JP2008143954A - Isocyanuric ring-containing polymer, method for producing the same, and composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an isocyanuric ring-containing polymer usable for an adhesive for an optical semiconductor, and a composition containing the polymer. <P>SOLUTION: The isocyanuric ring-containing polymer has a repeating unit represented by formula (1) (wherein, R<SB>1</SB>is a monovalent organic group; and R<SB>2</SB>is a divalent organic group), and has 1,000-1,000,000 weight-average molecular weight. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel isocyanuric ring-containing polymer. More specifically, the present invention relates to a novel isocyanuric ring-containing polymer excellent in transparency, UV durability, and heat resistance.

Conventionally, as an optical semiconductor sealing resin, an epoxy compound mainly composed of bisphenol A glycidyl ether has been generally used. Since such an epoxy compound has an aromatic ring, an optical semiconductor that emits blue or ultraviolet light. In order to use for sealing, the durability against ultraviolet rays (UV durability) was insufficient.
In order to improve the UV durability of the optical semiconductor sealing resin, it has been proposed to use an alicyclic epoxy compound (see Patent Document 1), but the UV durability is still not sufficient. It was.
On the other hand, it is known that a resin having a siloxane skeleton is excellent in weather resistance, and in recent years, studies using a resin having polydimethylsiloxane as a main skeleton as an optical semiconductor sealing material have been extensively conducted. However, in the case of this resin, the hardness of the cured product is insufficient and it has tackiness, so dust is easily attached, gold wires used for wiring are cut by vibration, and adhesion to the substrate is insufficient. It has been pointed out that it is easy to peel off.
JP 2003-82062 A

  The objective of this invention is providing the isocyanuric ring containing polymer used suitably for the sealing material for optical semiconductors, the adhesive agent for optical semiconductors, etc.

  Another object of the present invention is to provide a method for producing the above-mentioned isocyanuric ring-containing polymer.

  Still another object of the present invention is to provide a composition for optical semiconductors excellent in transparency, UV durability, and heat resistance, which is suitable as a sealing material or adhesive for optical semiconductors, containing the isocyanuric ring-containing polymer. It is to provide.

  Still another object of the present invention is to provide an optical semiconductor element using the above composition as a sealing material or an adhesive.

  Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are firstly
Following formula (1)

Here, R ₁ is a monovalent organic group, and R ₂ is a divalent organic group.
And a polymer having a weight average molecular weight of 1,000 to 1,000,000.

According to the present invention, the above objects and advantages of the present invention are secondly,
In the above formula (1), R ₂ represents the following formula (2)

Here, R ₃ and R ₄ may be the same or different and are a methyl group, an ethyl group, a phenyl group, a vinyl group, a glycidyl group, a hydrogen atom or a hydroxyl group, and R ₅ is an oxygen atom, a methylene group, or a phenylene group. Or a direct bond and n is an integer from 0 to 20,
And R ₁ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an epoxy group, a hydroxyl group or a carboxyl group. This is achieved by the polymer of the present invention, which is a monovalent organic group.

According to the present invention, the above objects and advantages of the present invention are thirdly,
This is achieved by the polymer of the present invention in which R ₁ is a monovalent organic group containing an epoxy group, R ₃ and R ₄ are a methyl group, an ethyl group, or a phenyl group, and R ₅ is an oxygen atom.

According to the present invention, the above objects and advantages of the present invention are fourthly,
The method for producing a polymer of the present invention, comprising reacting an N-monosubstituted isocyanuric acid represented by the following formula (3) with a dihalogen compound represented by the following formula (4) in the presence of an alkali metal compound: Achieved by:

Here, R ₁ is a monovalent organic group, R ₂ is a divalent organic group, and X is a halogen atom.

According to the present invention, the above objects and advantages of the present invention are
This is achieved by an optical semiconductor composition comprising the polymer of the present invention.

According to the present invention, the above objects and advantages of the present invention are sixth,
This is achieved by a semiconductor element using the semiconductor composition of the present invention as a sealing material or an adhesive.

  Hereinafter, the present invention will be described in detail.

Isocyanuric Ring-Containing Polymer The polymer of the present invention is an isocyanuric ring-containing polymer having a repeating unit represented by the above formula (1) and having a weight average molecular weight of 1,000 to 1,000,000. A preferred weight average molecular weight is 1,000 to 100,000.
In the above formula (1), R ₁ is a monovalent organic group, and R ₂ is a divalent organic group.
R ₁ is preferably a monovalent organic group containing, for example, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an epoxy group, a hydroxyl group, or a carboxyl group.
Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n- A hexyl group is preferred. As the aryl group having 6 to 20 carbon atoms, for example, a phenyl group and a tolyl group are preferable. As a C2-C20 alkenyl group, a vinyl group and an allyl group are preferable, for example. As the monovalent organic group containing an epoxy group, a hydroxyl group or a carboxyl group, for example, groups represented by the following formulas (8) to (12) are preferable. More preferably, it is group represented by Formula (8).

