JP5914991B2 - Heat curable silicone resin composition - Google Patents

Description

  The present invention relates to a thermosetting silicone resin composition.

  Conventionally, silicone resin is superior in gas permeability compared to other resins. Therefore, when a composition containing a silicone resin (for example, Patent Document 1) is used as an electronic material, noble metals such as silver plating are sulfur in the atmosphere. There is a problem in that it is sulfurized and discolored by a system compound (for example, hydrogen sulfide).

Japanese Patent Laid-Open No. 2001-200161

  Then, an object of this invention is to provide the thermosetting silicone resin composition which is excellent in sulfidation resistance.

  As a result of intensive studies to solve the above problems, the present inventor has found that (A) an organopolysiloxane having a silanol group, (B) an organopolysiloxane having an alkoxylyl group, and (C) a condensation catalyst. Furthermore, the present inventors have found that a silicone resin composition containing a thiazole compound and / or a triazine compound is excellent in sulfidation resistance, and completed the present invention.

That is, this invention provides the following 1-12.
1. (A) an organopolysiloxane having a silanol group,
(B) an organopolysiloxane having an alkoxylyl group,
(C) A condensation catalyst, and (D) a thermosetting silicone resin composition containing a thiazole compound and / or a triazine compound.
2. 2. The thermosetting silicone resin composition according to 1 above, wherein the component (D) contains at least 2-mercaptobenzothiazole.
3. 3. The thermosetting silicone resin composition according to 1 or 2 above, wherein the condensation catalyst (C) is a metal compound containing at least one selected from the group consisting of Al, Zn, Sn, Zr, Hf, Ti, and a lanthanoid.
4). The component (C) includes at least a metal salt compound of Zn, a metal salt compound of Sn and / or a metal salt compound of lanthanoid, and the metal salt compound of Sn and / or lanthanoid metal with respect to the metal salt compound of Zn 4. The thermosetting silicone resin composition according to any one of 1 to 3, wherein the salt compound has a weight ratio of 1 or less.
5. The component (A) is
Diorganopolysiloxane represented by the following formula (1), and / or
R ₃ (R in the formula are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms.) SiO _1/2 units and said SiO _4/2 repeating units of SiO _4/2 units 1 to 4 above containing a silicone resin having a ratio of the R ₃ SiO _1/2 unit of 0.5 mol to 1.2 mol with respect to 1 mol of the unit and having less than 6.0% by mass of the silanol group. The heat-curable silicone resin composition according to any one of the above.

[In Formula (1), R ¹ is the same or different alkyl group and aryl group, and n is an integer of 10 or more. ]
6). The thermosetting property in any one of said 1-5 whose quantity of said (D) component is 0.01-10 mass parts with respect to a total of 100 mass parts of said (A) component and said (B) component. Silicone resin composition.
7). The thermosetting property in any one of said 1-6 whose quantity of the said (C) component is 0.001-10 mass parts with respect to a total of 100 mass parts of the said (A) component and the said (B) component. Silicone resin composition.
8). The thermosetting silicone resin composition according to any one of 1 to 7, wherein the amount of the component (B) is 0.1 to 5000 parts by mass with respect to 100 parts by mass of the component (A).
9. Furthermore, the thermosetting property in any one of said 1-8 containing at least 1 sort (s) chosen from the group which consists of bis (alkoxy silyl) alkane, bis (alkoxy silyl alkyl) amine, and an isocyanurate compound as (E) component. Silicone resin composition.
10. 10. The thermosetting silicone resin composition according to 9, wherein the amount of the component (E) is 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B).
11 The silicone resin further contains R ₂ SiO _2/2 units (wherein R is an unsubstituted or substituted allyl group, alkyl group or aryl group, respectively) and RSiO _{3 with} respect to 1 mol of SiO _4/2 units. _{/ 2} units (wherein each R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms) is at least one of the R ₂ SiO _2/2 unit, the RSiO _{3 / The two} units are each 1.0 mol or less, and the total of the R ₂ SiO _2/2 unit and the RSiO _3/2 unit is 1.0 mol or less. Heat curable silicone resin composition.
12 The optical semiconductor sealing body formed by sealing the optical semiconductor with the thermosetting silicone resin composition according to any one of 1 to 11 above.

The heat-curable silicone resin composition of the present invention is excellent in sulfidation resistance.
The sealed optical semiconductor of the present invention is excellent in sulfidation resistance.

FIG. 1 is a cross-sectional view schematically showing an example of a laminate in the present invention. FIG. 2 is a cross-sectional view schematically showing another example of the laminate in the present invention. FIG. 3 is a cross-sectional view schematically showing an example of the sealed optical semiconductor of the present invention. FIG. 4 is a cross-sectional view schematically showing another example of the sealed optical semiconductor of the present invention. FIG. 5 is a cross-sectional view schematically showing another example of the sealed optical semiconductor of the present invention. FIG. 6 is a diagram schematically showing an example of an LED display using the composition of the present invention and / or the sealed optical semiconductor of the present invention.

  The present invention will be described in detail below. First, the thermosetting silicone resin composition of the present invention will be described. The thermosetting silicone resin composition of the present invention (the composition of the present invention) comprises (A) an organopolysiloxane having a silanol group, (B) an organopolysiloxane having an alkoxyl group, (C) a condensation catalyst, and ( D) A thermosetting silicone resin composition containing a thiazole compound and / or a triazine compound.

The organopolysiloxane (A) having a silanol group (organopolysiloxane (A)) contained in the composition of the present invention is an organopolysiloxane having at least one silanol group, preferably at least two in one molecule. is there.
The hydrocarbon group that the organopolysiloxane (A) has is not particularly limited, and examples thereof include an aromatic group (aryl group) such as a phenyl group; an alkyl group; an alkenyl group.
The main chain of the organopolysiloxane (A) may be linear, branched, or network.

The organopolysiloxane (A) is a diorganopolysiloxane represented by the following formula (1) and / or R ₃ SiO _1/2 unit (from the viewpoint of excellent room temperature stability, heat curability, and heat resistance. In the formula, each R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms.) And R ₄ SiO _2/2 units as repeating units, and R ₃ SiO ₁ per 1 mol of SiO _4/2 units. _It is preferable to include a silicone resin having a _{/ 2} unit ratio of 0.5 mol to 1.2 mol and having a silanol group of less than 6.0 mass%.

In formula (1), R ¹ is the same or different alkyl group or aryl group, and n can be an integer of 10 or more. The alkyl group can have 1 to 18 carbon atoms, and the aryl group can have 6 to 18 carbon atoms. The diorganopolysiloxane represented by the formula (1) is a chain.

In the formula (1), examples of the alkyl group represented by R ¹ include linear or branched groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group. An alkyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; and the like. Examples of the aryl group represented by R ¹ include a phenyl group and a naphthyl group. Of these, a methyl group and a phenyl group are preferable, and a methyl group is more preferable.
In formula (1), n can be made into the numerical value corresponding to the weight average molecular weight of organopolysiloxane (A), and it is preferable that it is an integer of 10-15,000.

As the organopolysiloxane (A), the silicone resin includes R ₃ SiO _1/2 units (wherein R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms) and SiO. You can have _4/2 units. Examples of the silicone resin that can have R ₃ SiO _1/2 units and SiO _4/2 units include MQ resin, MT resin, MTQ resin, MDT resin, and MDTQ resin.
As the organopolysiloxane (A), the silicone resin includes R ₃ SiO _1/2 units (wherein R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms) and SiO. _It is preferable that the ratio of R ₃ SiO _1/2 units is 0.5 mol to 1.2 mol with respect to 1 mol of SiO _4/2 units in terms of repeating units of _4/2 units. Moreover, it is preferable that a silicone resin has less than 6.0 mass% of silanol groups.

In the silicone resin, R in the R ₃ SiO _1/2 unit includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, tert-butyl group, pentyl group. Alkyl groups such as hexyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group; aryl groups such as phenyl group; And halogenated alkyl groups such as a methyl group, a 3-chloropropyl group, a 1-chloro-2-methylpropyl group, and a 3,3,3-trifluoropropyl group; among others, a methyl group, a vinyl group, and a phenyl group It is preferably a group, and more preferably a methyl group.

In the silicone resin, the ratio of R ₃ SiO _1/2 units to 1 mol of SiO _4/2 units is 0.5 to 1.2 mol, preferably 0.65 to 1.15 mol. If the ratio of R ₃ SiO _1/2 units is within this range, the cured product of the composition of the present invention has appropriate strength and excellent transparency.

  Silicone resins have silanol groups. The amount of silanol groups contained in the silicone resin is preferably less than 6.0% by mass of the silicone resin from the viewpoint of excellent room temperature stability. The content of silanol groups is preferably 0.1% by weight or more, and more preferably 0.2 to 3.0% by weight. When the content of the silanol group is within this range, the hardness of the cured product of the composition of the present invention is appropriate, the adhesiveness is good, and the strength is also appropriate.

From the viewpoint of excellent heat resistance and light resistance, the silicone resin further has R ₂ SiO _2/2 units (wherein R is an unsubstituted or substituted allyl group, alkyl group or aryl group, respectively) and RSiO _{3. / 2} unit (wherein each R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms. The unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms is as defined above. As well as at least one or both. Silicone resin, heat, from the viewpoint of excellent light resistance, the R ₂ SiO _2/2 units at least one of R ₂ SiO _2/2 units and RSiO _3/2 units to SiO _4/2 units 1 mole The RSiO _3/2 unit is preferably 1.0 mol or less, and the total of the R ₂ SiO _2/2 unit and the RSiO _3/2 unit is preferably 1.0 mol or less. More preferably, each unit of R ₂ SiO _2/2 units and RSiO _3/2 units is 0.2 to 0.8 mol, and the total of each unit is 1.0 mol or less. Thus, if it is a mixture ratio, the composition of this invention is excellent in transparency. Specific examples of such a blending ratio include a combination of 0.2 mol of R ₂ SiO _2/2 units and 0.7 mol of RSiO _3/2 units with respect to 1 mol of SiO _4/2 units.

