a range of 800 to 50,000 . If the weight average molecular weight of the silicon-containing polymer is less than 300, thermal stability may deteriorate. If it is more than 100,000, the silicon-containing polymer may not melt at the treatment temperature in transfer molding, And the moldability may be lowered.

The silicon-containing polymer containing the unit represented by the general formula (4) may be used after being denatured. Modifications to be carried out on the silicon-containing polymer are not particularly limited, and various modifications that can be carried out to make a silicone resin into a reactive silicone resin are possible, and more specifically, amino modification, epoxy modification, carboxy modification, , Methacrylic modification, mercapto modification, phenol modification and the like can be carried out by a conventional method.

As described above, the silicon-containing polymer containing the unit represented by the above-mentioned general formula (4) can be used singly or as a mixture of two or more thereof.

Examples of the silicone compound preferably usable as the above (A-β) include a siloxane compound containing at least one carbon-carbon double bond having reactivity with Si-H groups in one molecule . The siloxane compound may be a siloxane compound containing at least one carbon-carbon double bond having reactivity with a Si-H group in one molecule and is not particularly limited. Examples thereof include linear, cyclic, Having a partial network, and the like. Among them, a siloxane compound containing two or more carbon-carbon double bonds having reactivity with Si-H groups in one molecule is preferable, and two or more carbon-carbon double bonds having reactivity with Si- Or a cyclic siloxane compound containing two or more carbon-carbon double bonds having reactivity with Si-H groups in one molecule is used, a silicon-containing curing composition having a higher adhesion strength can be obtained Particularly preferred.

The linear siloxane compound containing two or more carbon-carbon double bonds having reactivity with the Si-H group in one molecule is preferably a linear siloxane compound having two or more carbon-carbon double bonds having reactivity with Si- Is a linear siloxane copolymer. The linear siloxane copolymer may be a random copolymer or a block copolymer. The number of carbon-carbon double bonds having reactivity with Si-H groups is preferably from 2 to 10, more preferably from 2 to 6 in terms of crosslinking density of the cured product. Examples of the carbon-carbon double bond include an alkenyl group such as a vinyl group, a 2-propenyl group and a 3-butenyl group. However, since the reactivity is good, a vinyl group bonded to a silicon atom (Si- ₂ group).

Among straight-chain siloxane copolymers containing two or more carbon-carbon double bonds having reactivity with Si-H groups in one molecule, those represented by the following general formula (A-8) And linear siloxane copolymers.

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

Examples of the alkenyl group having 2 to 6 carbon atoms represented by R ¹² and R ³¹ in the general formula (A-8) and represented by R ²¹ , R ²² , and R ²³ include the same groups as listed above as R ³ .

In addition, the alkyl group of R ¹² and R ^31, and ^{R 13, R 14, R 15} , R 16, R 20, R 24, R 28, R 29 and the number of carbon atoms represented by R ³⁰ 1 ~ 6, as the R ⁷ And the like.

Examples of the epoxy group having 2 to 10 carbon atoms represented by R ¹² and R ³¹ , and R ²⁵ , R ²⁶ and R ²⁷ include the same groups as those listed for R ¹¹ above.

The general formula (A-8) in R ¹² and R ³¹ are, and the vinyl group or a 2-propen group preferable in view of ^{reactivity, R 13, R 14, R} 15, R 16, R 20, R 24, R ²⁸ , R ²⁹ and R ³⁰ are preferably a methyl group or an ethyl group in terms of industrial availability, and R ²¹ , R ²² and R ²³ are preferably a vinyl group or a 2-propenyl group in terms of industrial availability .

Among these, preferable specific examples of the linear siloxane copolymer containing two or more carbon-carbon double bonds having reactivity with the Si-H group in one molecule are represented by the following formulas (A-9) to (A-17) A straight chain siloxane compound represented by the following formula

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

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

(In the formula, p is the same as in the general formula (A-8).)

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

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

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

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

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

In the cyclic siloxane compound containing at least two carbon-carbon double bonds reactive with Si-H groups in one molecule, the number of carbon-carbon double bonds is preferably from 2 to 10, and the crosslinking density And therefore, it is more preferably 2 to 6. In addition, the carbon-carbon double bond as a vinyl group, 2-propene group, but 3-butene can be mentioned alkenyl groups such as a group, because the reactivity is preferably a vinyl group (bonded to the silicon atom Si-CH = CH ₂ Group).