R ₂ is a divalent organic group. Examples thereof include an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and a divalent organic group represented by each of the following formulas (13) to (16). (Wherein R ₃ , R ₄ , R ₆ , R ₇ , R ₉ , R ₁₀ may be the same or different, and may be a methyl group, an ethyl group, a phenyl group, a vinyl group, a glycidyl group, a hydrogen atom or a hydroxyl group. R ₅ , R ₈ and R ₁₁ are each independently an oxygen atom, a methylene group, a phenylene group or a direct bond, and l, m and n are each independently an integer of 0 to 20. Among these, as R ₂ , an alkylene group having 1 to 12 carbon atoms, a p-phenylene group, and an m-phenylene group are preferable, and as R ₃ , R _4, R ₆ , R ₇ , R ₉ , and R ₁₀ , a methyl group A phenyl group is preferable, and an oxygen atom is preferable as R ₅ , R ₈ , and R _11. Among the divalent organic groups represented by formulas (13) to (16), the group is represented by formula (13). Particularly preferred are the groups

Method for producing isocyanuric ring-containing polymer I
The isocyanuric ring-containing polymer can be produced by reacting an N-monosubstituted isocyanuric acid represented by the following formula (3) with a dihalogen compound represented by the following formula (4) in the presence of an alkali metal compound.

The definition of R ₁ in Formula (3) and the definition of R ₂ in Formula (4) are the same as those in Formula (1). Moreover, X in Formula (4) is a halogen atom.
Examples of the halogen atom for X include a fluorine atom, a chlorine atom, and an iodine atom. Of these, X is preferably a chlorine atom.
Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, n-butyl lithium, s-butyl lithium, t-butyl lithium and the like.
The compound of formula (4) is preferably used in an amount of 0.5 to 1.5 equivalents relative to 1 equivalent of the compound of formula (3).
Moreover, 0.1-2.0 equivalent can be used for an alkali metal compound with respect to 1 equivalent of compounds of Formula (3).

Method for producing isocyanuric ring-containing polymer II
The isocyanuric ring polymer of the present invention is further subjected to a hydrosilylation reaction between an N, N ′, N ″ -trisubstituted isocyanuric acid represented by the following formula (5) and a silane compound represented by the following formula (6). Obtainable.

The definition of R ₁ in the formula (5) and the definitions of R ₃ , R ₄ , R ₅ and n in the formula (6) are the same as those in the above formulas (1) and (2). In addition, when the monovalent organic group representing R ₁ includes a functional group represented by each of formulas (9) to (12), the functional group may be protected as necessary.

In the reaction, 0.5 to 2.0 equivalents of the compound of formula (6) can be used with respect to 1 equivalent of the compound of formula (5).
In the hydrosilylation reaction, for example, a compound containing platinum, rhodium or palladium can be used as a catalyst. Of these, compounds containing platinum are preferred. Specifically, hexachloroplatinic acid (IV) hexahydrate, platinum carbonyl vinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex can be used. . Alternatively, platinum supported on activated carbon may be used. The amount of the catalyst is preferably 0.01 to 10,000 ppm, more preferably 0.1 to 100 ppm relative to the compound of formula (5) as a metal.

A solvent can be added as needed. Toluene, xylene, mesitylene, diethylbenzene, tetrahydrofuran, diethyl ether, 1,4-dioxane, diphenyl ether and the like can be used.
The reaction temperature is, for example, room temperature to 250 ° C, preferably 50 to 180 ° C. The reaction time is, for example, 0.1 to 120 hours, preferably 1 to 10 hours.
The resulting isocyanuric ring-containing polymer can be used very suitably as a main component in each of the optical semiconductor sealing compositions and optical semiconductor adhesives described below. For example, molded products, films, laminates, paints It is also useful as a protective film.
The composition for optical semiconductors of this invention contains the said isocyanuric ring containing polymer. When the isocyanuric ring-containing polymer contains an epoxy group, the composition for an optical semiconductor of the present invention includes (B) a carboxylic acid anhydride or a polyvalent carboxylic acid, (C) a thermal acid generator, or (D) a metal chelate compound. And (E) Silanol or phenol is preferably contained.

(B) Carboxylic anhydride and polyvalent carboxylic acid The composition of the present invention can contain a carboxylic anhydride or a polyvalent carboxylic acid, particularly when the isocyanuric ring-containing polymer contains an epoxy group. This component (B) is a curing agent that is a component that causes a curing reaction with the (A) isocyanuric ring polymer.
The (B) carboxylic acid anhydride or polyvalent carboxylic acid is not particularly limited, but an alicyclic carboxylic acid anhydride is preferable.
Examples of the alicyclic carboxylic acid anhydride include compounds represented by the following formulas (17) to (27).

Diels-Alder of alicyclic compounds with conjugated double bonds such as 4-methyltetrahydrophthalic anhydride, methyl nadic anhydride, dodecenyl succinic anhydride, α-terpinene, allocymene and maleic anhydride Reaction products and hydrogenated products thereof can be exemplified. In addition, arbitrary structural isomers and arbitrary geometric isomers can be used as the Diels-Alder reaction product and hydrogenated products thereof.
Moreover, the compound represented by following formula (28) can also be used as a hardening | curing agent.

Specific examples of the compound represented by the formula (28) include compounds represented by the following formulas (29) to (33).

In addition, the alicyclic carboxylic acid anhydride can be used after being appropriately chemically modified as long as the curing reaction is not substantially hindered.
Among these alicyclic carboxylic acid anhydrides, from the viewpoint of fluidity and transparency of the composition, the formula (17), formula (19), formula (21), formula (22) or formula (23), formula The compound represented by (28) is preferred. Particularly preferred are compounds represented by formula (17), formula (19), formula (21), and formula (28).