When the diorganopolysiloxane represented by the formula (1) and a silicone resin having R ₃ SiO _1/2 units and SiO _4/2 units are used in combination as the component (A), R ₃ SiO _1/2 units The amount of the silicone resin having a SiO _4/2 unit is 200 to 10 parts by mass with respect to 100 parts by mass of the diorganopolysiloxane represented by the formula (1) from the viewpoint of excellent physical properties and workability. Is preferable, and it is more preferable that it is 150-50 mass parts.

The method for producing the organopolysiloxane (A) is not particularly limited, and for example, a conventionally known production method can be used.
The molecular weight of the organopolysiloxane (A) is preferably 1,000 to 1,000,000, and more preferably 1000 to 100,000.
In the present invention, the molecular weight of the organopolysiloxane (A) is a weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent.
Organopolysiloxane (A) may be used individually by 1 type, and may use 2 or more types together.

  The composition of this invention contains (B) organopolysiloxane [organopolysiloxane (B)] which has an alkoxyl group from a viewpoint that it is excellent in heat-hardening property. The organopolysiloxane (B) contained in the composition of the present invention is an organopolysiloxane having one or more, preferably two or more alkoxysilyl groups in one molecule. It does not specifically limit as a hydrocarbon group which organopolysiloxane (B) has, For example, the thing similar to organopolysiloxane (A) is mentioned. The main chain of the organopolysiloxane (B) may be linear, branched, or network.

  Examples of the organopolysiloxane (B) include silicone alkoxy oligomers such as methylmethoxy oligomer. The silicone alkoxy oligomer is a silicone resin whose main chain is an organopolysiloxane and whose molecular ends are blocked with alkoxysilyl groups. As a methyl methoxy oligomer, the compound represented by a following formula (b2-2) is mentioned, for example.

In formula (b2-2), R ⁹ represents a methyl group, a represents an integer of 1 to 100, and b represents an integer of 0 to 100.
A commercially available product can be used as the methyl methoxy oligomer, and examples thereof include x-40-9246 (weight average molecular weight: 6000, manufactured by Shin-Etsu Chemical Co., Ltd.).

Specific examples of the compound represented by the formula (b2-2) include a compound represented by the following formula (b2-1).
R ⁷ _m Si (OR ⁸ ) _n O _{(4-mn) / 2} (b2-1)
In formula (b2-1), R ⁷ is an organic group, R ⁸ is an alkyl group, m is 0 <m <2, n is 0 <n <2, and m + n is 0 <m + n ≦ 3.
Examples of the organic group represented by R ⁷ include a hydrocarbon group that may contain at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. Specific examples thereof include an alkyl group (carbon 1 to 6 are preferable.), (Meth) acrylate groups, alkenyl groups, aryl groups, combinations thereof, and the like. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 2-methyl-1-propenyl group, and a 2-methylallyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Of these, a methyl group, a (meth) acrylate group, and a (meth) acryloxyalkyl group are preferable.
The alkyl group represented by R ⁸ has the same meaning as described as the alkyl group as the organic group represented by R ⁷ .

In addition to the methylmethoxy oligomer [for example, the compound represented by the formula (b2-2)], the organopolysiloxane (B) has, for example, an alkoxysilyl group at least at one end and 3 per molecule. And a compound having at least one alkoxy group (derived from an alkoxysilyl group) (hereinafter also referred to as “organopolysiloxane (b3)”).
The organopolysiloxane (b3) can be obtained, for example, as a reaction product obtained by dealcoholization condensation of 1 mol or more of a silane compound having an alkoxylyl group with respect to 1 mol of a polysiloxane having both terminal silanol groups.
Examples of the polysiloxane having silanol groups at both ends used for producing the organopolysiloxane (b3) include dialkyl polysiloxanes having silanol groups at both ends (specifically, for example, silanol groups at both ends). Dimethylpolysiloxane).
Examples of the silane compound having an alkoxy group used for producing the organopolysiloxane (b3) include a compound represented by the following formula (b1), a hydrolysis condensate thereof, and the above-described formula (b2-1). ) And the like.

Si (OR ⁵ ) _n R ⁶ _4-n (b1)
In the formula (b1), n represents 2, 3 or 4, R ⁵ represents an alkyl group, and R ⁶ represents an organic group. The organic group represented by R ⁶ has the same meaning as that described as the organic group that the organopolysiloxane (B) can have.

Examples of the compound represented by the formula (b1) include dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane; methyltrimethoxysilane , Trialkoxysilanes such as methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropyloxysilane; γ -(Meth) acryloxyalkyltrialkoxy such as (meth) acryloxypropyltrimethoxysilane and γ- (meth) acryloxypropyltriethoxysilane Silane; and the like.
Note that (meth) acryloxytrialkoxysilane means acryloxytrialkoxysilane or methacryloxytrialkoxysilane. The same applies to (meth) acrylate groups and (meth) acryloxyalkyl groups.

As organopolysiloxane (b3), what is represented by a following formula (b3-1) is mentioned, for example.

In formula (b3-1), n can be a numerical value corresponding to the molecular weight of the organopolysiloxane (b3).
The compound represented by the formula (b3-1) is produced, for example, by modifying polysiloxane having silanol groups at both ends with tetramethoxysilane (corresponding to the compound represented by the formula (b1)). be able to.

  As the organopolysiloxane (B), those represented by the formula (b2-1), those represented by the formula (b3-1), and diorganopolysiloxane blocked with a hydrolysis condensate of alkoxysilane are preferable. .

  The molecular weight of the organopolysiloxane (B) is preferably 500 to 1,000,000, and more preferably 1,000 to 100,000. In addition, the molecular weight of organopolysiloxane (B) shall be the weight average molecular weight of polystyrene conversion by the gel permeation chromatography (GPC) which uses chloroform as a solvent.

It does not specifically limit as a manufacturing method of organopolysiloxane (B), For example, a conventionally well-known thing is mentioned.
A compound (B) may be used individually by 1 type, and may use 2 or more types together.
The amount of the organopolysiloxane (B) is preferably 0.1 to 5000 parts by mass, preferably 0.5 to 5000 parts per 100 parts by mass of the organopolysiloxane (A) from the viewpoint of excellent heat curability. More preferably, it is 5 parts by mass, and even more preferably 5 to 1,000 parts by mass.

The (C) condensation catalyst contained in the composition of the present invention is not particularly limited as long as it is a catalyst used for condensation of silanol groups and hydrolyzable silyl groups.
(C) The condensation catalyst can be a metal salt; complex; alcoholate; oxide; multi-metal oxide, salt and / or complex thereof; (C) The condensation catalyst is preferably a metal salt compound from the viewpoint of excellent room temperature stability and curability.
(C) The condensation catalyst can be a compound having a metal (for example, at least one selected from the group consisting of Al, Zn, Sn, Zr, Hf, Ti, and a lanthanoid) and an organic group. The metal can be bonded to the organic group, for example, through a heteroatom such as an oxygen atom, nitrogen atom, sulfur atom, and / or via a linking group such as an ester bond. The organic group includes an aliphatic hydrocarbon group (including chain, branched, cyclic, and combinations thereof. The aliphatic hydrocarbon group can have an unsaturated bond), aromatic hydrocarbon groups, and combinations thereof Is mentioned. The organic group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the organic group include an organic carboxylate (—O—CO—R); an alkoxy group or a phenoxy group in which a hydrocarbon group is bonded to an oxy group (—O—R); a ligand; These combinations are mentioned.
(C) The condensation catalyst is preferably a metal compound containing at least one selected from the group consisting of Al, Zn, Sn, Zr, Hf, Ti and a lanthanoid from the viewpoint of excellent curability and room temperature stability. More preferably, it is a metal salt compound.

Examples of the aluminum compound include aluminum such as tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, alkylacetoacetate aluminum diisopropylate such as ethylacetoacetate aluminum diisopropylate, and aluminum butoxybisethylacetoacetate. Chelate;
Aluminum salts such as aluminum octylate, compounds containing cyclic aluminum oxide (for example, compounds represented by the following formula (7)), aluminum triacetate, aluminum tristearate;
Aluminum alcoholates such as aluminum sec-butylate, aluminum triethoxide, aluminum triisopropoxide, alkoxyaryl aluminates.

Examples of the zinc compound (metal salt compound of zinc) include those represented by the following formula (1) and formula (2); group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and zinc nitrate One obtained from reacting an acid with 1.5 mol or more and less than 2 mol with respect to 1 mol of at least one selected from:

In formula (1), R ¹ is an alkyl group having 1 to 18 carbon atoms, an aryl group.
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, and undecyl. . Examples of the aryl group include a phenyl group, a naphthyl group, and azulene.

The zinc compound represented by Formula (2) is as follows.

In formula (2), R ² and R ³ are the same or different monovalent hydrocarbon groups having 1 to 18 carbon atoms and alkoxy groups. In formula (2), R ² and R ³ in the same (R ² COCHCOR ³ ) may be interchanged.
Examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms include an alkyl group having 1 to 18 carbon atoms and an aryl group. A C1-C18 alkyl group and an aryl group are synonymous with the above.
Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

Examples of zinc compounds (zinc metal salt compounds) include aliphatic carboxylic acids such as zinc acetate, zinc acetyl acetate, zinc 2-ethylhexanoate, zinc octylate, zinc neodecanoate, zinc laurate, and zinc stearate. Carboxylates such as zinc, zinc alicyclic carboxylates such as zinc naphthenate, zinc benzoate, zinc p-tert-butylbenzoate, zinc aromatic carboxylates such as zinc salicylate; zinc (meth) acrylates; Zinc chelates such as zinc acetylacetonate [Zn (II) acetylacetonate, Zn (acac) ₂ ], 2,2,6,6-tetramethyl-3,5-heptanedionate Zn.

