TW201437287A - Curable resin composition - Google Patents

Abstract

Provided is a curable resin composition having excellent adhesiveness, especially adhesiveness after a moisture resistance reflow test. This curable resin composition contains: (A) a branched organopolysiloxane having an alkenyl group (B) a linear organopolysiloxane having at least two silicon atom-linked hydrogen atoms per molecule (C) a block copolymer containing (c1) a polysiloxane block and (c2) a hydrocarbon polymer block and (D) a catalyst for a hydrosilylation reaction.

Description

Curable resin composition

The present invention relates to a curable resin composition.

A curable resin composition containing a hydrazine resin has been known, and is used, for example, as a composition for optical semiconductor sealing.

For example, Patent Document 1 [Request 1] discloses "a curable organopolyoxane composition comprising at least (A) at least three alkenyl groups in one molecule and bonded to a ruthenium atom bond. a branched organopolyoxane having at least 30 mol% of an organic group as an aryl group; (B) a linear organopolyoxane having an aryl group at both ends of the molecular chain and terminated by a diorganohydroquinoneoxy group (C) a branched organopoly group having at least 3 diorganohydroquinoneoxy groups in one molecule and at least 15 mol% of all organic groups bonded to the ruthenium atom bonded to an aryl group a siloxane (...) and (D) a catalyst for hydrogenation reaction...".

[Practical Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-1336

In recent years, the performance level required for the curable resin composition containing an anthracene resin has been increasing, for example, it is required to have better adhesion to the adherend.

In particular, when the reflow test (wet resistance reflow test) is carried out after standing for a long time in a high-humidity environment, it is also required to exhibit excellent adhesion.

The present invention has been made in view of the above points, and an object thereof is to provide a curable resin composition excellent in adhesion, particularly in adhesion after wet-resistance reflow test.

As a result of intensive studies to achieve the above object, the present inventors have found that the adhesion of the specific block copolymer to the curable resin composition can improve the adhesion after the wet reflow test, and thus the present invention has been completed.

That is, the present invention provides the following (I) to (V).

(I) A curable resin composition comprising a branched organopolysiloxane having an alkenyl group (A) and a linear organopoly group having at least two hydrogen atoms bonded to a halogen atom in one molecule A siloxane (B), a block copolymer (C) containing a polyoxyalkylene block (c1) and a hydrocarbon-based polymer block (c2), and a catalyst (D) for hydrogenation reaction.

(II) The curable resin composition according to the above (I), wherein the hydrocarbon-based polymer block (c2) contains a (meth) propylene-based polymer block and/or an isobutylene-based polymer block.

(III) The curable resin composition according to the above (I) or (II), wherein the block copolymer (C), the polyoxyalkylene block (c1) and the hydrocarbon-based polymer block ( The mass ratio (c1/c2) of c2) is 20/80~80/20.

The curable resin composition according to any one of the above-mentioned (1), wherein the branched organopolyoxane (A) is organic represented by the following average unit formula (1). Polyoxane, (R ¹ SiO _3/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (X ¹ O _1/2 ) _e …(1)

(In the formula (1), each R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, and at least one of R ^{1 in} the sole molecule is an alkenyl group, and at least one of R ¹ is an aryl group, in the formula (1), X ¹ is a hydrogen atom or an alkyl group.

In the formula (1), a is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is 0 or a positive number, e is 0 or a positive number, and b/a is a number in the range of 0 to 10, c/a For the range of 0 to 5, d/(a+b+c+d) is a number in the range of 0 to 0.3, and e/(a+b+c+d) is a number in the range of 0 to 0.4).

(V) The curable resin composition according to any one of the above (1) to (IV), which is a composition for sealing an optical semiconductor element.

According to the present invention, it is possible to provide a kind of adhesion, especially resistance A curable resin composition excellent in adhesion after the wet reflow test.

The curable resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") is a curable resin composition containing a branched chain organopolyoxane (A) having an alkenyl group, a linear organopolyoxane (B) having at least two hydrogen atoms bonded to a halogen atom in one molecule, and a polyoxyalkylene-containing block (c1) and a hydrocarbon-based polymer block (c2) The segment copolymer (C) and the catalyst (D) for hydrogenation reaction.

Hereinafter, each component contained in the composition of the present invention will be described in detail.

<branched organopolyoxane (A)>

The branched organopolyoxane (A) is a branched organopolyoxane having an alkenyl group.

Examples of the alkenyl group include an alkenyl group having 2 to 18 carbon atoms such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group or an octenyl group, and a vinyl group (hereinafter sometimes referred to as a vinyl group). Expressed as "Vi").

The alkenyl group in one molecule is preferably from 2 to 12% by mass, more preferably from 3 to 10% by mass.

The branched organopolyoxane (A) preferably has at least one aryl group, more preferably at least 30 mol% of the total organic groups bonded to the fluorene atom, and more preferably at least 40 mol%. Aryl.