Of the cyclic siloxane compounds containing two or more carbon-carbon double bonds having reactivity with the Si-H group in one molecule, cyclic siloxane compounds represented by the following formula (A-18) are particularly preferable from the viewpoint of the physical properties of the cured product .

(Wherein R ³² , R ³³ and R ³⁴ each represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, n R ^{32 s} may be the same or different, and m R ³³ , m R ³⁴ N is a number of 2 to 10, m is 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 include the same groups as those listed for R ⁷ above. Among the above-mentioned general formula (A-18), R ³² , R ³³ and R ³⁴ are preferably a methyl group or a phenyl group in terms of industrial availability. n is preferably from 2 to 4, and m is preferably from 1 to 3 in terms of viscosity since the crosslinking density is good.

Among these, preferable specific examples of the cyclic siloxane copolymer containing two or more carbon-carbon double bonds in the molecule having reactivity with Si-H groups are represented by the following formulas (A-19) to (A-21) And cyclic siloxane compounds.

In addition, although a compound having a carbon-carbon double bond capable of reacting with a SiH group may have a SiH group (for example, a compound represented by the above formula (A-17)), these compounds are not a component (B) (A). (B) does not have a carbon-carbon double bond having reactivity with SiH groups.

The component (B) in the silicon-containing curable composition of the present invention is a siloxane compound having a SiH group. (B) may be a siloxane compound having at least one SiH group in one molecule, and is not particularly limited, but a siloxane compound having at least two SiH groups in one molecule can be preferably used.

The content of the component (B) in the silicon-containing curable composition of the present invention is preferably from 0.1 to 100 parts by mass, more preferably from 1 to 60 parts by mass, per 100 parts by mass of the component (A) And more preferably in the range of 5 to 40 parts by mass.

Among the siloxane compounds having two or more SiH groups in one molecule, at least one selected from the cyclic siloxane compounds represented by the following formula (B-1) and the following formula (B-2) (B-a) having at least two SiH groups in one molecule, obtained by subjecting at least one compound selected from compounds represented by the following general formula (B-4) or (B-4) ) Can be preferably used.

(Wherein, R ^35, R ³⁶ and R ³⁷ are, each independently, if it is substituted with an alkyl group carbon atom number of 1 to 6 alkyl groups or 1 to 6 carbon atoms in the Figure represents a phenyl group, f of R ³⁵ is in some cases other also equal, g of R ^36, g of R ³⁷ when also the same respectively, also are other cases. f represents a number of 2 ~ 10, g represents a number of 0 ~ 8, f + g ≥2.)

(Wherein R ³⁸ represents an alkenyl group having 2 to 10 carbon atoms, R ³⁹ and R ⁴⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a carbon atom Represents an epoxy group of 2 to 10, and h represents 1 or 2.)

The alkyl group having 1 to 6 carbon atoms represented by R ³⁵ , R ³⁶ and R ³⁷ in the general formula (B-1) can be any of linear, branched and cyclic. Specific examples thereof include methyl, ethyl, Propyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl and cyclohexyl groups.

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 4 to 6, and g is preferably 0 to 1 in terms of the crosslinking density of the curing reaction. When both the methyl group and the phenyl group are contained, it is preferable that the ratio of the number of methyl groups to the number of phenyl groups (electron: latter) in the total number of R ³⁵ to R ³⁷ substituents is in the range of 4: 1 to 1: 4 Because the molecular weight can be controlled.

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

The alkyl group having 1 to 10 carbon atoms represented by R ³⁹ and R ⁴⁰ in the general formula (B-4) can be any of straight chain, branched and cyclic groups. Specific examples thereof include methyl, ethyl, An ethyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an isobutyl group, an isoamyl group, a t-amyl group, a hexyl group, a cyclohexyl group, a heptyl group, And practical training.

The epoxy group having 2 to 10 carbon atoms represented by R ³⁹ and R ⁴⁰ in the general formula (B-4) is a substituent having a cyclic ether of a 3-membered ring and includes, for example, epoxy ethyl group, glycidyl group, Epoxycyclohexyl group, a 2- (3,4-epoxycyclohexyl) ethyl group, a 2,3-epoxycyclohexyl group, a 2,3-epoxycyclohexyl group, Epoxycarbonyl ethyl 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, 1 , 3,5,7,9,11-hexamethylcyclohexasiloxane, and the like, and 1,3,5,7-tetramethylcyclotetrasiloxane is preferable. The cyclic siloxane compound represented by the general formula (B-1) may be used alone, or two or more kinds may be used in combination.