  In addition, as a zinc compound (zinc metal salt compound), for example, at least one selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and zinc nitrate: What is obtained by making it react 1.5 mol or more and less than 2 mol (zinc compound-1) can be used. By containing such a zinc compound, it is excellent in sulfidation resistance, and particularly excellent in long-term sulfidation resistance.

The acid used in producing the zinc compound-1 is not particularly limited, and examples thereof include inorganic acids and organic acids [organic carboxylic acids: for example, R- (COOH) _n (n is an integer of 1 or more)]. . ], Any of these esters. Examples of the inorganic acid include phosphoric acid and boric acid. The hydrocarbon group that the organic carboxylic acid has other than the carboxyl group is not particularly limited. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. Examples of the organic acid include a saturated carboxylic acid having 2 to 30 carbon atoms such as stearic acid, palmitic acid, lauric acid, and 2-ethylhexanoic acid; and an unsaturated carboxylic acid such as (meth) acrylic acid. The hydrocarbon group forming the ester in the ester of the acid is not particularly limited. For example, the same thing as the above is mentioned. Among these, phosphoric acid, 2-ethylhexanoic acid, benzoic acid, and esters thereof are preferred from the viewpoint of excellent transparency and superior sulfidation resistance (especially long-term sulfidation resistance).
In the present invention, the amount of the acid used in producing the zinc compound-1 is at least one selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and zinc nitrate: 1 mol. The amount is preferably 1.5 mol or more and less than 2 mol. In such a range, transparency and sulfidation resistance (especially sulfidation resistance over a long period) are excellent. The amount of the acid is 1.5 to 1 with respect to at least one selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and zinc nitrate for the same reason as above. 0.9 mol is preferable, and 1.6 to 1.8 mol is more preferable.

Examples of the zinc compound-1 include those represented by Zn _a (O) _x (OH) _y (—O—CO—R) _z , phosphates having zinc, and borates having zinc. In the formula, R is a hydrocarbon group. The hydrocarbon group is as defined above. When there are a plurality of R, the plurality of R may be the same or different. In the formula, a is 1 or more (an integer of 1 or more), x and y are 0 or more (an integer of 0 or more), z is 1 or more (an integer of 1 or more), and z / a is 2 And [(2x + y + z) / a] = 2.
Specific examples of the zinc compound-1 include Zn (OH) (— O—CO—R), R—CO—O—Zn—O—Zn—O—CO—R; O—Zn—O—P. -, The phosphate which has zinc like Zn-O-Zn-OPO-.
When x is 1 or more, the zinc compound-1 can have a bond such as -Zn-O-Zn- in its structure. Such bonds can be formed, for example, by dehydration condensation of the product in the production of zinc compounds.
Zinc compound-1 can contain as raw materials zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate, zinc nitrate; and raw acid as unreacted materials.

  The zinc compound-1 reacts at least one selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate, and zinc nitrate: 1 mol to 1.5 mol or more and less than 2 mol of acid. Except for this, the production is not particularly limited. For example, it can be produced by stirring at least one member selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and zinc nitrate and an acid under room temperature conditions or by heating. it can.

Examples of the tin compound include a divalent tin compound and a tetravalent tin compound.
Examples of the divalent tin compound (divalent tin metal salt compound) include bis (2-ethylhexanoic acid) tin and bis (neodecanoic acid) tin.

Examples of the tetravalent tin compound (tetravalent tin metal salt compound) include those represented by the following formula (II), bis type and polymer type represented by the formula (II).
_{^{R 3 a -Sn- [O-CO}} -R 4] 4-a (II)
In the formula, R ³ is an alkyl group, R ⁴ is a hydrocarbon group, and a is an integer of 1 to 3.
Examples of the alkyl group include those having 1 or more carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and an octyl group.
The hydrocarbon group is not particularly limited. Examples of the hydrocarbon group (including chain, branched, cyclic, and combinations thereof) include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. It can be an integer having 1 to 18 carbon atoms of the hydrocarbon group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylpentyl group, and an octyl group. The tetravalent tin compound is preferably a tetravalent tin compound having at least one alkyl group and at least one ester bond.

  Among these, tin compounds are tetravalent such as dibutyltin diacetate, dibutyltin dioleate, dibutyltin dilaurate, dibutyltin oxyacetate dibutyltin oxyoctylate and dibutyltin oxylaurate from the viewpoint of excellent curability and room temperature stability. A metal salt compound of divalent tin such as bis (2-ethylhexanoic acid) tin is preferred.

Zirconium compound (zirconium metal salt compound) is a compound represented by formula (1) [zirconyl [(Zr = O)] from the viewpoint of obtaining a cured product having excellent curability, excellent adhesiveness, and hardly discolored. ²⁺ ] as a component. And / or a compound represented by formula (2).

Formula (1)
(In the formula, R ¹ is a hydrocarbon group having 1 to 18 carbon atoms.)

Formula (2)
(In the formula, R ² is a hydrocarbon group having 1 to 16 carbon atoms, R ³ is a hydrocarbon group having 1 to 18 carbon atoms, and m is an integer of 1 to 3).
The hydrocarbon group in Formula (1) and Formula (2) has the same meaning as the organic group that (C) the condensation catalyst can have.

  The zirconium compound represented by the formula (1) is preferably an aliphatic carboxylate and / or an alicyclic carboxylate, and more preferably an alicyclic carboxylate. Examples of the zirconium compound represented by the formula (1) include aliphatic carboxylates such as zirconyl dioctylate and zirconyl dineodecanoate; alicyclic carboxylates such as zirconyl naphthenate and zirconyl cyclohexane; zirconyl benzoate; An aromatic carboxylate such as From the viewpoint of obtaining a cured product that is excellent in adhesion and hardly discolored, the zirconium compound represented by the formula (1) is preferably one or both of zirconyl dioctylate and zirconyl naphthenate.

The zirconium compound of formula (2), if it is the formula (2) was m is 2 or more, plural R ² may be the same or different. Moreover, when m is 1-2, several R < ³ > may be the same or different.
From the viewpoint of excellent heat-resistant coloring stability and compatibility (for example, compatibility with a silicone resin), the hydrocarbon group represented by R ² in the above formula (2) preferably has 3 to 16 carbon atoms. More preferably, it is 4-16. The hydrocarbon group represented by R ² has the same meaning as described above.

The hydrocarbon group represented by R ² preferably has a cyclic structure from the viewpoint that a cured product that is excellent in adhesiveness and hardly discolors can be obtained. Examples of the cyclic structure include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. R ² can have a cyclic structure in combination with, for example, an aliphatic hydrocarbon group.
Among these, from the viewpoint of excellent heat-resistant coloring stability and compatibility, the hydrocarbon group represented by R ² is preferably an alicyclic hydrocarbon group or an aromatic hydrocarbon group, such as cyclopropyl group, cyclopentyl. Group, cyclohexyl group, adamantyl group, naphthene ring (naphthate group as R ² COO—) and phenyl group are more preferable, and cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group and naphthene ring are more preferable.

Moreover, excellent heat coloration stability, from the viewpoint of excellent compatibility, the number of carbon atoms in the hydrocarbon group represented by R ³ is preferably 3-8. The hydrocarbon group represented by R ³ has the same meaning as R ² except for the number of carbon atoms. R ³ is preferably an aliphatic hydrocarbon group from the viewpoint of excellent heat-resistant coloring stability and excellent compatibility.
R ³ O— (alkoxy group) having an aliphatic hydrocarbon group is, among others, R ³ O— (alkoxy group) having an aliphatic hydrocarbon group from the viewpoint of excellent heat-resistant coloring stability and excellent compatibility. Is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, or an isopropoxy group.

  Among these, from the viewpoint of excellent heat-resistant coloring stability and compatibility, a compound having an alicyclic hydrocarbon group as a cyclic structure and a compound having an aromatic hydrocarbon group as a cyclic structure are preferable, and a zirconium trialkoxy monoester Zirconium tributoxy mononaphthate, zirconium tributoxy monoisobutyrate, zirconium tributoxy mono 2-ethylhexanoate, zirconium tributoxy monocyclopropane carboxylate, zirconium tributoxy monocyclopentane carboxylate, zirconium tributoxy More preferred are monocyclohexane carboxylate, zirconium tributoxy monoadamantane carboxylate, and zirconium tributoxy mononaphthate.

  The hafnium compound is not particularly limited as long as it is a compound having a hafnium atom and an organic group. A hafnium compound (hafnium metal salt compound) is represented by the following formula (f1) and / or the following formula (f2) because the long-term reliability of the composition of the present invention is excellent at high temperatures. It is preferable that it is a compound.

In formula (f1), n represents an integer of 1 to 4, R ¹⁵ represents a hydrocarbon group, and R ¹⁶ represents an alkyl group having 1 to 18 carbon atoms.

In the formula (f2), m represents an integer of 1 to 4, R ¹⁶ represents an alkyl group having 1 to 18 carbon atoms, R ¹⁷ and R ¹⁸ each independently represents a hydrocarbon group or alkoxy having 1 to 18 carbon atoms. It represents a group, when R ¹⁷ and R ¹⁸ are a plurality, a plurality of R ¹⁷ and R ¹⁸ may each be the same or different.

First, the hafnium compound represented by the above formula (f1) will be described.
The hydrocarbon group represented by R ¹⁵ in the formula (f1) may be linear or branched, may have an unsaturated bond, and has a hetero atom (for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc.). be able to.
Examples of the hydrocarbon group represented by R ¹⁵ include an aliphatic hydrocarbon group having 1 to 18 carbon atoms (including an alkyl group; an unsaturated aliphatic hydrocarbon group such as an allyl group; etc.), an alicyclic hydrocarbon group. , Aryl groups (aromatic hydrocarbon groups), combinations thereof and the like.
Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, and an undecyl group. Etc.
Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; naphthene ring (cycloparaffin ring derived from naphthenic acid); adamantyl A condensed ring hydrocarbon group such as a group or a norbornyl group;
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and azulene.
Among these, from the viewpoint of excellent heat curability, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof is preferable, and a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group. More preferably at least one selected from the group consisting of a group, a cyclooctyl group, a naphthene ring, an adamantyl group, a norbornyl group, a phenyl group, a naphthyl group and an azulene, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group , A naphthene ring (naphthate group as R ¹⁵ COO—) and a phenyl group are more preferable, and a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group and a naphthene ring are particularly preferable.