The aryl group may, for example, be an aryl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group or a xylyl group, and is preferably a phenyl group.

Thereby, the attenuation of the obtained cured product due to refraction, reflection, scattering, and the like of light is reduced, and when the linear organopolyoxane (B) described later has an aryl group as well, the linear form The organic polyoxyalkylene (B) is excellent in compatibility, turbidity and the like are suppressed, and the cured product is excellent in transparency.

Examples of the group bonded to the other ruthenium atom in the branched organopolyoxane (A) include, for example, a substituted or unsubstituted one-valent hydrocarbon group other than the alkenyl group and the aryl group, and specific examples thereof include a methyl group. Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, various pentyl groups, various hexyl groups, various octyl groups, various fluorenyl groups, cyclopentyl groups, cyclohexyl groups An alkyl group having 1 to 18 carbon atoms; an aralkyl group having 7 to 18 carbon atoms such as benzyl group or phenethyl group; and a carbon number of 3-chloropropyl group, 3,3,3-trifluoropropyl group or the like a halogenated alkyl group of 1 to 18; etc., as other small amount groups, may have a hydroxyl group bonded to a halogen atom and an alkoxy group bonded to a halogen atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

Such a branched organopolyoxane (A) is preferably an organopolyoxane represented by the following average unit formula (1).

(R ¹ SiO _3/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (X ¹ O _1/2 ) _e (1)

In the formula (1), each R ^{1 is} independently a substituted or unsubstituted one-valent hydrocarbon group. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a t-butyl group, various pentyl groups, various hexyl groups, and various octane groups. a carbon number of 1 to 18, such as a fluorenyl group, a cyclopentyl group, a cyclohexyl group or the like; a carbon number of a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, an octenyl group or the like Alkenyl group of ~18; aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group or xylyl group; aralkyl group having 7 to 18 carbon atoms such as benzyl group and phenethyl group; 3-chloropropyl group a halogenated alkyl group having 1 to 18 carbon atoms such as 3,3,3-trifluoropropyl group;

Among them, at least one of R ¹ in one molecule is an alkenyl group, and R ¹ which is an alkenyl group is preferably from 2 to 12% by mass, more preferably from 3 to 10% by mass.

Further, in one molecule, preferably at least one of R ¹ is an aryl group, more preferably at least 30 mol % of all R ¹ is an aryl group, and more preferably at least 40 mol% is an aryl group.

In the formula (1), X ¹ is a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a third butyl group, various pentyl groups, various hexyl groups, and various octyl groups. And an alkyl group having 1 to 18 carbon atoms, such as a mercapto group, a cyclopentyl group, and a cyclohexyl group, preferably a methyl group.

In the formula (1), a is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is 0 or a positive number, e is 0 or a positive number, and b/a is a number in the range of 0 to 10, c/a For the range of 0 to 5, d/(a+b+c+d) is a number in the range of 0 to 0.3, and e/(a+b+c+d) is a number in the range of 0 to 0.4.

The weight average molecular weight (Mw) of the branched organopolyoxane (A) is preferably from 1,000 to 300,000, more preferably from 2,000 to 100,000.

In the present invention, the weight average molecular weight means a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) using chloroform as a solvent.

Further, the branched organopolyoxane (A) is a very viscous semi-solid or solid, and it is difficult to measure the viscosity.

<linear organic polyoxane (B)>

The linear organopolyoxane (B) is an organic polyoxyalkylene having at least two hydrogen atoms bonded to a halogen atom in one molecule. The linear organopolyoxane (B) may have a small amount (for example, less than 2 mol% of the total oxane unit) branch as long as it is mainly linear.

The linear organopolyoxane (B) is subjected to an addition reaction (hydrazine hydrogenation reaction) to the alkenyl group of the above branched organopolyoxane (A). In this case, since the linear organopolyoxane (B) has at least two hydrogen atoms (Si-H) bonded to a halogen atom, it can be used as a branch between the branched organopolyoxane (A). The linker works.

The degree of polymerization of the linear organopolyoxane (B) is preferably more than 10, more preferably more than 30, more preferably more than 30 and 1,000 or less, still more preferably more than 30 and less than 500. Thereby, the composition of the present invention is more excellent in adhesion. The reason for this is considered to be that the hardened material will have toughness by containing a polymer component. In addition, workability has also become good.

The linear organopolyoxane (B) preferably has at least one aryl group, more preferably bonded to all of the ruthenium atoms, based on the reduction of the attenuation of the resulting cured product due to light refraction, reflection, scattering, and the like. At least 30 mole % of the organic group is an aryl group, and more preferably at least 40 mole % is an aryl group.

The aryl group may, for example, be an aryl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group or a xylyl group, and is preferably a phenyl group.