In this invention, an alicyclic carboxylic acid anhydride can be used individually or in mixture of 2 or more types.
Moreover, when using as a composition for optical semiconductor sealing, 1 or more types of aliphatic carboxylic acid anhydride and aromatic carboxylic acid anhydride can also be used as (B) carboxylic acid anhydride. These are preferably used in combination with an alicyclic carboxylic acid anhydride.
The aliphatic carboxylic acid anhydride and the aromatic carboxylic acid anhydride can also be appropriately chemically modified as long as the curing reaction is not substantially hindered.
The total use ratio of the aliphatic carboxylic acid anhydride and the aromatic carboxylic acid anhydride is preferably 50% by weight or less, more preferably 30% by weight or less, based on the total amount with the alicyclic carboxylic acid anhydride. .

In the composition for optical semiconductor encapsulation, the amount of (B) carboxylic acid anhydride or polyvalent carboxylic acid used is carboxylic acid anhydride group or carboxyl relative to 1 mol of epoxy group in the isocyanuric ring-containing polymer of component (A). The group equivalent ratio is preferably 0.3 to 1.5, more preferably 0.5 to 1.3. In this case, even if the amount ratio is less than 0.3 or more than 1.5, there is a possibility that inconveniences such as a decrease in the glass transition point (Tg) and coloring of the obtained cured product may occur.
Furthermore, in the composition for optical semiconductor sealing, in addition to (B) carboxylic acid anhydride or polyvalent carboxylic acid, it is known as a curing agent for epoxy compounds and epoxy resins as long as the desired effects of the present invention are not impaired. These components (hereinafter referred to as “other curing agents”), for example, phenols, dicyandiamides, organic hydrazides such as adipic hydrazide, phthalic hydrazide, and the like can be used in combination.
The use ratio of the other curing agent is preferably 50% by weight or less, more preferably 30% by weight or less based on (B) the carboxylic acid anhydride or the polyvalent carboxylic acid anhydride.

The composition for optical semiconductors of the present invention may contain a curing accelerator for the purpose of increasing the curing rate. Such a curing accelerator is not particularly limited, for example,
Tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine;
2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- ( 2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (Hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-fur Nyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenyl Imidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s -Triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ' )] Ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6- [2′-methyl] Imidazolyl - (1 ')] such imidazoles of isocyanuric acid adduct of ethyl -s- triazine;
Organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite;
Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetrabutylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, methyltributylphosphonium dimethyl fos Fate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butyl Phosphonium tetraphenyl borate, tetraphenyl phosphonium tetraphenyl borate, triphenyl benzyl phosphonium tetraphenylborate, quaternary phosphonium salts such as tetra -n- butyl phosphonium tetrafluoroborate;
Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;
, Organometallic compounds such as tin octylate, aluminum acetylacetone complex;
Tetraethylammonium bromide, tetra-n-butylammonium bromide, the following formula (34)

A quaternary ammonium salt such as
Boron compounds such as boron trifluoride and triphenyl borate; metal halides such as zinc chloride and stannic chloride,
High melting point dispersion type latent curing accelerators such as amine addition type accelerators such as dicyandiamide and adducts of amine and epoxy resin; surfaces of curing accelerators such as imidazoles, organophosphorus compounds and quaternary phosphonium salts Microcapsule-type latent curing accelerator coated with polymer; amine salt-type latent curing accelerator; high-temperature dissociation type thermal cationic polymerization type latent curing accelerator such as Lewis acid salt and Bronsted acid salt Can be mentioned.

Of these curing accelerators, imidazoles, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds, and quaternary ammonium salts are colorless and transparent, and a cured product that is difficult to discolor even when heated for a long time is obtained. This is preferable.
The said hardening accelerator can be used individually or in mixture of 2 or more types.
In the composition for optical semiconductor encapsulation, the use amount of the curing accelerator is preferably 0 to 6 parts by weight, more preferably 0 to 4 parts by weight with respect to 100 parts by weight of the component (A) isocyanuric ring-containing polymer. It is. When the usage-amount of a hardening accelerator exceeds 6 weight part, there exists a possibility of producing inconveniences, such as coloring, in the hardened | cured material obtained.

(C) Thermal acid generator The (C) thermal acid generator in the present invention is a component that generates an acid by heating, thereby causing a curing reaction of the (A) isocyanuric ring-containing polymer.
The (C) thermal acid generator is not particularly limited, and examples thereof include zinc octylate and compounds represented by the following formulas (35) to (41) (hereinafter, “compound (35)”. ) "To" Compound (41) ")

_Here, R 15 _{to R 21} is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, shows a 6-20 aryl group, may be the same or different from each other.

And so on. Of these, compounds (38) to (41) are preferred. The amount of the thermal acid generator used is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, still more preferably 0.05 to 5 parts per 100 parts by weight of the polyorganosiloxane (A). Parts by weight.

(D) Metal Chelate Compound The (D) metal chelate compound used in the present invention can be preferably represented by the following formula (42).

[In the formula (42), M is selected from Al, Ti, Zr, Fe, V, Mo, Sn, Cr, Rh, Co, Ni, Cu and Zn, and Z is an alkyl group having 1 to 20 carbon atoms or halogen. It is an atom, L is a bidentate ligand, N is the coordination number of M, and p is an integer of 1 to N / 2. ]
In the formula (42), M is preferably Al, Ti, or Zr, and particularly preferably Al.
L is preferably a β diketone or a compound represented by the following formula (43).