The number of carbon atoms of the alkyl group represented by R ¹⁶ in the formula (f1) is 1 to 18, and is preferably 3 to 8 because it is more excellent in thermosetting and excellent in resistance to sulfidation.

Examples of the alkyl group represented by R ¹⁶ include a methyl group, an ethyl group, a propyl group (n-propyl group, isopropyl group), a butyl group, a pentyl group, a hexyl group, an octyl group, and the like. , Ethyl group, propyl group (n-propyl group, isopropyl group), butyl group, and pentyl group are preferable.

Examples of the hafnium compound represented by the formula (f1) having an alicyclic hydrocarbon group as the hydrocarbon group represented by R ¹⁵ include, for example, hafnium alkoxy (mono-tri) cyclopropanecarboxylate, hafnium tetra Cyclopropanecarboxylate, hafnium alkoxy (mono-tri) cyclopentanecarboxylate, hafnium tetracyclopentanecarboxylate, hafnium alkoxy (mono-tri) cyclohexanecarboxylate, hafnium tetracyclohexanecarboxylate, hafnium alkoxy (mono-tri) adamantanecarboxylate Examples thereof include rate, hafnium tetraadamantane carboxylate, hafnium alkoxy (mono-tri) naphthate, and hafnium tetranaphthate.

Examples of the hafnium compound represented by the formula (f1) having an aromatic hydrocarbon group as the hydrocarbon group represented by R ¹⁵ include, for example, hafnium alkoxy (mono-tri) benzene carboxylate, hafnium tetrabenzenecarboxyl. Rate and the like.

Examples of the hafnium compound represented by the formula (f1) having an aliphatic hydrocarbon group as the hydrocarbon group represented by R ¹⁵ include, for example, hafnium alkoxy (mono-tri) butyrate, hafnium tetrabutyrate, hafnium. Examples include alkoxy (mono-tri) 2-ethyl hexanoate, hafnium tetra 2-ethyl hexanoate, hafnium alkoxy (mono-tri) neodecanate, and hafnium tetraneodecanate.

  In the present specification, “(mono to tri)” means any one of mono, di and tri.

  Among these, hafnium trialkoxy mononaphthate, hafnium trialkoxy monoisobutyrate, hafnium trialkoxy mono 2-ethylhexanoate, hafnium trialkoxy monocyclopropanecarboxylate, hafnium trialkoxy for reasons of excellent heat curability. Preferred are cyclobutanecarbochelate, hafnium trialkoxy monocyclopentane carboxylate, hafnium trialkoxy monocyclohexane carboxylate, hafnium trialkoxy monoadamantane carboxylate, hafnium trialkoxy monobenzene carboxylate, hafnium dialkoxy dinaphthate, Hafnium tributoxy mononaphthate, hafnium tributoxy monoisobutyrate, ha Nitrobutoxymono-2-ethylhexanoate, hafnium tributoxymonocyclopropanecarboxylate, hafnium tributoxymonocyclopentanecarboxylate, hafnium tributoxymonocyclohexanecarboxylate, hafnium trialkoxymonobenzenecarboxylate, hafnium tributoxymonoadamantanecarboxylate More preferred are rate, hafnium dibutoxy dinaphthate, and hafnium tripropoxy mononaphthate.

Next, the hafnium compound represented by the above formula (f2) will be described.
R ¹⁶ in the formula (f2) has the same meaning as R ¹⁶ in the formula (f1).
The hydrocarbon group having 1 to 18 carbon atoms represented by R ¹⁷ and R ^{18 in} formula (f2) is the same as the hydrocarbon group having 1 to 18 carbon atoms among the hydrocarbon groups represented by R ¹⁵ in formula (f1). It is.
As an alkoxy group which R < ¹⁷ >, R < ¹⁸ > in Formula (f2) shows, C1- ^C18 alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, are mentioned, for example.
R ¹⁷ and R ¹⁸ in the formula (f2) may have a halogen such as a chlorine atom, a bromine atom, or a fluorine atom.
In the formula (f2), R ¹⁷ and R ¹⁸ may be interchanged.

  Examples of the hafnium compound represented by the formula (f2) include, for example, hafnium alkoxide (mono-tri) 2,4-pentadionate, hafnium-2,4-pentadionate, hafnium alkylpentadionate, hafnium fluoro And pentafionate. Among them, hafnium di-n-butoxide (bis-2,4-pentadionate), hafnium-2,4-pentadionate, hafnium tetramethylpentadionate, hafnium trifluoropentadionate Nate is preferred.

In the present invention, the “lanthanoid compound” refers to a compound having a lanthanoid atom (Ln) such as lanthanum (La), cerium (Ce), dysprosium (Dy), ytterbium (Yb) and the like.
The lanthanoid compound (C) contained in the composition of the present invention is not particularly limited as long as it is a “lanthanoid compound”, but for the reason that the thermosetting property of the composition of the present invention is excellent, the following formula (c1) Preferred are the compounds represented.

In formula (c1), each R ^c independently represents an alkyl group having 1 to 30 carbon atoms, an allyl group or an aryl group. Ln represents a lanthanoid atom.
Examples of the alkyl group having 1 to 30 carbon atoms represented by R ^c in the formula (c1) include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n -Linear alkyl groups such as heptyl group, n-octyl group, n-nonyl group, n-decyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, sec-pentyl group, isopentyl group, Neopentyl group, 1-methylhexyl group, 1-ethylpentyl group, 1-propylbutyl group, 2-ethyl-1-methylbutyl group, 1-ethyl-3-methylbutyl group, 1,2-dimethylpentyl group, 1-ethyl 2-methylbutyl group, 1-methylheptyl group, 1-ethylhexyl group, 1-propylpentyl group, 1-ethyl-2-methylpentyl group, 3-methyl-1-propiyl Butyl group, 2-methyl-1-propylbutyl group, 1-methyloctyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-butylpentyl group, 1,3-diethylpentyl group, 1,5-dimethyl Heptyl, 1-ethyl-3-methylhexyl, 1-methylnonyl, 1-ethyloctyl, 1-propylheptyl, 1-butylhexyl, 3-ethyl-1-propylpentyl, 1,7- Branched alkyl groups such as dimethyloctyl group, 1-ethyl-4-methylheptyl group, 2-methyl-1-propylhexyl group, neononyl group, neodecyl group; cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 4- Ethylcyclohexyl group, 4-tert-butylcyclohexyl group, 4- (2-ethylhexyl) cyclohexyl Group, bornyl group, isobornyl group, adamantyl group and the like; naphthene ring (cycloparaffin ring derived from naphthenic acid); and the like.
The allyl group represented by R ^c in formula (c1) is a 2-propenyl group (—CH ₂ CH═CH ₂ ).
The aryl group represented by R ^c in formula (c1) is preferably an aryl group having 6 to 30 carbon atoms, and specifically includes, for example, a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, and a pyrenyl group. Perylenyl group, fluorenyl group, biphenyl group, terphenyl group, rubrenyl group, chrycenyl group, triphenylenyl group and the like.

Of these, the group represented by R ^c in formula (c1) is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 6 to 18 carbon atoms, and 1-ethyl A pentyl group and a naphthene ring are more preferable.

  Examples of the lanthanoid compound represented by the formula (c1) include lanthanoid 2-ethylhexanoate, lanthanoid naphthenate, and the like. Of these, lanthanum, cerium, dysprosium or ytterbium 2-ethylhexanoate is preferred from the viewpoint of excellent heat curability of the composition of the present invention, and cerium 2-ethylhexanoate (tris (2-ethylhexane Acid) cerium) is more preferred.

  Examples of titanium compounds include alcoholates such as tetraethoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, and tetraoctoxy titanium; titanium compounds such as diisopropoxy titanium ethyl acetoacetate and diisopropoxy titanium acetylacetonate. A metal salt compound is mentioned.

(C) A condensation catalyst can be used individually or in combination of 2 types or more, respectively.
The (C) condensation catalyst preferably contains at least a metal salt compound of Zn and a metal salt compound of Sn and / or a metal salt compound of lanthanoid from the viewpoint of excellent heat curability and room temperature stability. The metal salt compound of Zn, the metal salt compound of Sn, and the metal salt compound of lanthanoid are the same as described above.
(C) When the condensation catalyst includes at least a metal salt compound of Zn and a metal salt compound of Sn and / or a metal salt compound of lanthanoid, the metal salt compound of Sn and / or a metal of lanthanoid with respect to the metal salt compound of Zn The weight ratio of the salt compound is preferably 1 or less, more preferably 0.001 to 0.1, from the viewpoint of excellent heat curability and work stability.

  The amount of the component (C) is 0.001 to 10 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B) from the viewpoint of excellent heat curability and room temperature stability. Preferably, it is 0.001-1 mass part, More preferably, it is 0.01-1 mass part.

The composition of this invention is excellent in sulfidation resistance by containing a thiazole compound and / or a triazine compound as the component (D).
The thiazole compound as the component (D) contained in the composition of the present invention is not particularly limited as long as it is a compound having a thiazole skeleton. Examples include benzothiazole which is unsubstituted or has a substituent (for example, a mercapto group). Specific examples include a benzothiazole; a thiazole compound having a mercapto group such as 2-mercaptobenzothiazole; and a thiazole compound having a substituent such as a hydrocarbon group, a fluoro group, and a silyl group. Of these, 2-mercaptobenzothiazole and a benzothiazole compound having a silyl group are preferable from the viewpoints of superior sulfurization resistance, color stability, and compatibility.