Examples of the group bonded to the ruthenium atom in the linear organopolyoxane (B) include, for example, a substituted or unsubstituted one-valent hydrocarbon group having no aliphatic unsaturated group, and specific examples thereof include a methyl group. Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, various pentyl groups, various hexyl groups, various octyl groups, various fluorenyl groups, cyclopentyl groups, cyclohexyl groups An alkyl group having 1 to 18 carbon atoms; an aryl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group or a xylyl group; an aralkyl group having 7 to 18 carbon atoms such as a benzyl group or a phenethyl group; a halogenated alkyl group having 1 to 18 carbon atoms such as 3-chloropropyl group, 3,3,3-trifluoropropyl group or the like;

The linear organopolyoxane (B) is preferably a linear organopolyoxane whose both ends of the molecular chain are blocked by a diorganohydroquinoneoxy group, and examples thereof include the following formula (2). The organic polyoxane represented by HR ² ₂ SiO(R ² ₂ SiO) _n SiR ² ₂ H‧‧‧(2)

In the formula (2), each R ^{2 is} independently a substituted or unsubstituted one-valent hydrocarbon group having no aliphatic unsaturated bond. Examples of the monovalent hydrocarbon group of R ² include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a t-butyl group, various pentyl groups, and various hexyl groups. Alkyl groups having 1 to 18 carbon atoms such as various octyl groups, various fluorenyl groups, cyclopentyl groups and cyclohexyl groups; aryl groups having 6 to 18 carbon atoms such as phenyl, tolyl or xylyl; benzyl and benzene An aralkyl group having 7 to 18 carbon atoms such as an ethyl group; a halogenated alkyl group having 1 to 18 carbon atoms such as 3-chloropropyl group, 3,3,3-trifluoropropyl group or the like; etc., among which carbon number is preferred. The alkyl group of 1 to 18 is more preferably a methyl group (hereinafter sometimes referred to as "Me").

Further, it is preferred that at least one of R ² is an aryl group, more preferably at least 30 mol % is an aryl group, and still more preferably at least 40 mol % is an aryl group. The aryl group is an aryl group having 6 to 18 carbon atoms, preferably a phenyl group (hereinafter sometimes referred to as "Ph").

In the formula (2), n is an integer of 1 or more, preferably an integer of more than 10, more preferably an integer of more than 30, more preferably an integer of more than 30 and 1,000 or less, and particularly preferably more than 30 and less than 500. Integer. When n is in the above range, the adhesion is more excellent.

The weight average molecular weight (Mw) of the linear organopolyoxane (B) is preferably from 500 to 1,000,000, more preferably from 1,000 to 30,000, based on the reason that the cured product can produce toughness.

In addition, the viscosity of the linear organopolyoxane (B) at 25 ° C is preferably 20 ~ 1,000,000 mPa. s, more preferably 200~100,000mPa. s.

Further, in the present invention, the viscosity means a viscosity measured at 25 ° C according to 4.1 (Brookfield-type rotational viscometer) of JIS K7117-1.

(Method for producing linear organopolyoxane (B))

The method for producing the linear organopolyoxane (B) is not particularly limited, and examples thereof include a method of forming an organopolyoxane (b1) having two or more sterol groups in one molecule and having a bond. The dioxane (b2) which is a hydrogen atom of a halogen atom is reacted to form water (H ₂ O) as a by-product, and the sterol group remaining after the reaction is dehydrated and condensed to obtain the above Polyoxyalkylene (B) is used as the main product.

In this case, for example, the reaction can be traced by ¹ H-NMR, and it is confirmed that the peak derived from the sterol group of the organopolyoxane (b1) disappears, or the component derived from the component used in the reaction is confirmed to be present. The appearance of a peak can be regarded as a reaction product of a linear organopolyoxane (B) containing a main product and a by-product, and is considered to be the end of the reaction.

The organopolyoxane (b1) to be used in the above-mentioned reaction is, for example, an organic polyoxane represented by the following formula (3), and examples of the dioxane (b2) include the following formula ( 4) Indicates dioxane.

HO(R ² ₂ SiO) _m H‧‧‧(3)

HR ² ₂ SiOSiR ² ₂ H‧‧‧(4)

Further, in the formulas (3) and (4), R ² has the same meaning as the above R ² . Further, in the formula (3), m is an integer of the above n or less.

In the above production method, for example, one of the sterol groups of the organopolyoxane (b1) of the formula (3) is derived from -SiR ² ₂ H derived from the dioxane (b2) of the formula (4). Part of the blocking is carried out to condense the residual sterol group and polymerize. Therefore, the degree of polymerization of the linear organopolyoxane (B) is related to the amount of dioxane (b2) fed.

The compounding ratio of each component in the above reaction is preferably from 10 mol of the sterol group in the organopolyoxane (b1), and the amount of the dioxane (b2) is from 0.001 to 0.2 mol.