[In the formula (43), R ₂₂ and R ₂₃ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms which may contain a fluorine atom and a carbon atom which may contain a fluorine atom. Is selected from ˜30 aryl groups, x is an integer from 1 to 4, and 1 is 0 or 1. ]
More specifically, examples of the compound L include compounds represented by each of (A) to (H).

Here, R _{24 to} R ₃₉ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms that may contain a fluorine atom, and 6 to 6 carbon atoms that may contain a fluorine atom. Selected from 30 aryl groups.
Q _{1 to} Q ₃ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms that may contain a fluorine atom, or an aryl having 6 to 30 carbon atoms that may contain a fluorine atom. Selected from the group. Q _{1 to} Q ₃ are preferably a hydrogen atom, a methyl group or an ethyl group.
x is an integer of 1-4.
In the above formula (42), p is preferably N / 2.
As the metal chelate compound represented by the formula (42), those having the following structures are particularly preferable.

The metal chelate compound (D) is preferably 0.0001 to 20 parts by weight, more preferably 0.001 to 1 part by weight, and still more preferably 0.001 to 0.1 parts by weight with respect to 100 parts by weight of the component (A). Used in the department. It was surprising that the curing proceeded sufficiently even at 0.1 parts by weight or less and had sufficient adhesive strength. The thermosetting resin composition of the present invention can have sufficient UV durability, heat resistance and storage stability since the amount of the metal chelate compound added is small.

(E) Silanol or phenol Silanols or phenols can also be added as component (E) to the thermosetting resin composition of the present invention for the purpose of more efficient curing. Silanols or phenols may be generated by heat or hydrolysis.
As a silanol, the compound represented, for example by following formula (44) can be mentioned.

Here, A is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a vinyl group, B is a hydroxyl group, and q is an integer of 1 to 3.
Examples of the silanol represented by the above formula (44) include diphenylsilanediol, triphenylsilanol, diphenylmethylsilanol, phenylvinylsilanediol, tri (paramethoxyphenyl) silanol, triacetylsilanol, diphenylethylsilanol, diphenylpropylsilanol, triphenyl. (Paranitrophenyl) silanol, phenyldivinylsilanol, vinyldiphenylsilanol, 2-butenyldiphenylsilanol, di (2-pentenyl) phenylsilanol, phenyldipropylsilanol, paramethylbenzyldimethylsilanol, triethylsilanol, trimethylsilanol, triisobutyl Examples include silanol.

Examples of silanol derivatives include diphenyldimethoxysilane, triphenylmethoxysilane, diphenylmethylmethoxysilane, phenylvinyldimethoxysilane, tri (paramethoxyphenyl) methoxysilane, triacetylmethoxysilane, diphenylethylmethoxysilane, diphenylpropylmethoxysilane. , Tri (paranitrophenyl) methoxysilane, phenyldivinylmethoxysilane, vinyldiphenylmethoxysilane, 2-butenyldiphenylmethoxysilane, di (2-pentenyl) phenylmethoxysilane, phenyldipropylmethoxysilane, paramethylbenzyldimethylmethoxysilane Methoxysilanes such as triethylmethoxysilane, trimethylmethoxysilane, triisobutylmethoxysilane; Nyldiethoxysilane, triphenylethoxysilane, diphenylmethylethoxysilane, phenylvinyldiethoxysilane, tri (paramethoxyphenyl) ethoxysilane, triacetylethoxysilane, diphenylethylethoxysilane, diphenylpropylethoxysilane, tri (paranitrophenyl) ) Ethoxysilane, phenyldivinylethoxysilane, vinyldiphenylethoxysilane, 2-butenyldiphenylethoxysilane, di (2-pentenyl) phenylethoxysilane, phenyldipropylethoxysilane, paramethylbenzyldimethylethoxysilane, triethylethoxysilane, trimethyl Mention may be made of condensates of ethoxysilanes such as ethoxysilane, triisobutylethoxysilane and the above silanols.
The composition for optical semiconductors of the present invention can further contain (F) a silane compound and (G) a curing catalyst having a transition metal.

(F) Silane Compound The (F) silane compound in the present invention is a component that causes a curing reaction of the epoxy group bonded to the (A) isocyanuric ring-containing polymer. (F) A silane compound can be represented by Formula (7).
H _r —Si—R ⁰ _(4-r) (7)
R ⁰ is selected from an alkyl group having 1 to 20 carbon atoms and an aryl group having 1 to 20 carbon atoms. Preferably hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group N-octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group , N-octadecyl group, n-nonadecyl group, n-eicosyl group, phenyl group, and tolyl group. r is preferably 2 or 3, more preferably r is 3.

(G) Curing catalyst having transition metal For example, a compound containing platinum, rhodium or palladium can be used. Of these, compounds containing platinum are preferred. Specifically, hexachloroplatinic acid (IV) hexahydrate, platinum carbonyl vinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex can be used. . In addition, since the residual catalyst contained in the isocyanuric ring-containing polymer of the component (A) sufficiently acts as a curing catalyst, the component (C) does not necessarily need to be added later.
Preferable amounts of (A), (F), and (G) are 0.01 to 10 parts by weight of (F) component, and (G) component is an isocyanurate of (A) with respect to 100 parts by weight of component (A). Preferably it is 0.01-10,000 ppm with respect to a ring containing polymer, More preferably, 0.1-100 ppm can be used.

-Other additives-
The thermosetting resin composition of the present invention may further contain an epoxy resin.
Examples of the epoxy resin include compounds represented by the following formulas (45) to (57).