The triazine compound as the component (D) contained in the composition of the present invention is not particularly limited as long as it is a compound having a triazine skeleton. Examples of the triazine compound include a triazine compound having a substituent such as a hydrocarbon group, a mercapto group, a fluoro group, a silyl group, a siloxane skeleton, or a combination thereof.
Of these, triazine thiol compounds (compounds having a triazine skeleton and a mercapto group) are preferred from the viewpoint of superior sulfidation resistance, coloring stability, and compatibility, and triazine thiol compounds having a silyl group and / or a siloxane skeleton are preferred. More preferred.
The triazine thiol compound having a siloxane skeleton includes, for example, a triazine compound having two or more (preferably three or more) mercapto groups and one or more functional groups (for example, amino groups) capable of reacting with the mercapto group (preferably amino groups). 2 or more) can be produced by reacting with polysiloxane (for example, reactive silicone oil). The polysiloxane used in the production is not particularly limited except that it has a functional group capable of reacting with a mercapto group. In addition to the functional group capable of reacting with a mercapto group, the polysiloxane can further have, for example, an alkoxysilyl group as an alkoxy group or a silyl group.
(D) component can be used individually or in combination of 2 types or more, respectively.

  The amount of the component (D) is 0.01 to 10 with respect to 100 parts by mass of the total of the component (A) and the component (B) from the viewpoint of being excellent in sulfidation resistance and excellent in work stability and heat-resistant colorability. It is preferably part by mass, more preferably 0.01 to 1 part by mass, and still more preferably 0.1 to 0.5 part by mass.

  From the viewpoint of excellent adhesion, the composition of the present invention further comprises at least one selected from the group consisting of bis (alkoxysilyl) alkanes, bis (alkoxysilylalkyl) amines and isocyanurate compounds as component (E). It is preferable to contain.

The bis (alkoxysilyl) alkane as (E) is an adhesion imparting agent (adhesion imparting agent) and is a compound having a divalent alkane (alkylene group) and two alkoxysilyl groups. When the composition of the present invention further contains a bis (alkoxysilyl) alkane, the adhesiveness and adhesion are excellent. The alkoxysilyl group can have, for example, an alkyl group such as a methyl group or an ethyl group in addition to the alkoxy group. The divalent alkane can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the bis (alkoxysilyl) alkane include those represented by the following formula (VII).

In the formula, R ^{7 to} R ⁸ are each an alkyl group, R ⁹ is a divalent alkane which may have a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, and a is 1 to 3 respectively. Is an integer. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the divalent alkane as R ⁹ include an alkylene group having 1 to 10 carbon atoms. A divalent alkane has the same meaning as described above.

  Bis (alkoxysilyl) alkanes are excellent in transparency, adhesion at high temperatures, curability, smoothness, and storage stability, and have a pot life and curing time of an appropriate length. Preferred are bis (trialkoxysilyl) alkanes, 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxy) At least one selected from the group consisting of (silyl) heptane, 1,8-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane. 1,6-bis (trimethoxysilyl) hexane is more preferable.

Bis (alkoxysilylalkyl) amine as (E) is an adhesion-imparting agent (adhesion-imparting agent) and is a compound having an imino group and two alkoxysilylalkyl groups. When the composition of the present invention further contains bis (alkoxysilylalkyl) amine, the adhesiveness and adhesion are excellent. The alkoxysilyl group can have, for example, an alkyl group such as a methyl group or an ethyl group in addition to the alkoxy group. The alkylene group which alkoxysilylalkyl has can have hetero atoms, such as an oxygen atom, a nitrogen atom, and a sulfur atom, for example. Examples of the bis (alkoxysilylalkyl) amine include those represented by the following formula (VIII).

In the formula, R ^{7 to} R ⁸ are each an alkyl group, R ¹⁰ is an alkylene group which may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, and a is an integer of 1 to 3, respectively. It is. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the alkylene group as R ¹⁰ include alkylene groups having 1 to 10 carbon atoms.

  Bis (alkoxysilylalkyl) amine is excellent in transparency, adhesion at high temperatures, curability, smoothness, and storage stability, and has a pot life and curing time of an appropriate length. Is preferable, bis (trialkoxysilyl) alkane is more preferable, and bis- (3-trimethoxysilylpropyl) amine is more preferable.

The isocyanurate compound as the component (E) is not particularly limited as long as it is a compound that forms an isocyanurate skeleton by an isocyanate trimer. When the composition of the present invention further contains an isocyanurate compound, the adhesiveness and adhesion are excellent. As an isocyanurate compound, the compound represented by following formula (1) is mentioned, for example.

In Formula 1, each R is a monovalent hydrocarbon group that may have an organic group or an aliphatic unsaturated bond. Furthermore, R can contain functional groups such as an epoxy group, a glycidoxy group, an alkoxysilyl group (for example, trialkoxysilyl group), a (meth) acryloyl group, and an isocyanate group. The functional group can be bonded to the isocyanurate skeleton via an organic group or a hydrocarbon group.
Examples of the isocyanurate compound include isocyanurate silane having an isocyanurate skeleton and a hydrolyzable silyl group. Specific examples include tris (trimethoxylyl) isocyanurate and tris (trimethoxylylalkyl) isocyanurate [tris (trimethoxylylpropyl) isocyanurate].

(E) A component can be used individually or in combination of 2 types or more, respectively.
The amount of the component (E) is preferably 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B) from the viewpoint of excellent adhesion.

The composition of this invention can contain an additive further as needed in the range which does not impair the objective and effect of this invention other than said component.
Examples of the additive include a curing agent, a catalyst (for example, a catalyst other than a condensation catalyst; a Lewis acid catalyst, a Lewis base catalyst; a cationic polymerization catalyst), a polymerization initiator (for example, a thermal polymerization initiator, a photopolymerization start). ), Inorganic fillers, antioxidants, lubricants, UV absorbers, heat-light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, curing accelerators, solvents, fluorescent substances (inorganic substances) ), Anti-aging agents, radical inhibitors, adhesion improvers, bis (alkoxysilyl) alkanes, bis (alkoxysilylalkyl) amines and coupling agents, and adhesion promoters such as isocyanurate compounds (adhesion) Imparting agent), phosphate ester, phosphite ester, boron compound, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, Agents, coupling agents, conductivity-imparting agents, phosphorus-based peroxide decomposers, pigments, metal deactivators include physical property modifiers. Various additives are not particularly limited. For example, a conventionally well-known thing is mentioned.

The composition of the present invention is not particularly limited for its production. For example, it can manufacture by mixing (A) component-(D) component and the (E) component and additive which can be used as needed.
The composition of the present invention can be produced as a one-pack type or a two-pack type.

The composition of this invention can be used as a composition for optical semiconductor sealing.
The optical semiconductor to which the composition of the present invention can be applied is not particularly limited. For example, a light emitting diode (LED), an organic electroluminescent element (organic EL), a laser diode, and an LED array are mentioned.
The adherend to which the composition of the present invention can be applied is not limited to an optical semiconductor. For example, semiconductors other than optical semiconductors; rubber; plastics such as polyphthalamide, polyimide, polycarbonate, (meth) acrylic resin; glass; metals such as silver, silver plating, aluminum, aluminum nitride, boron nitride, and / or Ceramic may be mentioned.
As a method of using the composition of the present invention, for example, the composition of the present invention is applied to an adherend (for example, a metal member such as an optical semiconductor, silver, or a plastic member), and the composition of the present invention is applied. Examples include heating the adherend to cure the composition of the present invention. The method for applying the composition of the present invention is not particularly limited. Examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, and injection molding.

The composition of the present invention can be cured by heating, and is excellent in heat curability, room temperature stability, and transparency.
The heating temperature of the composition of the present invention is excellent in adhesion and thin film curability, the curing time and pot life can be set to appropriate lengths, and the by-product alcohol resulting from the condensation reaction is inhibited from foaming. From the viewpoint of being able to suppress cracks in the cured product and being excellent in the smoothness, moldability and physical properties of the cured product, it is preferably cured at around 80 ° C. to 150 ° C., more preferably around 150 ° C.
The heating can be performed under substantially anhydrous conditions from the viewpoints of excellent curability and excellent transparency. In the present invention, “heating under substantially anhydrous conditions” means that the atmospheric humidity of the environment during heating is 10% RH or less.

  The cured product (silicone resin) obtained by heating and curing the composition of the present invention can maintain high transparency against long-term use of LEDs (in particular, white LEDs), and is resistant to heat-resistant coloring. Excellent in heat resistance, thin film curability, adhesion, and heat crack resistance. The cured product obtained is superior in heat-resistant coloring stability than conventional silicone resins because the crosslinked part and skeleton are all siloxane bonds.

  A cured product obtained by using the composition of the present invention (when the thickness of the cured product is 2 mm) is an ultraviolet / visible absorption spectrum measuring apparatus (manufactured by Shimadzu Corporation, the same applies hereinafter) according to JIS K0115: 2004. The transmittance measured at a wavelength of 400 nm is preferably 80% or more, more preferably 85% or more.

  In addition, the cured product obtained using the composition of the present invention is subjected to a heat resistance test after initial curing (a test in which the cured product after initial curing is placed at 150 ° C. for 10 days), and then the cured product (thickness: 2 mm). ), The transmittance measured at a wavelength of 400 nm using an ultraviolet / visible spectrum measuring device according to JIS K0115: 2004 is preferably 80% or more, more preferably 85% or more.

  The cured product obtained using the composition of the present invention preferably has a transmittance retention (transmittance after heat resistance test / transmittance at initial curing × 100) of 70 to 100%, 80 to More preferably, it is 100%.

  In addition to optical semiconductors, the composition of the present invention is used for applications such as display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, and semiconductor integrated circuit peripheral materials. Can be used.