The above reaction is preferably carried out by stirring. When stirring, for example, it is preferably heated in a temperature range of 50 to 65 ° C, and the stirring time (reaction time) is preferably, for example, 1 to 5 hours.

The content of the linear organopolyoxane (B) is preferably from 20 to 60 parts by mass, more preferably from 30 to 50 parts by mass, per 100 parts by mass of the branched organopolyoxane (A). . Linear organic poly When the content of the oxyalkylene (B) is in this range, the composition of the present invention is excellent in hardenability and more excellent in adhesion.

<Block copolymer (C)>

The block copolymer (C) contained in the composition of the present invention is a block copolymer containing a polyoxyalkylene block (c1) and a hydrocarbon-based polymer block (c2).

Such a block copolymer (C) can be obtained, for example, by a polyalkylene oxide (c1') having a terminal reactive group and a hydrocarbon-based polymer having a terminal group reactive with the above-mentioned terminal reactive group ( C2') The reaction is carried out under the conditions in which the terminal reaction group is reacted with the terminal group to form a copolymer chain containing the polyoxyalkylene block (c1) and the hydrocarbon-based polymer block (c2).

As a method of obtaining the block copolymer (C), for example, a catalyst for hydrogenation reaction is used, and the terminal reactive group is a polyoxyalkylene (c1) bonded to a hydrogen atom (Si-H) of a halogen atom (c1). a method of performing a hydrazine hydrogenation reaction with the above-mentioned terminal group-based alkenyl group-based hydrocarbon polymer (c2'); bonding the above-mentioned terminal reactive group to an alkenyl group polyoxyalkylene oxide (c1') to the above terminal group A hydrocarbon-based polymer (c2') of a hydrogen atom (Si-H) of a halogen atom, a method of performing a hydrogenation reaction in the same manner; In this case, as the catalyst for the hydrogenation reaction, a catalyst (D) for hydrogenation reaction described later can be used.

In the composition of the present invention, the branched organopolysiloxane (A) and the linear organopolyoxane (B) are used together, and the block copolymer (C) is contained, so the adhesion is Especially the wet reflow test After the adhesion is excellent. The reason for this is considered as follows.

First, since the block copolymer (C) contains a polyoxyalkylene block (c1), compatibility with the above-mentioned branched organopolyoxane (A) and linear organopolyoxane (B) High, able to integrate.

Next, the block copolymer (C) contains a hydrocarbon-based polymer block (c2) such as an isobutylene polymer block or a (meth) propylene-based polymer block, and the hydrocarbon-based polymer blocks (c2) In addition, since the main chain is composed of a hydrocarbon chain and a plurality of hydrocarbon groups are also present in the side chain, the moisture resistance is relatively high (the water vapor permeability is low) as compared with the polysiloxane. It is considered that the cured product of the composition of the present invention can suppress the intrusion of moisture even in a high-humidity environment, and the adhesion after the wet reflow-resistant test is good.

On the other hand, if the composition of the present invention contains, for example, only the polyisobutylene which is not block copolymerized in place of the block copolymer (C), the polymer does not blend into the branched organopolyoxane (A). In the linear organopolyoxane (B), since it is in an isolated state, the effect of suppressing moisture from entering the cured product is lowered. Further, since the polymer has poor compatibility with the branched organopolyoxane (A) and the linear organopolyoxane (B), the cured product is cloudy and has poor transparency.

(polyoxyalkylene block (c1))

The polyoxyalkylene block (c1) contained in the block copolymer (C) has a polyoxyalkylene structure composed of a plurality of units of a siloxane. Further, the polyoxyalkylene block (c1) may have a small amount (for example, less than 2 mol% of all units of helium oxide) branched as long as it is mainly linear.

The polyoxyalkylene block (c1) is as described above, for example, derived from a polyoxyalkylene (c1') having the above terminal reactive group. Examples of the terminal reactive group of the polyoxyalkylene oxide (c1′) include a hydrogen atom (Si—H) bonded to a halogen atom; and a vinyl group, an allyl group, a butenyl group, a pentenyl group, and the like. An alkenyl group such as a hexenyl group or an octenyl group having 2 to 18 carbon atoms;

As such a polyoxyalkylene (c1'), for example, a polyoxyalkylene represented by the following formula (5) can be suitably used.

R ³² R ³¹ ₂ SiO(R ³¹ ₂ SiO) _k SiR ³¹ ₂ R ³² ‧‧‧(5)

In the formula (5), R ^{31 is} independently a hydrogen atom or a substituted or unsubstituted one-valent hydrocarbon group. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a t-butyl group, various pentyl groups, various hexyl groups, and various octane groups. a carbon number of 1 to 18, such as a fluorenyl group, a cyclopentyl group, a cyclohexyl group or the like; a carbon number of a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, an octenyl group or the like Alkenyl group of ~18; aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group or xylyl group; aralkyl group having 7 to 18 carbon atoms such as benzyl group and phenethyl group; 3-chloropropyl group And a halogenated alkyl group having 1 to 18 carbon atoms such as 3,3,3-trifluoropropyl group; and the like, wherein an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferred. Is a methyl group, a phenyl group.