The compound represented by the above general formula (B-2) represents divinylbenzene when h is 1, and o-divinylbenzene, m-divinylbenzene or p-divinylbenzene are all possible. Represents trivinylbenzene, and 1,2,3-trivinylbenzene, 1,2,4-trivinylbenzene and 1,3,5-trivinylbenzene are all possible. The compound represented by the above general formula (B-2) may have a functional group other than the vinyl group (for example, an alkyl group such as a methyl group) bonded to the benzene ring, or a mixture thereof.

Among the compounds represented by the general formulas (B-2), (B-3) and (B-4), divinylbenzene is preferred. The compounds represented by the general formulas (B-2), (B-3) and (B-4) may be used singly or in combination of two or more.

(B-2), (B-3) or (B-3), at least one kind selected from cyclic siloxane compounds represented by the general formula (B- 4) may be subjected to a hydrosilylation reaction. (B-2), the compound represented by the formula (B-3) or the compound represented by the formula (B-4), and at least one compound selected from the cyclic siloxane compounds represented by the above- The blending ratio of at least one 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 at least one cyclic siloxane compound represented by the formula (B-1) and the number of SiH groups contained in the cyclic siloxane compound represented by the formula (B-2), the formula (B-3) (Electron: latter) of the number of carbon-carbon double bonds having reactivity with the SiH group, contained in at least one selected from the compounds represented by the general formula (B-4) is in the range of 10: 1 to 2: 1 And more preferably in the range of 4: 1 to 2: 1.

The SiH group concentration of (B-?) Is preferably from 0.0001 mmol / g to 100 mmol / g, more preferably from 0.01 mmol / g to 20 mmol / g since the curing property becomes good.

The (B-alpha) preferably has a weight-average molecular weight of 500 to 500,000, and more preferably 1000 to 300,000 because heat resistance is good. The weight average molecular weight can be measured by GPC or by polystyrene conversion.

The hydrosilylation reaction may be carried out using a platinum catalyst. As the platinum-based catalyst, a known catalyst containing at least one metal of platinum, palladium and rhodium which promotes the hydrosilylation reaction can be used. Examples of the platinum-based catalysts used as the catalyst for the hydrosilylation reaction include platinum-carbonylvinylmethyl complexes, platinum-divinyltetramethyldisiloxane complexes, platinum-cyclovinylmethylsiloxane complexes and platinum-octylaldehyde complexes A platinum-based catalyst, and a compound containing palladium, rhodium, or the like, which is a platinum group metal, instead of platinum. One of these compounds may be used alone, or two or more of them may be used in combination. In particular, platinum is preferably contained in view of curability. Specifically, platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) and platinum-carbonylvinylmethyl complex (Ossko catalyst) are preferable. Also, a so-called Wilkinson catalyst containing the platinum-based metal such as chlorotris (triphenylphosphine) rhodium (I) is included in the platinum-based catalyst in the present invention. The amount of the platinum-based catalyst to be used may be at least one selected from the cyclic siloxane compounds represented by the general formula (B-1) in view of reactivity, and at least one kind selected from the group consisting of the general formulas (B-2) Is preferably 5 mass% or less, more preferably 0.0001 to 1.0 mass%, based on the total amount of at least one compound selected from the compounds represented by the general formula (B-4). The conditions for the hydrosilylation reaction are not particularly limited and may be carried out under conventionally known conditions using the above catalyst. However, from the viewpoint of the curing rate, the hydrosilylation reaction is preferably carried out at room temperature to 130 ° C, A conventionally known solvent such as hexane, MIBK (methyl isobutyl ketone), cyclopentanone, PGMEA (propylene glycol monomethyl ether acetate) or the like may be used. Further, the catalyst may be removed after the hydrosilylation reaction, and the catalyst may be used as it is for the silicon-containing curing composition without being removed.