Said epoxy compound can also be used as a condensed condensate. The compounds represented by each of the above formulas (45) to (57) can be obtained as the following commercial products. That is, (45) is HBE100 (manufactured by Nippon Nippon Chemical Co., Ltd.), YX8000 (manufactured by Japan Epoxy Resin Co., Ltd.), (46) is YL7040, (47) is YL6753, (48) is YED216D (above, Japan Epoxy Resin Co., Ltd.), (49) is CE2021 (Daicel Chemical Industries, Ltd.), (50) is LS7970 (Shin-Etsu Chemical Co., Ltd.), and (51) to (55) are CE2080, CE3000, respectively. Epolide GT300, Epolide GT400, EHPE3150 (above, manufactured by Daicel Chemical Industries, Ltd.), (56) SR-HHPA (manufactured by Sakamoto Pharmaceutical Co., Ltd.), (57) Tepic (manufactured by Nissan Chemical Industries, Ltd.) Can be obtained as YL7170, YL8034 (manufactured by Japan Epoxy Resin Co., Ltd.), W-100 (manufactured by Shin Nippon Rika Co., Ltd.) and the like can also be used. In addition to these, alicyclic epoxy compounds obtained by hydrogenating the following aromatic epoxy compounds may be used. Bisphenol type epoxy glycidylated bisphenol such as bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A Resin, dihydroxynaphthalene, epoxy resin obtained by glycidylation of divalent phenol such as 9,9-bis (4-hydroxyphenyl) fluorene, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- ( Epoxy resin obtained by glycidylation of trisphenol such as 1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol, -Mention may be made of epoxy resins obtained by glycidylation of tetrakisphenol such as tetrakis (4-hydroxyphenyl) ethane, novolak-type epoxy resins obtained by glycidylation of novolaks such as phenol novolak, cresol novolak, bisphenol A novolak, brominated bisphenol A novolak, etc. Can do.
The aliphatic or alicyclic epoxy compound can be added in an amount of 0.1 to 1,000 parts by weight per 100 parts by weight of the polyorganosiloxane (A).

Moreover, you may contain the above aromatic epoxy compounds as needed.
In addition, an adhesion aid can be further added to the thermosetting resin composition of the present invention for the purpose of improving the adhesion to the lead frame. Examples of adhesion assistants include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropylmethyldi Ethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxy Silane, dodecandichi Lumpur, the compound of formula (58), (59).

また、式（６０）、（６１）のようなチタネート系密着助剤を使用することもできる。

In addition, titanate adhesion assistants such as formulas (60) and (61) can also be used.

Among these, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ -Glycidoxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, dodecanedithiol, and compounds of formulas (58) and (59) are preferred.
The addition amount of the adhesion assistant is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the component (A).
Furthermore, a stress relaxation agent can be added for the purpose of preventing cracks and peeling from the lead frame. Examples of the stress relaxation agent include epoxy-modified silicone, carboxyl group-modified silicone, mercapto-modified silicone, both-end carboxy-modified hydrogenated polybutadiene, and both-end hydroxy-modified polybutadiene.

  Examples of the epoxy-modified silicone include KF-105, X-22-163A, X-22-163B, X-22-163C, KF-1001, KF-101, X-22-2000, X-22-169AS, X-22. -169B, KF-102 (manufactured by Shin-Etsu Chemical Co., Ltd.), SF8421 (manufactured by Toray Dow Co., Ltd.), X-22-162C, X-22-3701E, X-22-3710 (carboxyl-modified silicone) As described above, manufactured by Shin-Etsu Chemical Co., Ltd.) and mercapto-modified silicones, for example, X-22-167B, KF-2001, KF-2004 (manufactured by Shin-Etsu Chemical Co., Ltd.), CI1000 as both-terminal carboxy-modified hydrogenated polybutadiene. (Manufactured by Nippon Soda Co., Ltd.), GI2000, GI3000 (both terminal hydroxy-modified polybutadiene On, it can be exemplified by Nippon Soda Co., Ltd., Ltd.).

Further, a surfactant can be added for the purpose of adjusting the surface tension of the resin.
Specifically, F-474, F-479 (above, Dainippon Ink Industries, Ltd.), FC-4430, FC-4432 (above, made by Sumitomo 3M Ltd.), KP323, KP341 (above, Shin-Etsu Chemical) Kogyo Co., Ltd.), PAINTAD32, PAINTAD54, DK8-8011 (manufactured by Toray Dow Co., Ltd.), Emulgen 104P, Emulgen 109P, Emulgen 123, and Rheodor 8P (above, manufactured by Kao Corporation).

In the thermosetting resin composition of the present invention, inorganic oxide particles can be blended as necessary for the purpose of further improving the UV durability and adjusting the viscosity.
The inorganic oxide particles are not particularly limited, but include, for example, at least one element selected from the group consisting of Si, Al, Zr, Ti, Zn, Ge, In, Sn, Sb, and Ce. And particles made of oxides. More specifically, silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium-tin oxide (ITO), antimony oxide, antimony-tin oxide (ATO), cerium oxide And the like.
Of these inorganic oxide particles, fine particles such as silica, alumina, zirconia, and antimony oxide are preferable.