Further, R ³¹ may be a hydrogen atom or an alkenyl group. In this case, preferably 2 to 4 R ^{31 in} one molecule are a hydrogen atom or an alkenyl group, and more preferably 2 to 3 R ³¹ are a hydrogen atom or an alkenyl group.

In the formula (5), R ^{32 is} independently a terminal reactive group, and specific examples thereof include a hydrogen atom; a carbon number of a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, an octenyl group or the like; 18 alkenyl; etc.

In the formula (5), k is an integer of 1 or more, preferably 1 to 1,000, and may be a value corresponding to the weight average molecular weight of the polyoxyalkylene (c1').

The polyoxymethane (c1') preferably has a weight average molecular weight of from 100 to 100,000, more preferably from 500 to 50,000, in view of elongation characteristics and transparency.

(hydrocarbon polymer block (c2))

The hydrocarbon-based polymer block (c2) contained in the block copolymer (C) has a structure composed of a hydrocarbon-based polymer, and contributes to improvement in moisture resistance.

Examples of such a hydrocarbon-based polymer block (c2) include an isobutylene polymer block, a (meth) propylene-based polymer block, and a hydrogenated polybutadiene block.

Among them, the isobutylene polymer block and/or the (meth) propylene polymer are preferred because the moisture resistance is more excellent and the adhesion of the composition of the present invention after the wet reflow test is better. The block is more preferably an isobutylene polymer block.

As described above, such a hydrocarbon-based polymer block (c2) is derived, for example, from a hydrocarbon-based polymer (c2') having the above terminal group.

Examples of the terminal group of the hydrocarbon-based polymer (c2') include a hydrogen atom (Si-H) bonded to a halogen atom; a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexene group; The alkenyl group having 2 to 18 carbon atoms, such as a octyl group or the like; and the like, preferably a vinyl group or an allyl group.

Examples of such a hydrocarbon-based polymer (c2') include the above-mentioned A (meth) propylene-based polymer having a terminal group, an isobutylene-based polymer having the above terminal group, and the like.

The weight average molecular weight of the hydrocarbon-based polymer (c2') is preferably from 1,000 to 100,000, more preferably from 2,000 to 50,000, for the reason that the moisture resistance is more excellent.

As the (meth) propylene-based polymer having the above terminal group, it is preferred that the main chain is polymerized mainly by a (meth) propylene monomer. Here, "mainly" means that 50 mol% or more of the monomer unit constituting the main chain is the above monomer, preferably 70 mol% or more.

Examples of the (meth)acrylic monomer include a (meth)acrylic monomer and a (meth)acrylate monomer, and a (meth)acrylate monomer is preferred.

Specific examples of the (meth) acrylate monomer include alkyl (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate.

In the present invention, the (meth) acrylate monomer may be copolymerized with another monomer to further perform block copolymerization. In this case, the (meth) acrylate monomer preferably has a mass ratio of 40. More than % by mass.

Further, the bonding form of the terminal group and the (meth)acrylic polymer main chain is not particularly limited, and examples thereof include a carbon-carbon bond, an ester bond, an ether bond, a carbonate bond, a guanamine bond, and an amine group. A bonding form of an ester bond or the like.

In the isobutylene polymer having the above terminal group, the "isobutylene polymer" is not limited to all the monomer units formed of isobutylene units, and is also included in the isobutylene polymer. The monomer of aggregation. Examples of such a monomer component include an olefin having 4 to 12 carbon atoms, a vinyl ether, an aromatic vinyl compound, a vinyl decane, and an allyl decane.

However, the monomer having copolymerization with isobutylene is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably all monomer units are formed of isobutylene units.

As the isobutylene-based polymer having the terminal group, for example, a diallyl-terminated polyisobutylene represented by the following formula (6) can be suitably used. Further, in the following formula (6), PIB represents polyisobutylene.

CH ₂ =CHCH ₂ -PIB-CH ₂ CH=CH ₂ ‧‧‧(6)

In the present invention, for example, R ³² represented by the above formula (5) represents a polyoxyalkylene (c1′) of a hydrogen atom or an alkenyl group, and a hydrocarbon-based polymer of an isobutylene polymer represented by the formula (6). C2') Polymerization is carried out to obtain a block copolymer (C) comprising a polyoxyalkylene block (c1) and a hydrocarbon-based polymer block (c2) composed of polyisobutylene.

The block copolymer (C) is agglomerated based on the excellent balance between the polyoxyalkylene block (c1) and the hydrocarbon-based polymer block (c2) and the better adhesion after the wet-back reflow test. The mass ratio (c1/c2) of the oxyalkylene block (c1) to the hydrocarbon-based polymer block (c2) is preferably from 20/80 to 80/20, more preferably from 35/65 to 65/35.