The component (C) in the silicon-containing curable composition of the present invention is the silane compound represented by the above general formula (1). Containing curing composition capable of producing a silicon-containing cured product having excellent adhesion to a silver substrate or a copper gas by using the component (C) in combination with the component (A), the component (B) and the component (D) Can be obtained. The content of the component (C) in the silicon-containing curable composition of the present invention is preferably 0.001 to 0.1 part by mass based on 100 parts by mass of the component (A). When the amount is less than 0.001 parts by mass, the effect of addition is difficult to manifest. Even if the amount is more than 0.1 part by mass, the compounding effect is hardly improved.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ in the general formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a butyl group and a tert- have. Among these, a methyl group or an ethyl group is preferable because the resulting cured product has a high effect of having excellent adhesion to a silver substrate or a copper substrate.

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by A in the general formula (1) include a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, a pentylene group, a hexylene group, Anthrylene, and the like. An alkanediyl group having 1 to 5 carbon atoms is more preferable, and a propylene group is particularly preferable because the resulting cured product has a high effect of having excellent adhesion to silver or copper.

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

Specific preferred examples of the compound represented by the general formula (1) include the compounds represented by the following general formulas (1) to (20). In the following formulas (Nos. 1 to 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. The cured product obtained by using the component (D) in combination with the above components (A) to (C) can be colored with a desired color and the hardness of the resulting 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 1,500 parts by mass, more preferably 100 to 1,400 parts by mass, further preferably 300 to 1,350 parts by mass based on 100 parts by mass of the component (A) More preferred is an addition. 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 added as a white coloring agent in order to increase whiteness. For example, titanium oxide is preferably used. The unit lattice of the titanium oxide may be any of rutile type, anatase type and blue kite type, Considering the light resistance, a rutile type is preferably used. The average particle diameter and shape are not limited, but the average particle diameter is usually 0.05 to 5.0 mu m. The titanium oxide can be surface-treated in advance with a hydrous oxide such as Al or Si in order to improve the compatibility with the resin or the inorganic filler and the dispersibility.

The average particle diameter can be determined by a mass average value D ₅₀ (or median diameter) in the particle size distribution measurement by the laser diffraction method.

As the white pigment, potassium titanate, zirconium oxide, zinc sulfide, alumina, zinc oxide, magnesium oxide, beryllium oxide, barium sulfate and the like may be used in addition to titanium oxide. Of these, magnesium oxide and zinc oxide are preferable. These white pigments can be used singly or in combination with titanium oxide.

As the inorganic filler, those generally used in a sealing material such as a silicone resin composition or an epoxy resin composition can be used. Examples thereof include silicas such as fused silica, spheroidal silica, crystalline silica, colloidal silica, fumed silica and silica gel; Metal oxides such as alumina, iron oxide, titanium oxide, and antimony trioxide; Ceramics such as silicon nitride, aluminum nitride, boron nitride, 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 or the like; Metal carbonates such as calcium carbonate, calcium silicate, magnesium carbonate, barium carbonate and the like, or those modified by organic modification treatment or the like; Pigments such as metal borates and carbon black; Silica glass, laminar clay mineral, clay, silicon carbide, quartz, aluminum, zinc, and the like can be given as examples of the carbon fiber, graphite, whisker, kaolin, talc, glass fiber, glass bead, glass microsphere. As the filler (D), organic fillers such as acrylic beads, polymer fine particles, transparent resin beads, wood powder, pulp, and cotton chips may be used.

The average particle diameter and shape of the inorganic filler and the organic filler are not particularly limited, but the average particle diameter is usually 0.1 to 80 탆. The average particle diameter can be determined by a mass average value D ₅₀ (or median diameter) in the particle size distribution measurement by the laser diffraction method.

The inorganic filler is preferably a silica, a metal oxide, a metal carbonate, or a pigment which may be modified, from the viewpoints of moldability and strength of the resin. Particularly preferred are fused silica, molten spherical silica, crystalline silica, Colloidal silica, aluminum oxide, titanium oxide, calcium carbonate, magnesium carbonate, carbon black, kaolin and glass fiber are preferable.

As the inorganic filler, a fused silica, a fused spherical silica, and a composite of titanium oxide and calcium carbonate are suitably used in view of moldability of the resin. The particle diameter is not particularly limited, but is preferably 4 to 40 占 퐉, particularly preferably 7 to 35 占 퐉 in terms of moldability and fluidity. Further, in order to obtain high fluidity, it is preferable to use a combination of a fine region of 3 탆 or less, an intermediate grain diameter region of 4 to 8 탆, and a rough grain diameter region of 10 to 40 탆.

