TW201803913A - Addition-curable silicone resin composition - Google Patents

Abstract

To provide an addition-curable silicone resin composition which has low viscosity and good dispense property before curing, has sufficient strength after curing, has good dicing property, and imparts a cured product with no tack, in particular, a methyl silicone resin composition. An addition-curable silicone resin composition contains (A) alkenyl group-containing branched organopolysiloxane, (B) alkenyl group-containing linear organopolysiloxane and (C) cyclic vinyl siloxane; (D) organo hydrogen polysiloxane having at least two hydrosilyl groups of 3-7 pts.mass with respect to 100 pts.mass of the total of (A) and (B), in the molecule and (E) a hydrosilylation catalyst.

Description

Addition hardening polysiloxane resin composition

The present invention relates to an addition-curable polysiloxane resin composition.

The addition-curable polysiloxane resin composition has been used as a sealing material for sealing semiconductor elements such as LEDs because of its excellent rapid curing properties, heat resistance of the cured material, and weather resistance. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2007-2234) proposes an addition-hardening type silicone resin composition that exhibits high adhesion to an LED package made of a thermoplastic resin such as PPA. In addition, Patent Document 2 (Japanese Patent Application Laid-Open No. 2006-93354) proposes a method of sealing an optical semiconductor element by compression molding of an addition-hardening type silicone resin composition.

In this manner, addition-curing polysiloxane resins are generally widely used as semiconductor sealing materials, but their characteristics are still unsatisfactory. In general, methyl silicone resins have the disadvantages of softness, poor cutting properties, and sticking in most cases. If the SiO _4/2 unit [Q unit] or RSiO _3/2 unit [T unit] component is added to improve the cuttability, although a hardened and non-sticky hardened product can be produced, it will become low strength and brittle. Of resin.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-2234

[Patent Document 2] Japanese Patent Laid-Open No. 2006-93354

The present invention has been made in view of the above problems, and an object thereof is to provide an addition-hardenable polysiloxane which has low viscosity before hardening and good dispensing properties, has sufficient strength after hardening, has good cutting properties, and does not stick to hardened materials. Resin composition, especially methyl silicone resin composition.

(式中，R¹與上述相同，n為3~6之整數)；(D)一分子中具有至少2個氫矽烷基之有機氫聚矽氧烷：相對於(A)~(C)成分中之烯基1莫耳，(D)成分中的氫矽烷基為0.4~4.0莫耳的量、及(E)氫矽烷化觸媒：進行氫矽烷化反應所足夠的量硬化前為低黏度且點膠性良好，硬化後產生具有充足的強度，切割性良好，不會沾黏的硬化物，而完成了本發明。 In order to solve the above-mentioned problems, the present inventors conducted a research and review, and found that the addition-curable polysiloxane resin composition containing the following components (A) to (E), (A) a branched form represented by the following formula (1) Organic polysiloxane (R ¹ ₃ SiO _1/2 ) _r (R ¹ ₂ SiO _2/2 ) _s (R ¹ SiO _3/2 ) _t (SiO _4/2 ) _u (1) (wherein R ¹ Are independently selected from substituted or unsubstituted monovalent saturated hydrocarbon groups having 1 to 12 carbon atoms and alkenyl groups having 2 to 6 carbon atoms, but at least two of R ¹ are alkenyl groups, and r is 0 to 100 Integer, s is an integer from 0 to 300, t is an integer from 0 to 200, and u is an integer from 0 to 200, but 1 ≦ t + u ≦ 400, 3 ≦ r + s + t + u ≦ 800); (B ) Linear organic polysiloxane (R ¹ ₃ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (2) represented by the following formula (2) (where R ¹ is the same as above) , But at least two of R ¹ are alkenyl groups, and x is an integer of 200 to 700); (C) a cyclic vinyl siloxane represented by the following formula (3): with respect to (A) and (B) The total content of the ingredients is 2 to 7 parts by mass

(In the formula, R ¹ is the same as above, and n is an integer of 3 to 6); (D) an organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule: relative to the components (A) to (C) The alkenyl group is 1 mole, the amount of hydrosilyl group in the component (D) is 0.4 to 4.0 mole, and (E) the hydrosilylation catalyst: a sufficient amount for the hydrosilylation reaction to have a low viscosity before hardening In addition, it has good dispensing properties, produces sufficient strength after hardening, has good cutting properties, and does not stick to hardened materials, and completed the present invention.

That is, the present invention provides the following addition-hardening polysiloxane Fat composition.