The content of the block copolymer (C) is preferably based on the branched organopolyoxane (A) and the linear organopolyoxane based on the reason that the adhesion after the wet reflow-resistant test is more excellent. 100 parts by mass of the alkane (B) is 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and more preferably 10 to 25 parts by mass.

<矽 Catalyst for hydrogenation reaction (D)>

The catalyst (D) for hydrogenation reaction contained in the composition of the present invention is used in combination with a linear organopolyoxane (B) having a hydrogen atom bonded to a halogen atom to promote its pair of branches. The alkenyl group of the organopolyoxyalkylene (A) is subjected to an addition reaction (hydrazine hydrogenation reaction) as a catalyst.

At this time, when the block copolymer (C) has a hydrogen atom or an alkenyl group bonded to a halogen atom, the groups are also reacted by the catalyst (D) for hydrogenation reaction.

As the catalyst (D) for the hydrogenation reaction, a conventionally known one can be used, and examples thereof include a platinum-based catalyst, a ruthenium-based catalyst, and a palladium-based catalyst, and a platinum-based catalyst is preferable. Specific examples of the platinum-based catalyst include chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-divinyltetramethyldioxane complex, and chloroplatinic acid-alcohol complex compound. And a platinum diketone complex or the like, which may be used alone or in combination of two or more.

The content of the catalyst (D) for the hydrogenation reaction is the amount of the catalyst, but it is preferably based on the branched organopolysiloxane (A) and the linear one based on the reason that the composition of the present invention is excellent in the hardenability. The total amount of the organic polysiloxane (B) is from 0.00001 to 0.1 parts by mass, more preferably from 0.0001 to 0.01 parts by mass.

<hardening retarder (E)>

The composition of the present invention may further contain a hardening retarder (E). hard The retardation agent (E) is a component for adjusting the hardening speed and the operation time of the composition of the present invention.

Specific examples of the hardening retarder (E) include 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and phenylbutynol, and 1 - an alcohol derivative having a carbon-carbon triple bond such as acetyl-1-cyclohexanol; 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexene-1- An alkyne compound such as an alkyne; an alkenyl group-containing low molecular weight oxirane such as tetramethyltetravinylcyclotetraoxane or tetramethyltetrahexenylcyclotetraoxane; methyl-tris(3-methyl) Alkyne-containing decane, such as -1-butyn-3-yloxy) decane, vinyl-tris(3-methyl-1-butyn-3-yloxy) decane, etc.; Two or more types may be used in combination.

The content of the hardening retarder (E) is appropriately selected depending on the method of use of the composition of the present invention, etc., but is preferably, for example, preferably relative to the above-mentioned branched organopolyoxane (A) and linear organopolyoxane. (B) The total amount of 100 parts by mass is 0.00001 to 0.1 part by mass, more preferably 0.0001 to 0.01 part by mass.

<Close agent (F)>

The composition of the present invention may further contain a binding agent (F).

Examples of the adhesion imparting agent (F) include a decane coupling agent. Specific examples of the decane coupling agent include amino decane, vinyl decane, epoxy decane, methacryl decane, isocyanate decane, imino decane, reactants thereof, and the like, and reacting with the polyisocyanate. The compound or the like obtained is preferably an epoxy decane.

As the epoxy decane, as long as it has an epoxy group and an alkoxyalkyl group The compound is particularly limited, and specific examples thereof include γ-glycidoxypropylmethyldimethoxydecane, γ-glycidoxypropylethyldiethoxydecane, and γ-glycidyloxygen. a dialkoxy epoxy decane such as propyl propyl diethoxy decane or β-(3,4-epoxycyclohexyl)ethyl methyl dimethoxy decane; γ-glycidoxy propyl propyl a trialkoxy epoxy decane such as a trimethoxy decane or a β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane;

Further, the adhesion-imparting agent (F) may be, for example, a dehydrated condensate of the above-mentioned epoxy decane, and specific examples thereof include γ-glycidoxypropyltrimethoxydecane, phenyltrimethoxydecane, and 1,3. - an epoxy decane dehydration condensate obtained by dehydration condensation of divinyl-1,1,3,3-tetramethyldioxane.

The content of the adhesion-imparting agent (F) is not particularly limited, and is preferably 0.5 to 10 parts by mass based on 100 parts by mass of the branched organopolyoxane (A) and the linear organopolyoxane (B). The mass part is more preferably 1 to 5 parts by mass.

The method for producing the composition of the present invention is not particularly limited, and examples thereof include a method in which the above-mentioned essential components and optional components are mixed and produced.

Further, the method of curing the composition of the present invention to obtain a cured product is not particularly limited, and examples thereof include a method of heating the composition of the present invention at 80 to 200 ° C for 10 to 720 minutes.