The silicon-containing curable composition of the present invention may further contain additives such as an organic peroxide, a metal catalyst, an adhesive aid, a free radical scavenger, various known resins , A releasing agent, an additive, and the like can also be incorporated. The amount of each optional component to be used is not particularly limited. However, in order to prevent the effect of the present invention from being impaired, it is preferable that the content is 10% by mass or less, preferably 5% by mass or less desirable.

As the above-mentioned organic peroxide, for example, those generally used for curing the silicone rubber composition can be used, and examples thereof include benzoyl peroxide, o-methylbenzoyl peroxide, p-methylbenzoyl peroxide, Dichlorobenzoyl peroxide, 2,4-dicumyl benzoyl peroxide, di-t-butyl benzoyl peroxide, t-butyl benzoate, t-butyl benzoyl peroxide, t-butyl benzoyl peroxide, -Butyl cumyl benzoyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (t- butylperoxy) Dicumylperoxycarbonate, t-butylperoxy 2-ethylhexylcarbonate, dicyclododecylperoxydicarbonate, dicyclohexylcarbodiimide, dicyclohexylcarbodiimide, dicyclohexylcarbodiimide, dicyclohexylcarbodiimide, ) Or (5 '), and the like. Of these, benzoyl peroxide compounds are preferable from the viewpoints of reactivity and workability, and benzoyl peroxide and 2,4-dicumyl benzoyl peroxide are particularly preferable.

(Wherein R and R 'are each independently a hydrocarbon group of 3 to 10 carbon atoms).

Examples of the hydrocarbon group having 3 to 10 carbon atoms and represented by R in the general formulas (5) and (5 ') and R' in the general formula (5 ') include propyl, isopropyl, butyl, Butyl, isobutyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, cyclohexylmethyl, 2-cyclohexylethyl, An alkyl group such as a methyl group, an ethyl group, an ethyl group, an ethyl group, a propyl group, an isopropyl group, an ethyl group, 2-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butyl Phenyl, 4-isobutylphenyl, 4- tert -butylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, Alkyl aryls such as 3,5-dimethylphenyl, 2,4-di- , Arylalkyl groups such as benzyl, 2-phenylpropan-2-yl, styryl, cinnamyl and the like, those in which they are interrupted by an ether bond or thioether bond such as 2-methoxyethyl, 3-methoxypropyl Methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-phenoxyethyl, 3-phenoxypropyl, 2- methylthioethyl , And 2-phenylthioethyl, and these groups may be substituted with an alkoxy group, an alkenyl group, a nitro group, a cyano group, a halogen atom, or the like.

The content of the organic peroxide is preferably 0.0001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the component (A).

Examples of the metal catalyst include platinum catalysts, tris (2,4-pentanedionato) aluminum, triisopropoxide aluminum, Al (ClO ₄ ) ₃ , tetraisopropoxide titanium, tetraisobutoxide titanium, dibutyl Metal catalysts such as Al-based, Ti-based, and Sn-based catalysts such as bis (2,4-pentanedionato) tin and Bu ₂ Sn (C ₇ H ₁₅ COO) ₂ .

Among these, platinum-based catalysts and Al-based catalysts are preferable from the viewpoints of reactivity and colorability, and particularly preferred are platinum-carbonylvinylmethyl complex (Ossko catalyst), platinum-divinyltetramethyldisiloxane complex (Karstedt complex), tris , 4-pentanedionato) aluminum are preferable.

The content of the metal catalyst is preferably 1 x 10 ^-4 to 0.5 parts by mass, more preferably 1 x 10 ^-3 to 0.2 parts by mass based on 100 parts by mass of the component (A) Do.

As the adhesive aid, for example, a compound having a cyanuric acid structure can be used. The compound having a cyanuric acid structure includes, for example, isocyanuric acid, triallyl cyanuric acid, 1,3,5-triglycidylisocyanuric acid, tris (2-hydroxyethyl) isocyanuric acid (2,3-dihydroxypropyl) isocyanuric acid, tris (2,3-epoxypropyl) isocyanuric acid, Japanese Patent No. 2768426, Japanese Patent Application Laid-Open No. 3-261769, 4-139211, 4-139174, and 10-333330, and the like can be used. These compounds may also be subjected to various modifying treatments such as silicone denaturation, ethylene oxide denaturation, and propylene oxide denaturation in some cases by conventional methods. When a compound having a cyanuric acid structure is used, the content of the compound in the silicon-containing curable composition of the present invention is preferably 0.0001 to 10 mass%, more preferably 0.01 to 1.0 mass%.