(式中，R¹與上述相同，n為3~6之整數)；(D)一分子中具有至少2個氫矽烷基之有機氫聚矽氧烷：相對於(A)~(C)成分中之烯基1莫耳，(D)成分中的氫矽烷基為0.4~4.0莫耳的量、及(E)氫矽烷化觸媒：進行氫矽烷化反應所足夠的量。 [1] An addition-curable polysiloxane resin composition characterized by containing the following (A) to (E) component (A) a branched organic polysiloxane represented by the following formula (1) ( R ¹ ₃ SiO _1/2 ) _r (R ¹ ₂ SiO _2/2 ) _s (R ¹ SiO _3/2 ) _t (SiO _4/2 ) _u (1) (wherein R ^{1 are} independently selected from each other A substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an alkenyl group having 2 to 6 carbon atoms, but at least two of R ¹ are alkenyl groups, r is an integer of 0 to 100, and s is 0 to An integer of 300, t is an integer of 0 to 200, and u is an integer of 0 to 200, but 1 ≦ t + u ≦ 400, 3 ≦ r + s + t + u ≦ 800); (B) The following formula (2 ) (R ¹ ₃ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (2) (where R ¹ is the same as above, but at least R ¹ 2 are alkenyl groups, x is an integer of 200 to 700); (C) a cyclic vinyl siloxane represented by the following formula (3): 100 parts by mass with respect to the total of the components (A) and (B) 2 to 7 parts by mass

(In the formula, R ¹ is the same as above, and n is an integer of 3 to 6); (D) an organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule: relative to the components (A) to (C) The alkenyl group in the compound is 1 mole, the amount of the hydrosilyl group in the component (D) is 0.4 to 4.0 moles, and (E) the hydrosilylation catalyst: an amount sufficient for the hydrosilylation reaction.

[2] The addition-curable polysiloxane resin composition according to [1], wherein the blending ratio of the component (A) and the component (B) is (A): (B) = 1: 1 ~ 2: 1.

[3] The addition-curable polysiloxane resin composition according to [1] or [2], wherein the component (D) is an organohydrogenpolysiloxane (R ² ₃ SiO) represented by the following formula (4) _1/2 ) _{r '} (R ² ₂ SiO _2/2 ) _s' (R ² SiO _3/2 ) _{t '} (SiO _4/2 ) _u' (4) (wherein R ² is a hydrogen atom independently of each other Or a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, at least two of R ² are hydrogen atoms, r 'is an integer of 0 to 100, s' is an integer of 0 to 300, and t' is 0 to An integer of 200 and u 'are integers of 0 to 200, but 2 ≦ r' + s' + t '+ u' ≦ 800).

[4] The addition-curable silicone resin composition according to any one of [1] to [3], wherein the blending amount of the component (E) is relative to the total of the components (A) to (D) The mass is 5 to 20 ppm.

According to the present invention, by adding a sufficient amount of cyclic vinyl siloxane, a low viscosity before hardening and good dispensability can be obtained, which is generated after hardening. Addition hardening silicone composition with sufficient strength, good cutting properties, and non-sticky hardened material.

Each component of the present invention will be described below.

[(A) Branched (resinous) organic polysiloxane]

The component (A) of the present invention is a main component of the addition-curable polysiloxane resin composition of the present invention, and is an organopolysiloxane represented by the following formula (1).

(R ¹ ₃ SiO _1/2 ) _r (R ¹ ₂ SiO _2/2 ) _s (R ¹ SiO _3/2 ) _t (SiO _4/2 ) _u (1) (where R ¹ is selected independently of each other From substituted or unsubstituted monovalent saturated hydrocarbon groups having 1 to 12 carbon atoms and alkenyl groups having 2 to 6 carbon atoms, but at least two of R ¹ are alkenyl groups, r is an integer of 0 to 100, and s is 0 An integer of ~ 300, t is an integer of 0 to 200, and u is an integer of 0 to 200, but 1 ≦ t + u ≦ 400, 3 ≦ r + s + t + u ≦ 800).

Here, R ¹ is a group selected from a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6, preferably 1 to 4, and an alkenyl group having 2 to 6 carbon atoms. Examples of the monovalent saturated hydrocarbon group include, specifically, alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, and the like bonded to these groups; A group in which a hydrogen atom of a carbon atom is partially or completely substituted with a halogen atom such as fluorine, bromine, chlorine, cyano, (meth) acryloxy, glycidyloxy, mercapto, amine, etc. Halogenated monovalent saturated hydrocarbon groups such as fluoropropyl and chloropropyl; cyanoalkyl groups such as β-cyanoethyl and γ-cyanopropyl; 3-methacryloxypropyl, 3-glycidyloxypropyl Group, 3-mercaptopropyl, 3-aminopropyl and the like. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a hexenyl group, and a styryl group. Among these, methyl and cyclohexyl are preferred, and methyl is particularly preferred. However, at least two of R ¹ are alkenyl, and the alkenyl is preferably vinyl.