The composition of the present invention can be used, for example, in display materials, optical recording media materials, optical instrument materials, optical component materials, optical fiber materials, In the fields of optical/electrical functional organic materials, semiconductor integrated circuit peripheral materials, and the like, for example, an adhesive, a primer, a sealing material, or the like is used.

In particular, since the composition of the present invention is excellent in adhesion, and the cured product exhibits good transparency and high refractive index, it can be suitably used as a composition for optical semiconductor sealing.

The optical semiconductor to which the composition of the present invention can be used is not particularly limited, and examples thereof include a light-emitting diode (LED), an organic electroluminescence device (organic EL), a laser diode, an LED array, and the like.

The method of using the composition of the present invention as a composition for sealing an optical semiconductor, for example, is a method in which a composition of the present invention is provided on an optical semiconductor, and an optical semiconductor to which the composition of the present invention is applied is heated to make the present invention The composition hardens.

In this case, the method of applying the composition of the present invention and hardening it is not particularly limited, and examples thereof include a method using a cloth coater, a potting method, screen printing, transfer molding, and injection molding.

[Examples]

The present invention will be specifically described below by way of examples, but the invention is not limited thereto.

<Manufacture of branched-chain organopolyoxane 1 of Si-Vi>

Into a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, 21.4 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane, 60 g of water, and trifluoroethylene were placed. 0.14 g of methanesulfonic acid and 200 g of toluene, and mixed. 151.5 g of phenyltrimethoxydecane was added dropwise thereto over 1 hour while stirring, and the mixture was heated under reflux for 1 hour. After cooling, the lower layer was separated, and the toluene solution layer was washed with water three times. 100 g of a 5% sodium hydrogencarbonate aqueous solution was added to the water-washed toluene solution layer, and the mixture was heated to 75 ° C with stirring, and then refluxed for 1 hour. After cooling, the lower layer was separated, and the upper layer of the toluene solution was washed with water three times. The residual toluene solution layer was concentrated under reduced pressure to obtain a methylphenylvinylpolyoxyl group having an average vinyl content of 3.6% by mass in the molecule represented by the following average unit formula (7) at a temperature of 25 ° C. A branched organopolyoxane 1 of an alkane resin.

(ViMe ₂ SiO _1/2 ) _0.25 (Ph ₂ SiO _3/2 ) _0.75 ‧‧‧(7)

<Manufacture of Linear-Organic Polyoxane 1 of Si-H System>

Into a flask equipped with a stirrer and a reflux condenser, 100 g of a linear organopolyoxane having a decyl group represented by the following formula (8), and 1,1,3,3-tetramethyldioxane are charged. 1.5 g and 0.1 g of trifluoromethanesulfonic acid were stirred and heated at 50 ° C for 2 hours. Thereafter, 150 g of toluene was added, and the generated water was discharged to the outside of the system. After washing the toluene layer three times, it was concentrated under reduced pressure to obtain a linear organopolyoxane 1 represented by the following formula (9).

HO(Ph ₂ SiO) ₃ (Me ₂ SiO) ₃ H‧‧‧(8)

HMe ₂ SiO(Ph ₂ SiO) ₃₀ (Me ₂ SiO) ₃₀ SiMe ₂ H‧‧‧(9)

<Manufacture of Block Copolymer 1>

Using 0.001 parts by mass of the catalyst 1 for hydrogenation reaction described later, the dimethyl hydrazine-terminated dimethyl oxa oxide ‧ diphenyl is terminated at both ends of the molecular chain 100 parts by mass of a polyoxyalkylene copolymer (weight average molecular weight: 12,000) and 50 parts by mass of a polyisobutylene (weight average molecular weight: 12,000) of a diallyl group, and hydrogenation reaction was carried out at 70 ° C for 4 hours. A block copolymer 1 comprising a polyoxyalkylene block and a polyisobutylene block is obtained.

The above mass ratio (c1/c2) in the obtained block copolymer 1 was 50/50.

[Examples 1 to 4, Standard Example 1, Comparative Example 1]

<Manufacture of Curable Resin Composition>

The components shown in the table are used in the amounts shown in the following Table (unit: parts by mass), and they are uniformly mixed using a vacuum mixer to produce a curable resin composition (hereinafter also simply referred to as "composition").

<transmittance rate>

The produced composition was heated at 150 ° C for 2 hours to be hardened to obtain a cured product (thickness = 2.0 mm). The obtained cured product was measured for transmittance (unit: %) at a wavelength of 400 nm using an ultraviolet-visible (UV-Vis) absorption spectrometer (manufactured by Shimadzu Corporation) in accordance with JIS K0115:2004. The measurement results are shown in the first table below. When the value of the transmittance is 80% or more, it can be evaluated as "transparent".