In addition, the inorganic oxide particles can be used after appropriately performing a surface treatment such as alkylation, polysiloxylation, (meth) acryloxyalkylation, glycoxyalkylation, aminoalkylation or the like.
The said inorganic oxide particle can be used individually or in mixture of 2 or more types.
The primary average particle diameter of the inorganic oxide particles is preferably 100 nm or less, more preferably 1 to 80 nm. In this case, when the primary average particle diameter of the inorganic oxide particles exceeds 100 nm, the transparency of the resulting cured product may be impaired.
The amount of the inorganic oxide particles to be used is preferably 90 parts by weight or less, more preferably 80 parts by weight or less with respect to 100 parts by weight of (A) polyorganosiloxane. When the usage-amount of inorganic oxide particle exceeds 90 weight part, there exists a possibility that a composition may thicken and processing may become difficult.
In some cases, the inorganic oxide particles can be used as a dispersion dispersed in an appropriate solvent.

The solvent is not particularly limited as long as it is inert to each component constituting the thermosetting resin composition and the curing reaction and has an appropriate volatility. For example, alcohols such as methanol, ethanol, i-propanol, n-butanol, n-octanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propyl glycol monomethyl ether, propyl glycol monoethyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone;
Esters or lactones such as ethyl acetate, n-butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Examples include amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, lactams, and the like.

These solvents can be used alone or in admixture of two or more.
The solid content concentration of the dispersion of inorganic oxide particles is preferably 1 to 60% by weight, more preferably 5 to 50% by weight.
Further, if necessary, one or more kinds of dispersants such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a polymer dispersant can be used in combination with the inorganic oxide particles.
Inorganic oxide particles and dispersions thereof are commercially available, and these commercially available products can also be used.

As a commercial item (trade name) of inorganic oxide particles and dispersions thereof, for example, as silica particle dispersions, methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-C, ST-N, ST-O, ST-OL, ST-20, ST-40, ST-50 (above, manufactured by Nissan Chemical Industries, Ltd.); Organosol PL- Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50 (above, Nippon Aerosil Co., Ltd.); 2PGME (propylene glycol monomethyl ether dispersion, manufactured by Fuso Chemical Industry Co., Ltd.) and the like as silica particles; Dex H31, Sildex H32, Sildex H51, Sildex H52, Sildex H121 Sildex H122 (manufactured by Asahi Glass Co., Ltd.); E220A, E220 (manufactured by Nihon Silica Industry Co., Ltd.); As alumina particle dispersions, alumina sol-100, alumina sol-200, alumina sol-520 (all of which are aqueous dispersions, manufactured by Nissan Chemical Industries, Ltd.); AS-1501 (i-propanol dispersion, Sumitomo Osaka Cement) AS-150T (toluene dispersion, manufactured by Sumitomo Osaka Cement Co., Ltd.), etc., as a zirconia particle dispersion, HXU-110JC (toluene dispersion, manufactured by Sumitomo Osaka Cement Co., Ltd.), etc. As a dispersion of zinc antimonate particles, Celnax (aqueous dispersion, manufactured by Nissan Chemical Industries, Ltd.), etc. As dispersion liquid, Nidoraru (aqueous dispersion, Taki Chemical Co., Ltd.) and the like, can be exemplified respectively.
Moreover, in order to suppress coloring of hardened | cured material, antioxidant, a light stabilizer, and a ultraviolet absorber can also be mix | blended with a thermosetting resin composition as needed.

  Examples of the antioxidant include trade names such as Sumizer BHT, Sumizer GM, Sumizer GS, Sumizer MDP-S, Sumizer BBM-S, Sumizer WX-R, Sumizer GA-80, Sumitizer TZ-S, TP. Chemical Industry Co., Ltd.); Irganox 1076, Irganox 565, Irganox 1520, Irganox 245, Irganox 1010, Irganox 1098, Irganox 1330, Irganox 1425, Irganox 3114, Irganox MD nox1790 (manufactured by Cytec); TNP (manufactured by Yokkaichi Gosei Co., Ltd.); Weston 618 (manufactured by Vorg Warner); Irgafos 168 (manufactured by Ciba Specialty Chemicals); Co., Ltd.), Sandstab P-EPQ, Ultranox 626, and the like.

Examples of the light stabilizer include, for example, Biosorb04 (manufactured by Kyodo Yakuhin Co., Ltd.); Tinuvin 622, Tinuvin 765 (manufactured by Ciba Specialty Chemicals); Cyasorb UV-3346 (manufactured by Cytec); AdekatabLA-57 (Manufactured by Asahi Denka Kogyo Co., Ltd.), Chimassorb 119, Chimassorb 944 and the like.
Examples of the ultraviolet absorber include, for example, Viosorb 80, Viosorb 110, Viosorb 130, Viosorb 520, Viosorb 583, Viosorb 590 (above, manufactured by Kyodo Yakuhin Co., Ltd.); -Specialty Chemicals Co., Ltd.); AdekatabLA-31 (Asahi Denka Kogyo Co., Ltd.) etc. can be mentioned.

Furthermore, in the thermosetting resin composition, if necessary, an aliphatic polyol such as ethylene glycol or propylene glycol, an aliphatic or aromatic carboxylic acid, or phenol, as long as the desired effects of the present invention are not impaired. Carbon dioxide generation inhibitors such as compounds; Stress relaxation agents such as polyalkylene glycols and polydimethylsiloxane derivatives; Impact modifiers such as various rubbers and organic polymer beads, plasticizers, lubricants, and other silane couplings Agent, flame retardant, antistatic agent, leveling agent, ion trapping agent, sliding property improving agent, far denaturing imparting agent, surface tension reducing agent, antifoaming agent, anti-settling agent, antioxidant, release agent, fluorescent agent Additives other than those described above, such as colorants and conductive fillers, may be blended.
The preparation method of a thermosetting resin composition is not specifically limited, It can prepare by mixing each component by a conventionally well-known method.