In addition, the alkenyl group has at least two in one molecule, and in the organopolysiloxane of the component (A), it is preferable to contain 0.005 to 0.5 mole / 100g, especially 0.01 to 0.2 mole / 100g.

In addition, the alkenyl group may be located in the R ¹ ₃ SiO _1/2 unit, the R ¹ ₂ SiO _2/2 unit, the R ¹ SiO _3/2 unit, or a plurality of these units, so that the R ¹ ₃ SiO _1/2 unit It is preferred to have an alkenyl group.

In addition, r is an integer from 0 to 100, preferably an integer from 0 to 75, and preferably an integer from 0 to 50. However, it is more preferable that r is 2 or more, especially 2 to 50, especially 3 to 40. best of 3 to 35, in this case, when the r ¹ ₃ SiO _1/2 unit having an alkenyl group, the alkenyl group having r r ¹ ₃ SiO _1/2 units of from 2 to 50 is desirable. s is an integer from 0 to 300, preferably an integer from 0 to 200, more preferably an integer from 0 to 100, t is an integer from 0 to 200, preferably an integer from 0 to 100, and more preferably an integer from 0 to 50. u is an integer from 0 to 200, preferably from 0 to 100, and more preferably from 0 to 50. However, 1 ≦ t + u ≦ 400, preferably 1 ≦ t + u ≦ 200, and more preferably 1 ≦ t + u ≦ 100. In addition, 3 ≦ r + s + t + u ≦ 800, preferably 4 ≦ r + s + t + u ≦ 600. This organic polysiloxane must have R ¹ SiO _3/2 units (T units) and / or SiO _4/2 units (Q units), and therefore has a branched (resin-like) structure.

[(B) linear organic polysiloxane]

The component (B) of the present invention is also the main component of the addition-curing polysiloxane resin composition of the present invention. By using it in combination with the branched organopolysiloxane of the component (A), it can exhibit reduced viscosity, and even The effect of improving the strength of hardened materials. The organic polysiloxane is an organic polysiloxane represented by the following formula (2).

(R ¹ ₃ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (2) (wherein R ¹ has the same definition as above, at least two of R ¹ are alkenyl groups, and x is 200 to 700 Integer).

R ¹ may be the same as the groups listed in the specific examples of the component (A), and x is an integer of 200 to 700, and preferably 300 to 600. When x is less than 200, the cured product cannot obtain sufficient strength, and when x is more than 700, the cured product becomes cloudy.

Further, alkenyl groups having in one molecule at least two, the component (B), the preferably contain ^{10 × 10 -3 ~ 10 × 10} -1 mole / 100g, especially ^{10 × 10 -3 ~ 10 × 10} - ² moles / 100g.

In addition, the alkenyl group may be located in an R ¹ ₃ SiO _1/2 unit, an R ¹ ₂ SiO _2/2 unit, or a plurality of these units, and it is preferable to have an alkenyl group in the R ¹ ₃ SiO _1/2 unit.

The blending amount of the component (B) is a total of 100 parts by mass with the component (A). The blending ratio of the component (A) and the component (B) is based on the mass ratio and is (A): ( B) = 1: 1 ~ 2: 1 is better, 1.2: 1 ~ 2: 1 is better, 1.4: 1 ~ 2: 1 is better. As long as it is within this range, the cured product is not sticky and has good cutting properties, so it is suitable.

[(C) Cyclic vinylsiloxane]

The component (C) of the present invention can be used together with the components (A) and (B) to adjust the crosslinking density. As a result, the viscosity of the composition, the hardness and the strength of the cured product can be improved. This cyclic siloxane is a cyclic siloxane represented by the following formula (3).

(式中，R¹與上述相同，n為3~6之整數)

(In the formula, R ¹ is the same as above, and n is an integer of 3 to 6)

R ¹ may be the same as those exemplified in the specific examples of the component (A), and is preferably an alkyl group such as methyl, ethyl, propyl, or butyl, and more preferably methyl. n is an integer from 3 to 6, preferably 3 or 4.

Specific examples include 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7 -Tetravinylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinylcyclopentasiloxane, etc.