Examples of the free radical scavenger include antioxidative substances such as antioxidants and stabilizers. (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], dibutylhydroxytoluene (BHT), 2,6- t-butyl-paracresol (DBPC), and the like. When a free radical scavenger is used, 0.1 to 10% by mass is preferable in the silicon-containing curable composition of the present invention in terms of heat resistance, electrical characteristics, curability, mechanical properties, storage stability and handling, % 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 glycols, polyphenylene ethers, polypropylene glycols Epoxy resins, phenol resins, polyester resins, melamine resins, polyamide resins, polyphenylene sulfide resins, and the like.

Examples of the releasing agent include carnauba wax, fatty acid ester, glyceric acid ester, stearic acid, montanic acid, behenic acid and metal salt thereof, alkali metal compound, organic titanium, organic zirconia, organic tin compound, imidazole compound, Group-containing polyolefin, polyethylene-polyoxyethylene resin, carnauba and the like.

Examples of the additives that can be arbitrarily compounded include additives such as a brightener, a wax, an ultraviolet absorber, an antistatic agent, an antioxidant, a deterioration inhibitor, a denaturant, a silane coupling agent, a defoamer, Based compounds, cyanate ester-based compounds, silicone gels, and silicone oils.

The silicon-containing curable composition of the present invention is solid at room temperature (25 캜), and therefore has excellent handling properties. The silicon-containing curable composition of the present invention may be in the form of a powder, a granule, a tablet or the like, and may be dissolved in a solvent before use. The silicon-containing curable composition of the present invention preferably has a melting point of from 50 캜 to 150 캜, more preferably from 50 캜 to 120 캜. The silicon-containing curable composition of the present invention is preferably melted at 50 ° C to 150 ° C and then cured by heat. Further, the cured product of the silicon-containing curable composition of the present invention is excellent in adhesion to silver and copper gases, and has excellent heat resistance and adhesion. Regarding heat resistance, a cured product having a temperature of 400 deg. C or higher, more preferably 500 deg. C or higher, which brings about a weight reduction of 5 mass% of the cured product, is suitably obtained. Further, a cured product having a small amount of cracks is suitably obtained from the silicon-containing curable composition of the present invention.

The silicon-containing curable composition of the present invention can be uniformly transparent, and in this case, it is also transparent to light such as ultraviolet rays, and photo-curing can also be achieved by adding a photoreactive catalyst. Of course, a photoreactive monomer or resin may be further blended, and at least one of the components in the silicon-containing curable composition may have a photoreactive group. The silicon-containing curable composition of the present invention can also be used as a curable composition for a semiconductor device which is excellent in weatherability, hardness, stain resistance, flame retardance, moisture resistance, gas barrier property, flexibility, mechanical properties such as elongation and strength, electrical insulation, Characteristics 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 carried out by a method in which the compounding components of the silicon-containing curing composition of the present invention are mixed and heated immediately before use, and the curing reaction is carried out by a method in which the components are mixed in advance and the curing reaction is carried out It is possible.

The heating temperature at the time of curing is preferably at least the temperature at which the resin is melted, for example, 35 to 350 DEG C, more preferably 50 to 250 DEG C. The curing time is preferably 2 to 60 minutes, more preferably 2 to 10 minutes. It may also be annealed or molded after curing. The annealing time varies depending on the temperature, but it is preferable to treat the annealing at 150 ° C for 5 to 60 minutes. By performing the curing reaction under these curing reaction conditions, a cured product having excellent performance 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, cast molding and the like can be used, and transfer molding is preferable in view of workability and dimensional stability.

The transfer molding is preferably carried out using a transfer molding machine at a molding pressure of 5 to 20 N / mm 2, at a molding temperature of 120 to 190 ° C for 30 to 500 seconds, particularly at 150 to 185 ° C for 30 to 180 seconds. The compression molding method is preferably carried out using a compression molding machine at a molding temperature of 120 to 190 DEG C for 30 to 600 seconds, particularly at 130 to 160 DEG C for 120 to 300 seconds. In any of the molding methods, curing can be carried out under the conditions of 150 to 185 ° C for 2 to 20 hours.

When the silicon-containing curable composition of the present invention is cured, a film forming method such as spin casting, potting, dipping and the like can be appropriately applied.