A laminate can be obtained by applying the composition of the present invention to an adherend. The obtained laminate can have a silicone resin layer obtained from the composition of the present invention and a member containing silver (a layer containing silver). As a laminated body obtained, an optical semiconductor sealing body (optical semiconductor sealing body of this invention), the sealing agent for solar cells, etc. are mentioned, for example.
One of the preferred embodiments of the obtained laminate is covering silver with a silicone resin layer obtained from the silicone resin composition. For example, the silicone resin layer may directly cover silver. Moreover, you may have another transparent layer (For example, a resin layer, a glass layer, an air layer) between a silicone resin layer and silver, for example.
One of the preferred embodiments of the laminate is to have an optical semiconductor. The optical semiconductor is not particularly limited. For example, the same thing as the above is mentioned. The optical semiconductor may be in a mode between the silicone resin layer and the member containing silver. The optical semiconductor may be in parallel with the member containing silver, and the silicone resin layer may seal the optical semiconductor and the member containing silver. The optical semiconductor is arranged in parallel with a member containing two silver, the optical semiconductor is located between the first member and the second member, and the silicone resin layer includes an optical semiconductor and a member containing two silver. It may be a mode of sealing.

The laminate will be described below with reference to the accompanying drawings. The present invention is not limited to the attached drawings.
FIG. 1 is a cross-sectional view schematically showing an example of a laminate in the present invention. In FIG. 1, a laminated body 100 includes a member (member containing silver) 120 and a silicone resin layer 102.

FIG. 2 is a cross-sectional view schematically showing another example of the laminate in the present invention.
In FIG. 2, the stacked body 200 includes a member (member containing silver) 220, an optical semiconductor 203, and a silicone resin layer 202. The laminate 200 can further include a transparent layer (not shown) between the optical semiconductor 203 and the silicone resin layer 202. Examples of the transparent layer include a resin layer, a glass layer, and an air layer.

The cured product obtained by curing the composition of the present invention has resistance to sulfidation.
In the present invention, the sulfidation resistance based on the spectral reflectance maintenance factor is evaluated as follows. First, the composition of the present invention is applied to a thickness of 1 mm on a silver member (a metal layer obtained by using silver) and cured to obtain a laminate having the member and the silicone resin layer, and the laminate. Was subjected to a sulfidation resistance test in a hydrogen sulfide gas having a theoretical value of 560 ppm at 25 ° C., and the spectral reflectance of the laminate was measured before the sulfidation resistance test and 24 and 72 hours after the start of the sulfidation resistance test. Is measured using a spectral reflectometer, and the spectral reflectance is applied to the formula [spectral reflectance maintenance ratio = (spectral reflectance after sulfidation test / spectral reflectance before sulfidation test) × 100]. The rate maintenance rate is calculated.
In the sulfidation resistance test, about 10 g of iron sulfide pulverized in powder form (a large excess with respect to 0.5 mmol of hydrochloric acid) is placed on the bottom of a 10 L desiccator. A dish (having a through-hole) was mounted in a desiccator, and the laminate was placed on the eye dish, and 0.5 mmol of hydrochloric acid was added dropwise to a large excess of iron sulfide to obtain 0.25 mmol of hydrogen sulfide (theoretical value). 560 ppm, the actual concentration is about 500 ppm) (reaction formula: FeS + 2HCl → FeCl ₂ + H ₂ S). The hydrogen sulfide concentration of 560 ppm is a theoretical value.
Spectral reflectivity was measured using a spectral reflectometer [URE-30 manufactured by USHIO INC.] For the laminate before and after the sulfidation test (24 and 72 hours after hydrogen sulfide generation). The spectral reflectance at 475 nm (measurement wavelength) is measured.
The spectral reflectance maintenance factor calculated in the present invention is preferably 80% or more, since it is excellent in sulfidation resistance, and more preferably 80% or more.

  Further, as an evaluation of the sulfidation resistance in the present invention, in the above sulfidation resistance test, evaluation was performed to visually confirm the discoloration of silver in the cured sample 24 hours and 72 hours after the generation of hydrogen sulfide. It is preferable that no discoloration is confirmed after 24 hours and 72 hours from the start of the sulfidation resistance test.

The sealed optical semiconductor of the present invention will be described below.
The optical semiconductor sealing body of the present invention (sealing body of the present invention) is an optical semiconductor sealing body formed by sealing the optical semiconductor with the thermosetting silicone resin composition of the present invention.
The sealed optical semiconductor of the present invention is a sealed optical semiconductor that can seal a member containing an optical semiconductor and silver with a silicone resin layer obtained from the composition of the present invention.
If the silicone resin composition used for the optical semiconductor sealing body of this invention is a composition of this invention, it will not restrict | limit in particular. The member containing silver used for the sealed optical semiconductor of the present invention is not particularly limited. For example, the same thing as the above is mentioned. The optical semiconductor used for the sealed optical semiconductor of the present invention is not particularly limited. For example, the same thing as the above is mentioned.
As an optical semiconductor sealing body, for example, it has an optical semiconductor, a frame body having a recess, and a sealing material, the optical semiconductor is disposed at the bottom of the recess, and the frame body is disposed on a side surface of the recess. Examples include a sealed optical semiconductor including a reflector containing silver or silver, the sealing material sealing the optical semiconductor and the reflector, and the sealing material obtained from the composition of the present invention.

The sealed optical semiconductor of the present invention will be described below with reference to the accompanying drawings.
FIG. 3 is a cross-sectional view schematically showing an example of the sealed optical semiconductor of the present invention.
In FIG. 3, the optical semiconductor sealing body 300 includes an optical semiconductor 303, a frame 304 having a recess 302, and a sealing material 308, and the optical semiconductor 303 is on the bottom (not shown) of the recess 302. The frame body 304 includes a reflector 320 obtained from a group 11 metal (for example, silver) on a side surface (not shown) of the recess 302, and a sealing material 308 seals the optical semiconductor 303 and the reflector 320. To do.
The sealing material 308 is obtained by curing the composition of the present invention. The recessed portion 302 may be filled with the composition of the present invention up to the shaded portion 306. Alternatively, the portion denoted by reference numeral 308 may be another transparent layer, and the hatched portion 306 may be a sealing material included in the optical semiconductor sealing body of the present invention. The sealing material can contain a fluorescent substance or the like.
One optical semiconductor encapsulant can have one or a plurality of optical semiconductors. The optical semiconductor may be disposed in the frame with the light emitting layer (the surface opposite to the surface in contact with the mount member) facing up.
The optical semiconductor 303 is disposed on the bottom (not shown) of the recess 302 formed from the frame body 304 and the substrate 310, and is fixed by the mount member 301.
As another aspect of the reflector, there is an example in which the end portions 312 and 314 included in the frame body 304 are integrally coupled, and the reflector forms a side surface and a bottom portion. In this case, an optical semiconductor can be disposed on the bottom of the reflector.
The reflector 320 may have a tapered opening end (not shown) whose sectional dimension increases as the distance from the bottom (not shown) of the recess 302 increases.
Examples of the mounting member include silver paste and resin. Each electrode (not shown) of the optical semiconductor 303 and the external electrode 309 are wire bonded by a conductive wire 307.
The optical semiconductor sealing body 300 can seal the concave portion 302 with a sealing material 308, 306, or 302 (a portion in which the portion 308 and the portion 306 are combined).
By sealing the optical semiconductor sealing body with a silicone resin layer, the resistance to sulfidation is enhanced, and corrosion (for example, discoloration. Specifically, discoloration, specifically, a metal layer, particularly silver, silver-containing layer, or silver plating layer). Can suppress silver discoloration) and does not lower the brightness and transparency of the sealed optical semiconductor.
Also, by sealing the recess with the sealing material, the sealing material has low hardness and small curing shrinkage, so that the sealing material can be prevented from peeling off from the recess or disconnection of the wire due to curing shrinkage. it can.

FIG. 4 is a cross-sectional view schematically showing another example of the sealed optical semiconductor of the present invention.
In FIG. 4, the optical semiconductor sealing body 400 has a lens 401 on the optical semiconductor sealing body 300 shown in FIG. The lens 401 may be formed using the composition of the present invention.

FIG. 5 is a cross-sectional view schematically showing another example of the sealed optical semiconductor of the present invention.
In FIG. 5, an optical semiconductor sealing body 500 includes an optical semiconductor 503, a substrate 510 including a frame body (not shown) having a recess (not shown), and a sealing material 502. The semiconductor 503 is disposed at the bottom (not shown) of the recess, and the frame is provided with a reflector 520 obtained from a group 11 metal (for example, silver) on the side surface (not shown) of the recess, and has a lamp function. The resin 506 has a substrate 510 and inner leads 505, the sealing material 502 is obtained from the above-described silicone resin composition, and the sealing material 502 seals the optical semiconductor 503 and the reflector 520. Is the body. The sealing material 502 has sulfidation resistance.
In FIG. 5, a frame (not shown) and the substrate 510 can be integrally formed.
The reflector 520 may be formed integrally with the side surface and the bottom (not shown) of the recess.
The optical semiconductor 503 is fixed on the substrate 510 with a mount member 501. Examples of the mount member include silver paste and resin.
Each electrode (not shown) of the optical semiconductor 503 is wire-bonded by a conductive wire 507.
Resin 506 can be formed using the composition of the present invention.

The case where the composition of the present invention and / or the sealed optical semiconductor of the present invention is used for an LED display will be described with reference to the accompanying drawings.
FIG. 6 is a diagram schematically showing an example of an LED display using the composition of the present invention and / or the sealed optical semiconductor of the present invention.
In FIG. 6, an LED display 600 includes an optical semiconductor sealing body 601 arranged in a matrix in a housing 604, and the optical semiconductor sealing body 601 is sealed with a sealing material 606. The light shielding member 605 is arranged in the part. The composition of the present invention can be used for the sealing material 606. Moreover, the optical semiconductor sealing body of the present invention can be used as the optical semiconductor sealing body 601.