Optical Semiconductor Encapsulant The thermosetting resin composition of the present invention can also be used as an optical semiconductor encapsulant.
When forming the optical semiconductor encapsulant, the thermosetting resin composition of the present invention is applied to a predetermined portion of the substrate having the optical semiconductor layer by, for example, coating, potting, impregnation, etc., and then heated. Harden.
As a more specific construction method of the composition, for example, a known method such as application or potting with a dispenser, application by screen printing under vacuum or normal pressure, reaction injection molding, or the like can be employed.

Moreover, as a method of hardening each composition for optical semiconductor sealing after construction, conventionally well-known hardening apparatuses, such as a closed-type hardening furnace and a tunnel furnace which can be continuously hardened, can be used, for example.
As a heating method for curing, for example, a conventionally known method such as hot air circulation heating, infrared heating, high frequency heating or the like can be employed.
The curing conditions are preferably about 80 to 250 ° C. and about 30 seconds to 15 hours, for example. At the time of curing, when it is intended to reduce the internal stress of the cured product, for example, after preliminary curing at 80 to 120 ° C. for about 0.5 to 5 hours, 0.1 to 120 to 180 ° C., for example. It is preferable to perform post-curing under conditions of about 15 hours, and when aiming at short-time curing, for example, it is preferable to perform curing at 150 to 250 ° C. for about 30 seconds to 30 minutes.

Adhesive for optical semiconductor The thermosetting resin composition of the present invention can be used as an adhesive for optical semiconductor.
The adhesive for optical semiconductor sealing of the present invention can be applied to the lead frame by a method such as stamping, and the LED chip can be placed on the lead frame and heated in an oven at 50 to 250 ° C. for 30 minutes to 4 hours for adhesion.

  The following examples further illustrate the embodiments of the present invention more specifically, but the present invention is not limited to these examples.

Measuring method of Mw (polystyrene conversion): Column: TSKgelGRCXLH manufactured by Tosoh, solvent: tetrahydrofuran, temperature: 40 ° C., pressure: 68 kgf / cm ²
The molding jig and curing conditions of the composition for optical semiconductor encapsulation, and the evaluation points of the appearance, UV durability and hardness of the cured product are as follows.

Molding jig:
Two glass plates with a polyethylene terephthalate film attached to the surface were opposed to each other, and a silicon rubber rod having a diameter of 2 mm was sandwiched between the ends of the glass plate in a U shape to form a molding jig.

Curing conditions:
The composition for optical semiconductor sealing was poured into the molding jig and cured by heating in an oven at 150 ° C. for 1.5 hours to obtain a cured product.

Guidelines for evaluating transparency:
The cured product was measured with a spectrophotometer.

○ ... (light transmittance at 470 nm) ≧ 90%
X ... (light transmittance at 470 nm) <90%

Evaluation procedure for UV durability:
The cured product was irradiated with ultraviolet rays (UV) continuously at 63 ° C. for 2 weeks using an ultraviolet long life fade meter (manufactured by Suga Test Instruments Co., Ltd.), and the transmittance at a wavelength of 470 nm before and after irradiation was measured spectrophotometrically. Measured with a meter.

○ ... (Transmission after irradiation) / (Initial transmittance) ≧ 0.9
× ... (Transmission after irradiation) / (Initial transmittance) <0.9

Heat-resistant:
The transmittance at 470 nm was measured at the initial stage of the cured product and after being left in an oven at 150 ° C. for 120 hours.

○ ... (Transmission after irradiation) / (Initial transmittance) ≧ 0.9
× ... (Transmission after irradiation) / (Initial transmittance) <0.9

Evaluation procedure for cracking and peeling:
Ten samples were prepared by injecting a semiconductor sealing composition into a lead frame and curing at 150 ° C. for 1.5 hours. After this sample was repeated 200 times at −50 to 100 ° C. heat cycle, cracks and peeling were observed with a microscope.
0 out of 10 samples with cracks / peeling
1-5 out of 10 samples with cracks / peeling
6 or more of 10 samples with cracks / peeling ×

Adhesiveness:
An optical semiconductor sealing adhesive was applied to the lead frame, and a sapphire chip was placed on it and heated in an oven at 150 ° C. for 1 hour to prepare 20 adhesive test samples. Next, the adhesion test sample was placed on a hot plate at 150 ° C., and the number of adhesion test samples that had peeled off when tucked with tweezers was counted.
◎ ・ ・ ・ Adhesion test sample peeled = 0 ○○ Adhesion test sample peeled 1 or 2 × ・ ・ ・ Adhesion test sample peeled ≧ 3

Example 1
In a 1 L three-necked flask equipped with a thermometer, a condenser, a stirrer, and a nitrogen introduction tube, 200.0 g of diallyl monoglycidyl isocyanuric acid, 20 μL of a 2 wt% platinum-divinyltetramethyldisiloxane complex xylene solution, 101.2 g of tetramethyldisiloxane Was added and reacted at 70 ° C. for 1 hour and at 90 ° C. for 5 hours to obtain a transparent viscous liquid. The weight average molecular weight measured by GPC was 9,500. ¹ H-NMR is shown in FIG.