The silicon-containing curable composition of the present invention can be used as a curable composition which is excellent in various properties such as heat resistance, light resistance, crack resistance and coloration, in addition to having excellent adhesion to silver and copper gases. The silicon-containing curable composition and the cured product of the present invention can be used as sealing materials for display materials, optical materials, recording materials, printed boards, semiconductors and solar cells in the field of electric and electronic materials; High-voltage insulation materials, insulation, dustproof, waterproof and moisture-proof materials. Examples of applications include a prototype model of a plastic part, a coating material, an interlayer insulating film, a prepreg, an insulating packing, a heat-shrinkable rubber tube, an O-ring, a sealant or a protective material for a display device, an optical waveguide, A heat-resistant sealing material, a heat-resistant sealing material, a member for a solar cell and a fuel cell, a solid electrolyte for a battery, an insulating covering material, a photosensitive drum for a radiator, a gas separation membrane . In addition, it can be applied to concrete protecting materials, lining, soil injecting agent, sealing agent, cold cooling material, glass coating, foam, and paint in the field of civil engineering and construction materials. In the field of medical materials, Materials, printed board applications, sealing materials for sterilization processing apparatuses, contact lenses, oxygen enrichment membranes, and the like. It can be applied to other films, gaskets, mold materials, various molding materials, rustproofing and waterproofing sealants for wire glass, automobile parts, and various mechanical parts.

Example

Hereinafter, the present invention will be further described with reference to Examples and the like, but the present invention is not limited to these Examples and the like. In the examples, "part" and "%" are based on the mass basis.

[Table 1]

* 1: A silicon compound having a carbon-carbon double bond having reactivity with a SiH group, which is a silicon-containing polymer containing a unit represented by the general formula (4)

* 2: A straight-chain siloxane compound having a carbon-carbon double bond reacting with SiH groups and containing at least two carbon-carbon double bonds having reactivity with Si-H groups Molecular weight 12,000)

* 3: An organic compound having a carbon-carbon double bond having reactivity with SiH groups

* 4: The compound (B-α)

* 5: A siloxane compound represented by the following formula (synthesized by the method disclosed in JP-A-2013-079328)

[Preparation Example 1] Synthesis of A-1

(A), 0.5 mol of methyltrimethoxysilane as a component (b), and 0.5 g of dimethyldimethoxysilane 0.25 as a component (c) were added to a 2000-mL four-necked flask equipped with a stirrer, 1.0 mol of phenyltrimethoxysilane as component (d), and 650 g of toluene were placed and 31.4 g of a 0.5% sodium hydroxide aqueous solution was added dropwise over 30 minutes while stirring, followed by dehydration polymerization at 60 to 65 ° C for 3 hours. After cooling to room temperature, 600 g of toluene and 1500 g of ion-exchanged water were added to extract the oil layer. After washing with water until neutral, the solvent was removed to obtain 232.6 g of the silicon-containing polymer A-1 as the component (A) (White powder). The weight average molecular weight (Mw) of the silicon-containing polymer A-1 was analyzed by GPC according to the following conditions, and found to be Mw = 15000 (in terms of polystyrene).

(Measurement conditions of GPC)

Column: Super Multipore HZ-M

Developing solvent: tetrahydrofuran

[Preparation 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 parts of platinum-carbonyl vinylmethyl complex (Ossko catalyst) were added and refluxed for 5 hours while stirring. did. From the reaction solution, the solvent was distilled off under reduced pressure at 70 캜 to obtain prepolymer B-1 as component (B).

The prepolymer B-1 had a weight average molecular weight Mw of 140,000 (in terms of polystyrene) and a content of hydrosilyl group (Si-H group) of 5.3 mmol / g from ¹ H-NMR .

[Example 1] Preparation of silicon-containing curing composition

The compositions shown in Table 1 were used to prepare Example Compositions Nos. 1 to 28 in the formulations shown in Table 2 below.

[Table 2]

[Comparative Example 1] Preparation of comparative silicon-containing curing composition

Comparative Examples 1 to 30 were prepared by using the compounds shown in Table 1 and the following Comparative Compounds 1 to 3 in the formulation shown in Table 3.

[Table 3]

[Example 2] Production of cured product 1

Example Composition Nos. 1 to 28 were each put in a mold provided on a silver base (length 50 mm x width 55 mm x thickness 0.25 mm), and then heated at 170 DEG C for 180 seconds (molding step) (After-baking process) for 2 hours to form hardened pieces No. 1 to No. 28 of Example of the shape of a pudding cup having a diameter of 3.5 mm and a height of 4 mm.