<CF>

The composition to be manufactured is made into a 12.5 mm × 25 mm joint area. After being sandwiched between the adherends (aluminum alloy plate, A1050P, manufactured by PALTEK Co., Ltd.), the mixture was heated at 150 ° C for 2 hours to be hardened to obtain a test piece. Using the obtained test piece, a tensile test was carried out in accordance with JIS K6850:1999, and the ratio (unit: %) of the area of the aggregation failure (CF) to the area of the subsequent layer was measured. The results are shown in the first table below. The closer the CF value is to 100, the more excellent the adhesion can be evaluated.

<Exfoliation evaluation>

The composition to be produced was applied onto an LED package (manufactured by ENOMOTO Co., Ltd.), and heated at 150 ° C for 2 hours to be hardened, and a plurality of test pieces were produced for each of the examples. Next, for each of the following examples, eight test pieces were provided for the following three types of tests, and the number of test pieces in which the cured product was not peeled off was counted. The larger the number, the more excellent the adhesion can be evaluated.

(reflow test)

The test piece was placed on a hot plate heated to 280 ° C for 40 seconds, and visually confirmed whether or not the cured product was peeled off.

(wet heat test)

The test piece was placed in an environment of a temperature of 85 ° C and a humidity of 85% for 1,000 hours, and visually confirmed whether or not the cured product was peeled off.

(wet resistance reflow test)

After the test piece was placed in an environment of a temperature of 30 ° C and a humidity of 60% for 192 hours, the above-mentioned reflow test was carried out to visually confirm the presence or absence of peeling of the cured product.

The following components are used for each component in the first table.

‧ Branched chain polyorganosiloxane 1: as described above (vinyl content: 5.6% by mass, phenyl content in all organic groups bonded to a ruthenium atom: 50 mol%, Mw: 2,500, viscosity: Very viscous semi-solid and unable to measure viscosity)

‧ linear organic polyoxane 1: as described above (the hydrogen atom content bonded to the ruthenium atom: 0.02 mass%, and the phenyl group content in all the organic groups bonded to the ruthenium atom: 49 mol%, Mw: 5,000, viscosity: 3,000 mPa.s)

‧ block copolymer 1: as above

‧Polyisobutylene 1: Polymer of isobutylene (weight average molecular weight: 12,000)

‧ Catalyst for hydrogenation reaction: chloroplatinic acid-divinyltetramethyldioxane complex (Gelest)

‧ Hardening retarder 1: 3-methyl-1-butyn-3-ol (manufactured by Tokyo Chemical Industry Co., Ltd.)

‧ adhesion imparting agent 1: γ-glycidoxypropyltrimethoxydecane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), phenyltrimethoxydecane (KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.), and Dehydration condensation of epoxy decane by 1,3-divinyl-1,1,3,3-tetramethyldioxane

As is apparent from the results shown in the first table, in Examples 1 to 4 in which the block copolymer 1 was used, the peeling evaluation was good and the adhesion was excellent, and in particular, the wet-resistance test results were good.

On the other hand, in the standard example 1 in which the block copolymer 1 was not used, the wet-resistance reflow test result was inferior.

Further, in Comparative Example 1 in which polyisobutylene 1 was used alone without block copolymerization, the compatibility was poor and turbid, and thus the transparency was poor, and the results of the wet reflow test were insufficient.

Claims (5)

A curable resin composition comprising a branched organopolyoxane having an alkenyl group (A) and a linear organopolyoxane having at least two hydrogen atoms bonded to a halogen atom in one molecule (B), a block copolymer (C) containing a polyoxyalkylene block (c1) and a hydrocarbon-based polymer block (c2), and a catalyst (D) for hydrogenation reaction. The curable resin composition of claim 1, wherein the hydrocarbon-based polymer block (c2) contains a (meth) propylene-based polymer block and/or an isobutylene-based polymer block. The curable resin composition of claim 1 or 2, wherein the mass ratio of the polyoxyalkylene block (c1) to the hydrocarbon-based polymer block (c2) in the block copolymer (C) (c1/ C2) is 20/80~80/20. The curable resin composition according to any one of claims 1 to 3, wherein the branched organopolyoxane (A) is an organopolyoxane represented by the following average unit formula (1), (R ¹ SiO _3/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (X ¹ O _1/2 ) _e (1) (Formula (1) In the formula, each R ¹ is a substituted or unsubstituted one-valent hydrocarbon group, and at least one of R ^{1 in} the sole molecule is an alkenyl group, and at least one of R ¹ is an aryl group, and in the formula (1), X ¹ is hydrogen. Atom or alkyl group, in the formula (1), a is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is 0 or a positive number, e is 0 or a positive number, and b/a is in the range of 0-10 Number, c/a is the number in the range of 0~5, d/(a+b+c+d) is the number in the range of 0~0.3, and e/(a+b+c+d) is the range of 0~0.4 The number inside). The curable resin composition according to any one of claims 1 to 4, which is a composition for sealing an optical semiconductor element.