The amount of the component (C) added is 2 to 7 parts by mass, preferably 2 to 6 parts by mass, and more preferably 3 to 6 parts by mass relative to 100 parts by mass of the total of the components (A) and (B). When it is less than 2 parts by mass, the viscosity cannot be sufficiently reduced, and even the obtained hardened product does not have sufficient strength. In addition, it is also known that cyclic vinyl siloxane has an inhibitory effect on hydrosilylation. Therefore, if it is added more than 7 parts by mass, the hardening time becomes long, and even the crosslinking density becomes too large, so it becomes brittle.

[(D) Organic hydrogen polysiloxane]

The component (D) of the present invention can function as a cross-linking agent and form a cross-linked structure with the aforementioned components (A) to (C) by a hydrosilylation reaction to harden the polysiloxane resin composition.

(D) The organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule is not particularly limited, and an organohydrogenpolysiloxane represented by the following formula (4) is suitably used.

(R ² ₃ SiO _1/2 ) _{r '} (R ² ₂ SiO _2/2 ) _s' (R ² SiO _3/2 ) _{t '} (SiO _4/2 ) _u' (4) (where R ^{2 are} mutually Independently a hydrogen atom or a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms; at least two of R ² are hydrogen atoms; r 'is an integer of 0 to 100; s' is an integer of 0 to 300; t 'is an integer from 0 to 200 and u' is an integer from 0 to 200, but 2 ≦ r '+ s' + t '+ u' ≦ 800).

Here, R ² is a hydrogen atom or a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, especially 1 to 6, and examples of the monovalent saturated hydrocarbon group. Specifically, methyl, ethyl, Alkyl groups such as propyl and butyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and hydrogen atoms of carbon atoms bonded to these groups are partially or totally replaced by halogen atoms such as fluorine, bromine, and chlorine; A group such as a cyano group and the like, and at least two of R ² are hydrogen atoms, and other substituents are preferably methyl groups.

r 'is an integer from 0 to 100, preferably an integer from 0 to 75, more preferably an integer from 0 to 50, especially preferably 2 or more, s' is an integer from 0 to 300, and preferably an integer from 0 to 200. More preferably, it is an integer from 0 to 100, especially 1 or more, especially 2 or more. t 'is an integer from 0 to 200, preferably from 0 to 100, more preferably from 0 to 50, u' is an integer from 0 to 200, preferably from 0 to 100, and more preferably from 0 to 50 An integer is preferably in the range of 2 ≦ r '+ s' + t' + u '≦ 800, 3 ≦ r' + s' + t '+ u' ≦ 400 is better, and 4 ≦ r '+ s The range of '+ t' + u '≦ 200 is more preferable.

In addition, the hydrogen atom has at least two in one molecule, and in the component (D), it is preferable to contain 0.1 to 10 moles / 100g, especially 0.5 to 5 moles / 100g.

In addition, the hydrogen atom may be located in the R ² ₃ SiO _1/2 unit, the R ² ₂ SiO _2/2 unit, the R ² SiO _3/2 unit, or a plurality of these units, so that the R ² ₃ SiO _2/2 unit It is preferable to have a hydrogen atom.

One component (D) is an organohydrogenpolysiloxane having at least two hydrosilyl groups in a molecule, and the addition amount is 1 mole relative to the alkenyl group contained in the components (A) to (C), (D) The amount of hydrosilyl in the composition is 0.4 to 4.0 moles, preferably 0.6 to 2.0 moles, and more preferably 0.8 to 1.6 moles. the amount. When it is less than 0.4 mol, the SiH group is insufficient, so the hardening is poor. If it exceeds 4.0 mol, the residual SiH group is liable to cause side reactions such as dehydrogenation.

[(E) Hydrosilylation catalyst]

(E) The component is a hydrosilylation catalyst. The catalyst is not particularly limited as long as it has the ability to advance a hydrosilylation reaction. In particular, it is a catalyst selected from a platinum group metal monomer and a platinum group metal compound. Examples include platinum (including platinum black), platinum chloride, chloroplatinic acid, platinum-olefin complexes such as platinum-divinylsiloxane complexes, platinum catalysts such as platinum-carbonyl complexes, Palladium catalyst, rhodium catalyst, etc. These catalysts can be used alone or in combination of two or more. Among these, particularly preferred are platinum-olefin complexes such as chloroplatinic acid and platinum-divinylsiloxane complexes.

The amount of the component (E) may be a catalyst amount. The amount of the catalyst may be an amount that allows the hydrosilylation reaction to proceed, and may be appropriately adjusted in accordance with a desired curing rate. For example, in the case of a platinum group metal catalyst, from the viewpoint of the reaction rate, based on the mass standard converted to a platinum group metal atom, the above-mentioned mass relative to the total mass of the components (A) to (D) is 5 to 20 ppm. The amount is preferably, and even an amount of 5 to 10 ppm is preferable.