Example 2
Into a 1 L three-necked flask equipped with a thermometer, a condenser, a stirrer, and a nitrogen inlet tube, 64.8 g of diallyl monoglycidyl isocyanuric acid, 10 μL of a 2% platinum-divinyltetramethyldisiloxane xylene solution, and 86.3 g of octamethyltetrasiloxane. In addition, a transparent viscous liquid was obtained by reacting at 150 ° C. for 5 hours. The weight average molecular weight measured by GPC was 4,300. ¹ H-NMR is shown in FIG.

Example 3
In a 1 L three-necked flask equipped with a thermometer, a condenser, a stirrer, and a nitrogen inlet tube, 50.0 g of diallyl monoglycidyl isocyanuric acid, 10 μL of a 2% platinum-divinyltetramethyldisiloxane xylene solution, a terminal hydrogen dimethylsiloxane oligomer (DMS- 113.1 g was added and reacted at 150 ° C. for 5 hours to obtain a transparent viscous liquid. The weight average molecular weight measured by GPC was 27,100. ¹ H-NMR is shown in FIG.

Example 4 (Optical semiconductor encapsulant evaluation)
Carboxylic anhydride of the formula (16) (trade name MH700, manufactured by Shin Nippon Rika Co., Ltd., 30 parts by weight, PX-4ET: tetra as a curing accelerator, based on 100 parts by weight of the isocyanuric ring-containing polymer obtained in Example 2. Add 0.3 parts by weight of n-butylphosphonium O, O-diethylphosphorodithionate (trade name Hishicolin PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.), mix uniformly, defoam and cure Table 1 shows the results of UV durability, heat resistance, and crack / peeling evaluation.

Example 5 (Optical semiconductor encapsulant evaluation and adhesive evaluation)
0.2 parts by weight of the thermal acid generator of the formula (39) is added to 100 parts by weight of the isocyanuric ring polymer obtained in Example 2, mixed uniformly, defoamed, cured, UV durability, heat resistance, Crack / peeling evaluation was performed. The results are shown in Table 1.

Comparative Example 1
90 parts by weight of YX8000, 10 parts by weight of CE2021 and 90 parts by weight of MH700 were uniformly mixed, defoamed, cured, and subjected to UV durability, heat resistance, crack / peeling evaluation. The results are shown in Table 1.

Comparative Example 2
Add 90 parts by weight of YX8000, 10 parts by weight of CE2021 and 0.2 parts by weight of thermal acid generator of formula (39), mix evenly, defoaming, curing, UV durability, heat resistance, crack / peeling evaluation went. The results are shown in Table 1.
YX8000 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.):

ＣＥ２０２１（商品名、ダイセル化学工業（株）製）：

CE2021 (trade name, manufactured by Daicel Chemical Industries, Ltd.):

¹ H-NMR spectrum diagram of the polymer obtained in Example 1. FIG. ¹ H-NMR spectrum diagram of the polymer obtained in Example 2. FIG. ¹ H-NMR spectrum diagram of the polymer obtained in Example 3. FIG.

Claims (12)

Following formula (1)

Here, R ₁ is a hydrogen atom or a monovalent organic group, and R ₂ is a divalent organic group.
And a polymer having a weight average molecular weight of 1,000 to 1,000,000. In the above formula (1), R ₂ represents the following formula (2)

Here, R ₃ and R ₄ may be the same or different and are a methyl group, an ethyl group, a phenyl group, a vinyl group, a glycidyl group, a hydrogen atom or a hydroxyl group, and R ₅ is an oxygen atom, a methylene group, or a phenylene group. Or a direct bond and n is an integer from 0 to 20,
And R ₁ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an epoxy group, a hydroxyl group or a carboxyl group. The polymer according to claim 1, which is a monovalent organic group. The polymer according to claim 2, wherein R ₁ is a monovalent organic group containing an epoxy group, R ₃ and R ₄ are a methyl group, an ethyl group, or a phenyl group, and R ₅ is an oxygen atom. The polymer according to claim 1, wherein an N-monosubstituted isocyanuric acid represented by the following formula (3) and a dihalogen compound represented by the following formula (4) are reacted in the presence of an alkali metal compound. Manufacturing method.

Here, R ₁ is a monovalent organic group, R ₂ is a divalent organic group, and X is a halogen atom. 3. The hydrosilylation reaction of N, N ′, N ″ -trisubstituted isocyanuric acid represented by the following formula (5) and a silane compound represented by the following formula (6): Production method of polymer.

Here, the definitions of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are the same as those in the above formula (2). An optical semiconductor composition comprising the polymer according to claim 1. (A) A composition for an optical semiconductor comprising the polymer according to claim 3 and (B) a carboxylic acid anhydride and / or a polyvalent carboxylic acid. (A) A composition for an optical semiconductor comprising the polymer according to claim 3 and (C) a thermal acid generator. (A) A composition for an optical semiconductor comprising the polymer according to claim 3, (D) a metal chelate compound, and (E) an acid. (A) An optical semiconductor composition comprising the polymer according to claim 3, (F) a silane compound represented by the following formula (7), and (G) a curing catalyst having a transition metal.
H _r —Si—R _{0 (4-r)} (7)
However, R ₀ is selected from an alkyl group having 1 to 20 carbon atoms and an aryl group having 1 to 20 carbon atoms. r is selected from 1, 2, 3; The optical semiconductor element which uses the composition for optical semiconductors of Claim 6 as a sealing material. An optical semiconductor device comprising the optical semiconductor composition according to claim 6 as an adhesive.

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