  Applications of the silicone resin-containing structure of the present invention or the sealed optical semiconductor of the present invention include, for example, automobile lamps (head lamps, tail lamps, directional lamps, etc.), household lighting equipment, industrial lighting equipment, stage Lighting fixtures, displays, signals, projectors.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
[Evaluation]
About the composition obtained as follows, sulfidation resistance, room temperature stability, heat-curing property, and the transmittance | permeability were evaluated by the method shown below. The results are shown in the table.
<Sulfurization resistance>
Preparation of cured sample: The composition obtained as described below was applied on silver plating so as to have a thickness of about 1 mm, and cured by heating for 12 hours under conditions of 150 ° C. hot air oven. Produced.
Test: Place about 10 g of iron sulfide ground in powder form (large excess with respect to 0.5 mmol of hydrochloric acid) on the bottom of a 10-liter desiccator. (With holes) was mounted in a desiccator and the cured sample was placed on the pan. Next, 0.25 mmol hydrogen sulfide (concentration: about 500 ppm, theoretical value 560 ppm) was generated by dropping 0.5 mmol hydrochloric acid into a large excess of iron sulfide (reaction formula: FeS + 2HCl → FeCl ₂ + H _2). S). The silver discoloration was visually confirmed 24 hours after hydrogen sulfide generation (room temperature). “◯” indicates that no discoloration was confirmed by visual inspection, “Δ” indicates that discoloration was slightly confirmed by visual observation, and “×” indicates that discoloration was largely confirmed by visual inspection.
In the present invention, the concentration of hydrogen sulfide in the sulfidation resistance test is a theoretical value of 560 ppm. In the sulfidation resistance test, 0.5 mmol of hydrochloric acid is added, so that 0.25 mmol (0.25 mmol × 22.4 liters = 5.6 ml) of hydrogen sulfide is generated. Therefore, the concentration of hydrogen sulfide is [5.6 ml / 10 liter (desiccator volume)] × 10 ⁶ = 560 ppm.

<Room temperature stability>
The viscosity (initial viscosity) of the composition obtained as described below and the composition obtained as described below were placed under conditions of 23 ° C. and 55% RH and after 24 hours (viscosity after 24 hours). Were measured under the conditions of RH 50% and 25 ° C. using an E-type viscometer, and the viscosity increase [(viscosity after 24 hours) / (initial viscosity)] 24 hours after mixing was evaluated.
<Heat curing>
The composition obtained as described below was measured for 8 hours under conditions of 150 ° C. and hot air oven, and the hardness of the cured product was measured using a hardness meter. 70% or more of the specified hardness was “◯”, and less than 70% was “x”.

<Transmission retention>
In the transmittance evaluation test, an initial cured product obtained by curing the composition obtained as described below at 150 ° C. for 12 hours, and a heat resistance test (the initial cured product was further subjected to a 150 ° C. condition). Test for heating for 10 days.) For each of the cured products (2 mm in thickness) after each, linear transmission at a wavelength of 400 nm using an ultraviolet / visible absorption spectrum measuring apparatus (manufactured by Shimadzu Corporation) in accordance with JIS K0115: 2004. The rate was measured. And the permeation | transmission retention with respect to the initial linear transmittance of the linear transmittance after a heat test was calculated | required by the following formula.
Transmission retention (%) = (Linear transmittance after heat test) / (Initial linear transmittance) × 100

[Production of composition]
The components shown in each table were used in the amounts (parts by mass) shown in the table, and these were uniformly mixed using a mixer (Awatori Rentaro, manufactured by Shinky Corporation) to produce a composition.

Details of each component shown in each table are as follows.
(A) Polysiloxane 1: Polydimethylsiloxane-α, ω-diol, weight average molecular weight 49,000, trade name ss10, manufactured by Shin-Etsu Chemical Co., Ltd. (A) Polysiloxane 2: PRX-413 (Toray Dow Corning Co., Ltd.), polydimethylsiloxane-α, ω-diol (weight average molecular weight 4,000)
-(A) Polysiloxane 3: SR-1000 (manufactured by Momentive Materials Japan), MQ resin (weight average molecular weight 4000) SR-1000 has a structure represented by the following formula (I).
(R ¹ SiO _3/2 ) a (R ² ₂ SiO _2/2 ) b (R ³ ₃ SiO _1/2 ) c (SiO _4/2 ) d (XO _1/2 ) e (I)
In the formula, a and b are 0, R ^{1 to} R ³ are methyl groups, X is a hydrogen group, d / (a + b + c + d) is 0.5, e / (a + b + c + d) is 0.07, and R ₃ SiO ratio of R ₃ SiO _1/2 units to SiO _4/2 units 1 mol of repeating units _1/2 units and SiO _4/2 units has at 0.5 mol to 1.2 mol.
(B) Alkoxysilyl compound 1: Trimethoxysilylsiloxane at both ends (trimethoxysiloxy-blocked dimethylpolysiloxane at both ends)
The alkoxysilyl compound 1 was produced as follows.
A 500 mL three-necked flask equipped with a stirrer and a reflux condenser and a polysiloxane having silanol groups at both ends (polydimethylsiloxane-α, ω-diol, weight average molecular weight 49,000, trade name ss10, manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts by mass, 10 parts by mass of tetramethoxysilane, and 0.1 part by mass of acetic acid were added and reacted under a nitrogen atmosphere at 100 ° C. for 6 hours. The disappearance of the silanol group possessed by ss10 was confirmed by ¹ H-NMR analysis. The obtained organosiloxane was designated as alkoxysilyl compound 1. The alkoxysilyl compound 1 is dimethylpolysiloxane represented by the following formula and having both ends blocked with trimethoxysiloxy groups. The weight average molecular weight of the alkoxysilyl compound 1 was 55,000. The weight average molecular weight of polysiloxane is expressed in terms of polystyrene by gel permeation chromatography (GPC) analysis using chloroform as a solvent. The viscosity of the alkoxysilyl compound 1 at 25 ° C. was 1,500 mPa · s.

(B) Alkoxysilyl compound 2: terminal polymethoxysilylsiloxane (both terminal polyfunctional alkoxysiloxy group-containing dimethylpolysiloxane)
The alkoxysilyl compound 2 was produced as follows.
A 500 mL three-necked flask equipped with a stirrer and a reflux condenser and a polysiloxane having silanol groups at both ends (polydimethylsiloxane-α, ω-diol, weight average molecular weight 21,000, trade name ss70, manufactured by Shin-Etsu Chemical Co., Ltd.) .) 100 parts by mass, Shin-Etsu Chemical Co., Ltd. KC-89S (alkoxysilane condensate, 45% by weight of methoxy group, viscosity 5 mPa · s) and 10 parts by mass of acetic acid are added under a nitrogen atmosphere. And reacted at 120 ° C. for 16 hours. The disappearance of the silanol group possessed by ss70 was confirmed by ¹ H-NMR analysis. Thereafter, acetic acid and low-boiling impurities are distilled off from the system for 3 hours under conditions of 140 ° C. and 1.3 kPa, and an alkoxy having 45% by weight of silicon-bonded alkoxy groups at both ends of the starting polysiloxane having silanol groups. Polydimethylsiloxane sealed (modified) with a silane oligomer was obtained. The obtained polysiloxane was designated as alkoxysilyl compound 2. The viscosity of the alkoxysilyl compound 2 at 25 ° C. was 2000 mPa · s.

· (B) alkoxysilyl compound 3: x-40-9246 (manufactured by Shin-Etsu Chemical Co., Ltd.), a silicone alkoxy oligomer _{[R m Si (OR ')} n O (4-mn) / 2, wherein, R is the number of carbon atoms 1 to 6 alkyl groups, alkenyl groups or aryl groups, R ′ is an alkyl group having 1 to 6 carbon atoms, m is 0 <m <2, n is 0 <n <2, m + n is 0 <m + n ≦ 3. Weight average molecular weight 6,000
-(B) alkoxysilyl compound 4: PRX-413 (Toray Dow Corning, (A) polysiloxane 2: similar to PRX-413) 100 g XR31-2733 (Momentive Co., alkoxy oligomer) 100 g and 0.2 g of acetic acid were added and reacted at 100 ° C. for 6 hr, and volatile components (reaction residue: acetic acid, methanol, etc.) were reacted at 100 ° C. for 2 hr to obtain alkoxysilyl compound 4 (413-2733).
-(C) Zirconium compound 1: zirconium tributoxy naphthenate Zirconium tributoxy naphthenate was produced as follows. Zirconium tetrabutoxide (manufactured by Kanto Chemical Co., Ltd., 0.026 mol) and naphthenic acid (manufactured by Tokyo Chemical Industry Co., Ltd., average number of carbon atoms of the hydrocarbon group bonded to the carboxy group: 15, neutralization value of 220 mg, and so on) 6 g (0.026 mol) was reacted by stirring at room temperature for about 2 hours in a nitrogen atmosphere to obtain a target compound.
The neutralization value of naphthenic acid is the amount of KOH required to neutralize 1 g of naphthenic acid.
The qualitative properties of the synthesized product were analyzed using a Fourier transform infrared spectrophotometer (FT-IR). As a result, absorption near 1700 cm ⁻¹ attributed to COOH derived from carboxylic acid disappeared after the reaction, and a peak derived from COOZr near 1450 to 1560 cm ⁻¹ was confirmed.
The resulting composite is referred to as zirconium compound 1. The average number of carbon atoms of R ^{1 in} the naphthate group (R ¹ COO—) of the zirconium compound 1 is 15.
(C) Hafnium compound 1: Hafnium tributoxynaphthenate Hafnium compound 1 was produced as follows. Hafnium tetrabutoxide (manufactured by Gelest, 0.01 mol) and naphthenic acid (manufactured by Tokyo Chemical Industry Co., Ltd., average number of carbon atoms of the hydrocarbon group bonded to the carboxy group: 15, neutralization value 220 mg. In addition, neutralization of naphthenic acid The value is the amount of KOH necessary to neutralize 1 g of naphthenic acid.) 2.55 g (0.01 mol) was reacted with stirring under a nitrogen atmosphere at room temperature for about 2 hours to obtain the target compound.
The qualitative properties of the synthesized product were analyzed using a Fourier transform infrared spectrophotometer (FT-IR). As a result, absorption near 1700 cm ⁻¹ attributed to COOH derived from carboxylic acid disappeared after the reaction, and a peak derived from COOHf near 1,450 to 1,560 cm ⁻¹ was confirmed. The resultant composite is referred to as hafnium compound 1. The average number of carbon atoms of R ^{1 in} the naphthate group (R ¹ COO—) of the hafnium compound 1 is 15.