In addition to the components (A) to (E) described above, the curable composition of the present invention may contain a phosphor, an inorganic filler, an adjuvant, a hardening inhibitor, and the like as necessary. Each component is explained below.

[Fluorescent body]

The phosphor is not particularly limited, as long as a conventionally known phosphor is used. For example, a substance that absorbs light from a semiconductor element, especially a semiconductor light-emitting diode with a nitride-based semiconductor as a light-emitting layer, and converts it into light of a different wavelength is preferred. Such a phosphor is preferably selected from, for example, nitride-based phosphors, oxynitride-based phosphors activated mainly by lanthanoids such as Eu, Ce, lanthanides, Mn, etc. Alkaline earth metal halogen apatite phosphor activated by transition metal elements, alkaline earth metal borate halogen phosphor, alkaline earth metal aluminate phosphor, alkaline earth metal silicate phosphor, alkaline earth metal sulfide Phosphors, alkaline earth metal thiogallate phosphors, alkaline earth metal silicon nitride phosphors, germanate phosphors, or rare earth aluminates activated primarily by lanthanides such as Ce Phosphors, rare earth silicate phosphors, or organic complex phosphors activated mainly by lanthanides such as Eu, Ca-Al-Si-ON oxynitride glass phosphors, etc. More than one.

Examples of the nitride-based phosphor activated by lanthanides such as Eu and Ce include M ₂ Si ₅ N ₈ : Eu (M is at least one selected from the group consisting of Sr, Ca, Ba, Mg, and Zn). In addition, MSi ₇ N ₁₀ : Eu, M _1.8 Si ₅ O _0.2 N ₈ : Eu, and M _0.9 Si ₇ O _0.1 N ₁₀ : Eu (M is at least one selected from the group consisting of Sr, Ca, Ba, Mg, and Zn )Wait.

Examples of the oxynitride phosphor mainly activated by lanthanides such as Eu and Ce include MSi ₂ O ₂ N ₂ : Eu (M is at least one selected from the group consisting of Sr, Ca, Ba, Mg, and Zn).

Alkaline earth metal halogen apatite phosphors mainly activated by transition metal elements such as lanthanide and Mn such as Eu, M ₅ (PO ₄ ) ₃ X: R (M is selected from Sr, Ca, Ba, At least one of Mg and Zn, X is at least one selected from F, Cl, Br, and I, and R is any one or more of Eu, Mn, Eu, and Mn).

Alkaline earth metal borate halogen phosphors include M ₂ B ₅ O ₉ X: R (M is at least one selected from the group consisting of Sr, Ca, Ba, Mg, and Zn, and X is selected from the group consisting of F, Cl, Br, and I (At least one type, and R is any one or more of Eu, Mn, Eu, and Mn).

Examples of the alkaline earth metal aluminate phosphor include SrAl ₂ O ₄ : R, Sr ₄ Al ₁₄ O ₂₅ : R, CaAl ₂ O ₄ : R, BaMg ₂ Al ₁₆ O ₂₇ : R, BaMg ₂ Al ₁₆ O ₁₂ : R, and BaMgAl ₁₀ O ₁₇ : R (R is any one or more of Eu, Mn, Eu, and Mn).

Examples of the alkaline earth metal sulfide phosphor include La ₂ O ₂ S: Eu, Y ₂ O ₂ S: Eu, and Gd ₂ O ₂ S: Eu.

Rare earth aluminate phosphors activated mainly by lanthanides such as Ce include Y ₃ Al ₅ O ₁₂ : Ce, (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce, Y ₃ (Al _0.8 Ga _0.2 ) ₅ O ₁₂ : Ce and a YAG-based phosphor represented by the composition formula of (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ . In addition, Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc., in which part or all of Y is replaced by Tb, Lu, or the like.

Other phosphors include _{ZnS: Eu, Zn 2 GeO 4} : Mr 1, MGa 2 S 4: Eu (M is selected from Sr, Ca, Ba, Mg, at least one of Zn) and the like.

The phosphor may contain at least one selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, and Ti in place of Eu, or together with Eu, if necessary.