[Comparative Example 2] Preparation of comparative cured product 1

COMPARATIVE EXAMPLE Compositions No. 1 to No. 30 were each put in a mold provided on a silver base (50 mm in length x 55 mm in width x 0.25 mm in thickness), heated at 170 DEG C for 180 seconds (molding step) (After-baking step) for 2 hours to form Comparative Examples 1 to 30 of pudding cups having a diameter of 3.5 mm and a height of 4 mm.

[Evaluation Example 1] Pudding cup test 1 (silver vapor)

EXAMPLES For the cured products No. 1 to 28 and the comparative cured products 1 to 30, the pudding cup test was carried out as follows. That is, the adhesion between the silver foil and the molding resin was measured using a bond tester, and when the adhesion was higher than 20 kg / cm < 2 > was taken as ++, when the adhesion was in the range of 5 to 20 kg / The case was evaluated as -, and the adhesion was evaluated. When the evaluation result is +, it means that excellent adhesion is exhibited. When the evaluation result is ++, it means that it shows particularly excellent adhesion. The results are shown in Tables 3-1 to 3-4.

[Table 3-1]

[Table 3-2]

[Table 3-3]

[Table 3-4]

As is evident from Tables 3-1 to 3-4, the comparative cured products 1 to 30 had poor adhesion. On the other hand, all of the hardened products Nos. 1 to 28 using the silicon-containing curable composition of the present invention had good adhesiveness to the gas. Among them, the cured products No. 1 to 18 had very high adhesiveness.

[Example 3] Production of cured product 2

Example Composition Nos. 1 to 28 were each put in a mold provided on a copper base (50 mm in length x 55 mm in width x 0.25 mm in thickness), heated at 170 DEG C for 180 seconds (molding step) (After-baking process) for 2 hours to form hardened pieces 29 to 56 of Example of the shape of a pudding cup having a diameter of 3.5 mm and a height of 4 mm.

[Comparative Example 3] Production of Comparative Cured Product 2

COMPARATIVE EXAMPLES Composition Nos. 1 to 30 were each put in a mold provided on a copper base (50 mm long x 55 mm x 0.25 mm thick), heated at 170 DEG C for 180 seconds (molding step), then at 150 DEG C For 2 hours (after-baking step) to form comparative cured products 31 to 60 having a pudding cup shape having a diameter of 3.5 mm and a height of 4 mm.

[Evaluation Example 2] Pudding cup test 2 (copper gas)

EXAMPLES For the cured products No. 29 to 56 and the cured products for comparison 31 to 60, the following pudding cup test was carried out. That is, the adhesive force between the copper substrate and the molding resin was measured by using a bond tester, and when the adhesion was higher than 20 kg / cm 2, it was taken as ++, while when the adhesion force was in the range of 5 to 20 kg / cm 2, - >, the adhesion was evaluated. When the evaluation result is +, it means that excellent adhesion is exhibited. When the evaluation result is ++, it means that it shows particularly excellent adhesion. The results are shown in Tables 4-1 to 4-4.

[Table 4-1]

[Table 4-2]

[Table 4-3]

[Table 4-4]

As is evident from Tables 4-1 to 4-4, the hardened materials 31 to 60 of Comparative Examples were poor in adhesion. On the other hand, the hardened pieces No. 29 to 56 of the examples using the silicon-containing curable composition of the present invention all had good adhesion to copper gas.

According to the present invention, it is possible to provide a silicon-containing curable composition which is excellent in adhesion to a silver substrate or a copper substrate and which is capable of producing a cured product useful for electric and electronic materials. The silicon-containing curable composition has good curability and can be molded into a mold such as a transfer mold or an injection molding. Since the cured product is excellent in heat resistance, crack resistance and mechanical strength, , A mold material for a package for a white LED, and the like.

Claims (3)

A compound having a carbon-carbon double bond having reactivity with SiH groups as the component (A)
A siloxane compound having a SiH group as the component (B)
(C) a silane compound represented by the following general formula (1)
And a filler as a component (D).

(Wherein 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, which comprises heating the silicon-containing curable composition of claim 1. A cured product obtained by curing the silicon-containing curable composition according to claim 1.