-(C) Tin compound 1: Neostan U-200, Dibutyltin diacetate (Nitto Kasei)
(C) Tin compound 2: Neostan U-28, bis (2-ethylhexanoic acid) tin (Nitto Kasei)
(C) Lanthanoid compound 1: Tris (2-ethylhexanoate) cerium (manufactured by Gelest)
・ (C) Aluminum compound 1: Aluminum trisacetylacetonate (Kawaken Fine Chemical)
-(C) Zinc compound 1: Trade name 22% Zn, 1.6 mol reactant 2-ethylhexanoate zinc (manufactured by Hope Pharmaceutical Co., Ltd.)
(C) Titanium compound 1: diisopropoxy-bis (ethyl acetoacetate) titanium (D) 2 mercaptobenzothiazole (manufactured by Shikoku Chemicals)
-(D) benzothiazole: unsubstituted benzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
(D) Triazinethiol 1: amino group-containing silicone oil X-22-161A: 100 g (amine equivalent 800, manufactured by Shin-Etsu Chemical Co., Ltd.), triazine trithiol 23.3 g, toluene 100 g thermometer, water-cooled condenser The reaction mixture was put into a 1 L separable flask equipped and heated and stirred at 100 ° C. for 12 hours to advance the reaction. As the reaction progressed, the viscosity of the mixture increased, and the reaction was terminated when the thickening stopped. Thereafter, the solvent was distilled off under reduced pressure, and hydrogen sulfide generated therewith was also removed. The obtained reaction product was a pale yellow waxy substance, and the weight average molecular weight was 2000. When the IR spectrum of this product was measured, the absorption derived from the N—H structure decreased compared with that before the reaction, and a new absorption derived from the triazine thiol structure was observed.
(D) Triazinethiol 2: amino group-containing silicone oil KF-857: 100 g (amine equivalent 800, manufactured by Shin-Etsu Chemical Co., Ltd.), triazine trithiol 23.3 g, toluene 100 g equipped with thermometer and water-cooled condenser It was put into a 1 L separable flask and heated and stirred at 100 ° C. for 12 hours to allow the reaction to proceed. As the reaction progressed, the viscosity of the mixture increased, and the reaction was terminated when the thickening stopped. Thereafter, the solvent was distilled off under reduced pressure, and hydrogen sulfide generated therewith was also removed. The obtained reaction product was a pale yellow waxy substance, and the weight average molecular weight was 2000. When the IR spectrum of this product was measured, the absorption derived from the N—H structure decreased compared with that before the reaction, and a new absorption derived from the triazine thiol structure was observed.
(D) Triazine thiol 3: amino group-containing silicone oil KF-8001: 100 g (amine equivalent 800, manufactured by Shin-Etsu Chemical Co., Ltd.), triazine trithiol 23.3 g, toluene 100 g were equipped with a thermometer and a water-cooled condenser. It was put into a 1 L separable flask and heated and stirred at 100 ° C. for 12 hours to allow the reaction to proceed. As the reaction progressed, the viscosity of the mixture increased, and the reaction was terminated when the thickening stopped. Thereafter, the solvent was distilled off under reduced pressure, and hydrogen sulfide generated therewith was also removed. The obtained reaction product was a pale yellow waxy substance, and the weight average molecular weight was 2000. When the IR spectrum of this product was measured, the absorption derived from the N—H structure decreased compared with that before the reaction, and a new absorption derived from the triazine thiol structure was observed.
(D) Triazine thiol 4: amino group-containing silicone oil KF 9192: 100 g (amine equivalent 800, manufactured by Shin-Etsu Chemical Co., Ltd.), triazine trithiol 23.3 g, toluene 100 g 1 L Separa equipped with thermometer and water-cooled condenser The reaction mixture was put into a bull flask and heated and stirred at 100 ° C. for 12 hours to advance the reaction. As the reaction progressed, the viscosity of the mixture increased, and the reaction was terminated when the thickening stopped. Thereafter, the solvent was distilled off under reduced pressure, and hydrogen sulfide generated therewith was also removed. The obtained reaction product was a pale yellow waxy substance, and the weight average molecular weight was 2000. When the IR spectrum of this product was measured, the absorption derived from the N—H structure decreased compared with that before the reaction, and a new absorption derived from the triazine thiol structure was observed.
・ Imidazolesilane (trade name: IM-1000, manufactured by Nippon Steel Chemical Co., Ltd.)
(E) Bistrimethoxyalkane: Bis (trimethoxysilyl) hexane (trade name: Z6830, manufactured by Toray Dow Corning)
(E) Isocyanurate silane: Tris (trimethoxysilylpropyl) isocyanurate (trade name: x-12-965, manufactured by Shin-Etsu Chemical Co., Ltd.)

As is clear from the results shown in the above table, Comparative Examples 1 and 2 not containing the component (D) and Comparative Example 3 containing no imidazole compound instead of the component (D) were inferior in sulfur resistance. (A) Comparative Example 4 containing no silanol group-containing organopolysiloxane was inferior in room temperature stability, heat curability, and sulfuration resistance. The comparative example 5 which does not contain (B) component did not harden | cure but heat-hardening property was bad. Comparative Example 6 containing no component (D) gelled and had low room temperature stability. (A) Comparative Example 7 containing no silanol group-containing organopolysiloxane was inferior in room temperature stability, heat curability, and sulfuration resistance.
On the other hand, Reference Examples I-1 to 7 and Examples II-1 to 7 are excellent in sulfidation resistance, room temperature stability, heat curability, and permeability.

100, 200 Laminate (silicone resin-containing structure)
102, 202 Silicone resin layer 120, 220 member 203 Optical semiconductor 300, 400, 500 Sealed optical semiconductor body 301, 501 Mount member 302, 502 Recessed part, Silicone resin layer 303, 503 Optical semiconductor 304 Frame body 306 Shaded portion (silicone resin) layer)
307, 507 Conductive wire 308 Silicone resin layer (other transparent layers)
309 External electrode 312, 314 End 310, 510 Substrate 320, 520 Reflector 401 Lens 506 Resin 600 LED display 601 Optical semiconductor sealing body 604 Housing 605 Light shielding member 606 Sealing material

Claims (11)

(A) an organopolysiloxane having a silanol group,
(B) an organopolysiloxane having an alkoxylyl group,
(C) condensation catalyst, and (D) Preparative triazine compound heat-curable silicone resin composition containing. The thermosetting silicone resin composition according to claim 1, wherein the condensation catalyst (C) is a metal compound containing at least one selected from the group consisting of Al, Zn, Sn, Zr, Hf, Ti, and a lanthanoid. The component (C) includes at least a metal salt compound of Zn, a metal salt compound of Sn and / or a metal salt compound of lanthanoid, and the metal salt compound of Sn and / or lanthanoid metal with respect to the metal salt compound of Zn The thermosetting silicone resin composition according to claim 1 or 2 , wherein the weight ratio of the salt compound is 1 or less. The component (A) is
Diorganopolysiloxane represented by the following formula (1), and / or
R ₃ (R in the formula are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms.) SiO _1/2 units and said SiO _4/2 repeating units of SiO _4/2 units unit 1 mole ratio of the R ₃ SiO _1/2 units to having 0.5 mol to 1.2 mol, and claim 1-3 comprising a silicone resin having less than 6.0 wt% of the silanol groups The heat-curable silicone resin composition according to any one of the above.
[In Formula (1), R ¹ is the same or different alkyl group and aryl group, and n is an integer of 10 or more. ] The amount of said (D) component is 0.01-10 mass parts with respect to a total of 100 mass parts of said (A) component and said (B) component, The heat curing in any one of Claims 1-4. Silicone resin composition. The amount of said (C) component is 0.001-10 mass parts with respect to a total of 100 mass parts of said (A) component and said (B) component, The heat curing in any one of Claims 1-5 Silicone resin composition. (B) the amount of component, wherein (A) heat-curable silicone resin composition according to any one of claims 1 to 6, which is 0.1 to 5000 parts by mass relative to 100 parts by weight of component. The heat curing according to any one of claims 1 to 7 , further comprising at least one selected from the group consisting of bis (alkoxysilyl) alkanes, bis (alkoxysilylalkyl) amines and isocyanurate compounds as component (E). Silicone resin composition. The amount of the said (E) component is 0.1-10 mass parts with respect to a total of 100 mass parts of the said (A) component and the said (B) component, The thermosetting silicone resin composition of Claim 8 . The silicone resin further contains R ₂ SiO _2/2 units (wherein R is an unsubstituted or substituted allyl group, alkyl group or aryl group, respectively) and RSiO _{3 with} respect to 1 mol of SiO _4/2 units. _{/ 2} units (wherein each R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms) is at least one of the R ₂ SiO _2/2 unit, the RSiO _{3 / 2} units of 1.0 mol or less, wherein R ₂ SiO _2/2 units, according to any one of claims 4-9 total of the RSiO _3/2 units has to be 1.0 mol or less Heat curable silicone resin composition. The optical semiconductor sealing body formed by sealing the optical semiconductor with the thermosetting silicone resin composition in any one of Claims 1-10 .