The Ca-Al-Si-ON-based oxynitride glass phosphor refers to a phosphor using oxynitride glass as a base material. The oxynitride glass is expressed in mole%, and CaCO ₃ is CaO Conversion is 20 ~ 50 mole%, Al ₂ O ₃ is 0 ~ 30 mole%, SiO is 25 ~ 60 mole%, AlN is 5 ~ 50 mole%, rare earth oxide or transition metal oxide is 0.1 ~ 20 Mol%, the total of the five ingredients is 100 Mol%. In addition, in the phosphor using oxynitride glass as a base material, the nitrogen content should be 15 mol% or less, and in addition to the rare earth oxide ions, it should contain other rare earth element ions as sensitizers. As a co-activator, its content in the fluorescent glass is in the range of 0.1 to 10 mole% based on the rare earth oxide.

In addition, phosphors other than the above-mentioned phosphors and having the same performance and effects can be used.

In the case of blending phosphors, the blending amount is preferably 0.1 to 2,000 parts by mass, and more preferably 0.1 to 100 parts by mass, relative to 100 parts by mass of the components (A) to (D). When the hardened | cured material of this invention is made into the wavelength conversion film containing a phosphor, it is preferable that the compounding quantity of a phosphor is 10-2,000 mass parts. In addition, the average particle diameter of the phosphor is preferably 10 nm or more, preferably 10 nm to 10 μm, and more preferably 10 nm to 1 μm. The average particle diameter can be measured by a particle size distribution measurement using a laser light diffraction method using a CILAS laser measurement device or the like.

[Inorganic filler]

Examples of the inorganic filler include silica, fumed silica, Fuming titanium dioxide, aluminum oxide, calcium carbonate, calcium silicate, titanium dioxide, iron (III) oxide, zinc oxide, and the like. These can be used alone or in combination of two or more. In the case of blending an inorganic filler, the blending amount is not particularly limited, as long as 100 parts by mass per (A) to (D) component total is 20 parts by mass or less, preferably in the range of 0.1 to 10 parts by mass It can be blended appropriately.

[Adhesive]

The curable composition of the present invention may contain a bonding aid as necessary in order to impart adhesion. Examples of the auxiliary agent include, for example, at least two functional groups selected from a hydrogen atom, an alkenyl group, an alkoxy group, and an epoxy group bonded to a silicon atom in one molecule, and preferably three kinds of organic siloxanes Oligomer. In the organosiloxane oligomer, the number of silicon atoms is preferably 4 to 50, and more preferably 4 to 20. As the adjuvant, an organosilyl-modified isocyanurate compound represented by the following general formula (5) and a hydrolyzed condensate thereof (organosiloxane-modified isocyanurate compound) can be used. ).

In the formula (5), R ^{3 is} independently an organic group represented by the following formula (6) or an aliphatic unsaturated monovalent hydrocarbon group which may have an oxygen atom. However, at least one of R ^{3 is} a group represented by the following formula (6).

(R⁴為氫原子或碳數1~6之甲基、乙基等的一價烴基，k為1~6之整數，宜為1~4之整數)。

(R ⁴ is a hydrogen atom or a monovalent hydrocarbon group such as a methyl group or an ethyl group having 1 to 6 carbon atoms, and k is an integer of 1 to 6, preferably an integer of 1 to 4).

In the above formula (5), the monovalent aliphatic unsaturated hydrocarbon group of R ³ which may have an oxygen atom is preferably a linear or branched alkenyl group having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, Examples include vinyl, allyl, 1-butenyl, 1-hexenyl, 2-methacryl, and (meth) acryl.

In the case of blending an adjuvant, the blending amount is preferably 10 parts by mass or less, more preferably 0.1 to 8 parts by mass, and particularly preferably 0.2 based on 100 parts by mass of the total of (A) to (D) components. ~ 5 parts by mass. As long as the blending amount is below the above upper limit value, the hardness of the cured product is high, and the surface stickiness can be suppressed.

In addition, in the case of blending an adjuvant, the blending amount is a ratio of the total number of hydrosilyl groups in the entire composition containing the adhesive agent to the total number of alkenyl groups in the entire composition. An amount of 0.4 to 4 is preferable, an amount of 0.6 to 3 is preferable, and an amount of 0.8 to 2 is more preferable.

[Sclerosis inhibitor]

The curable composition of the present invention may contain a hardening inhibitor in order to control reactivity and improve storage stability. Hardening inhibitor, which can be selected from Triallyl isocyanurate, alkyl maleate, acetylene alcohols, and their silane modifiers and siloxane modifiers, hydrogen peroxide, tetramethylethylenediamine, benzotriazole, and the like A mixture of compounds. In the case of blending a hardening inhibitor, the blending amount is preferably 5 to 100 times the molar effective ratio of the catalyst in the hydrosilylation catalyst of the (E) component. It is preferably 5 to 50 times the amount.

[Other additives]

The curable composition of the present invention may contain other additives in addition to the aforementioned components. Other additives include, for example, anti-aging agents, free radical inhibitors, flame retardants, surfactants, ozone deterioration inhibitors, light stabilizers, tackifiers, plasticizers, antioxidants, heat stabilizers, and conductivity imparting agents. , Antistatic agent, radiation shielding agent, nuclear agent, phosphorus peroxide decomposing agent, lubricant, pigment, metal deactivator, physical property adjusting agent, organic solvent, etc. These arbitrary components can be used individually by 1 type or in combination of 2 or more types.

The simplest embodiment of the curable composition of the present invention is a composition composed of (A) component, (B) component, (C) component, (D) component, and (E) component. Preferably, it is a composition consisting of (A) component, (B) component, (C) component, (D) component, (E) component, and a phosphor. In particular, in order to obtain a hardened material having high transparency, an inorganic filler such as silicon dioxide is preferably not contained. Examples of the inorganic filler are as described above.

The method for preparing the curable composition of the present invention is not particularly limited as long as it is based on a conventionally known method. For example, (A), The components (B), (C), (D), and (E) are prepared by mixing them by any method. Or just combine (A), (B), (C), (D), (E) components with phosphors, or (A), (B), (C), (D), (E) components, And arbitrary components may be mixed and prepared by any method. For example, a commercially available blender (THINKY CONDITIONING MIXER (manufactured by Thinky Co., Ltd.), etc.) can be incorporated into the blender for uniform mixing for about 1 to 5 minutes.

The method for hardening the curable composition of the present invention is not particularly limited as long as it is in accordance with a conventionally known method. For example, it can be hardened at 60 to 180 ° C for about 1 to 12 hours. Especially, it is better to harden it by step hardening at 60 ~ 180 ℃, preferably 60 ~ 150 ℃. In the case of stage hardening, it is preferable to pass through the following two stages. First, the curable composition is heated at a temperature of 60 to 100 ° C. for 0.5 to 2 hours to sufficiently defoam. Next, the curable composition is heat-hardened at a temperature of 120 to 180 ° C. for 1 to 10 hours. By passing through these stages, even when the hardened material is thick, it can be sufficiently hardened, and bubbles do not occur, and it is colorless and transparent. In addition, in the present invention, a colorless and transparent hardened material means a hardened material having a light transmittance at 450 nm of 80% or more, preferably 85% or more, and particularly preferably 90% or more when the thickness is 1 mm. The measurement of the light transmittance will be described later.

The curable composition of the present invention can produce a cured product having a high optical transmittance. Therefore, the curable composition of the present invention is a useful article in terms of LED element sealing applications, especially in blue LED or ultraviolet LED element sealing applications. A method of sealing the LED element or the like with the curable composition of the present invention may be any method that is conventionally known. For example, it can be performed by a dispensing method, a compression molding method, or the like.

The hardenable composition and hardened product of the present invention, among other things, have excellent properties such as crack resistance, heat resistance, light resistance, transparency, etc., and are therefore used in display materials, optical recording medium materials, optical machine materials, Optical component materials, optical fiber materials, photoelectromechanical organic materials, and semiconductor integrated circuit peripheral materials are also useful.

[Example]

The present invention will be described in more detail by the following examples and comparative examples. However, the present invention is not limited by the following examples.

The weight average molecular weight (Mw) disclosed in the following examples is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The measurement conditions are described below.

[GPC measurement conditions]

Development solvent: tetrahydrofuran

Flow rate: 0.6mL / min

Column: TSK Guardcolumn SuperH-L

TSKgel SuperH4000 (6.0mm I.D. × 15cm × 1)

TSKgel SuperH3000 (6.0mm I.D. × 15cm × 1)

TSKgel SuperH2000 (6.0mm I.D. × 15cm × 2)

(Either is made by Tosoh Corporation)

Column temperature: 40 ℃

Sample injection volume: 20 μL (sample concentration: 0.5% by mass-tetrahydrofuran solution) detector; differential refractive index meter (RI)

The Vi (vinyl) valence (Moore / 100g) and SiH valence (Moore / 100g) shown in the following examples are the ¹ H-NMR spectra of a compound at 400 MHz, and dimethylarsine is used as the internal standard. The product is calculated from the integral value of the hydrogen atom of the obtained vinyl or hydrosilyl group.

The (C) component used in an Example and a comparative example is shown below. In the following formula, Me represents a methyl group.

(C-1) 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (Vi value = 1.16 mol / 100g)

(C-2) 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane (Vi value = 1.16 mol / 100g)

(C-1 ') Two-terminal vinyl dimethyl silicone oil represented by the following formula (manufactured by Shin-Etsu Chemical Industry Co., Ltd., Vi price = 0.217 mole / 100g)

(C-2 ') Both terminal vinyl (dimethyl) (methyl vinyl) silicone oils represented by the following formula (manufactured by Shin-Etsu Chemical Industry Co., Ltd., Vi price = 1.14 moles / 100 g)

(C-3 ’) 1,3,5,7-tetramethylcyclotetrasiloxane (SiH value = 1.18 mole / 100g)

The components (A), (B), (D), and (E) used in the examples and comparative examples are described below. In the following formula, Me represents a methyl group.

(A) Methyl polysiloxane resin (manufactured by Shin-Etsu Chemical Industry Co., Ltd., Vi price = 9.12 × 10 ^-2 mole / 100g)

(B) Two-terminal vinyl dimethyl silicone oil represented by the following formula (manufactured by Shin-Etsu Chemical Industry Co., Ltd., Vi price = 5.12 × 10 ^-3 mole / 100g)

(D) SiH group-containing linear silicone oil represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., SiH price = 1.63 moles / 100g)

(E) Divinylsiloxane complex of chloroplatinic acid

[Example 1]

53 parts by mass of (A), 36 parts by mass of (B), 4 parts by mass of (C), and 7 parts by mass of (D) were mixed, and 5 ppm by weight of platinum (E) of chloroplatinic acid was added A divinylsiloxane complex is mixed to prepare a hardenable composition.

[Examples 2 to 4 and Comparative Examples 1 to 5]

Except that the blending amount of each component was changed as described in Table 1, the same operation as in Example 1 was repeated to prepare a curable composition.

Modulated for the above Examples 1 to 4 and Comparative Examples 1 to 5 The resulting curable composition was subjected to the tests shown below.

[Viscosity of hardening composition]

According to JIS Z 8803: 2011, the viscosity of the curable composition at 23 ° C. was measured using a B-type viscometer. The results are described in Table 1.

[Hardness of hardened material]

A 50 mm diameter × 10 mm thick aluminum shallow dish was filled with the prepared hardening composition, and the samples were hardened in stages in the order of 60 ° C × 1 hour, 100 ° C × 1 hour, and 150 ° C × 4 hours to produce samples . The hardness of the obtained hardened product (Shore A or Shore D) was measured in accordance with the method described in JIS K 6253-3: 2012. The results are described in Table 1.

[Transmittance of hardened material]

A 1mm thick Teflon (registered trademark) spacer with a concave shape is sandwiched between two 50mm × 20mm × 1mm thick glass slides. After fixing these, a hardening composition is poured and the temperature is 60 ° C. × 1 hour, 100 ° C. × 1 hour, and 150 ° C. × 4 hours were sequentially cured in stages to produce a transmittance measurement sample. The light transmittance of the obtained sample at 450 nm was measured with a spectrophotometer U-4100 (manufactured by Hitachi High Technologies). The results are described in Table 1.

[Tensile strength of hardened material and elongation at cutting]

150mm x 200mm x 2mm thick Teflon (registered trademark) gold A prepared hardening composition is poured into a mold, and the sample is hardened in stages in the order of 60 ° C. × 1 hour, 100 ° C. × 1 hour, and 150 ° C. × 4 hours. According to JIS K 6251: 2010, EZ TEST (EZ-L, manufactured by Shimadzu Corporation) was used to measure the tensile strength of the sample at a test speed of 500 mm / min, a distance between fixtures of 80 mm, and a punctuation distance of 40 mm Elongation at cutting. The results are described in Table 1.

[Tackiness of hardened material]

The thumb was pressed against the surface of the hardened material for 1 second, and the resistance when pulled apart was evaluated. Those who felt resistance were rated "yes" and those who did not feel resistance were rated "no". The results are shown in Table 1.

[Cutability of hardened material]

The prepared Teflon (registered trademark) metal mold was filled with the prepared hardening composition, and then stepwise hardened in the order of 60 ° C × 1 hour, 100 ° C × 1 hour, and 150 ° C × 4 hours to produce 100 mm. × 100mm × 2mm thick hardened sheet. The obtained sheet was evaluated by blade cutting with a blade of ZP07-SD2000-F1B333NBC-ZB1050 (DISCO Co., Ltd.). The evaluation was rated as "good" for the case where there was no dent after cutting, and as "bad" for the part after cutting. The results are shown in Table 1.

As shown in Table 1, the curable polysiloxane resin composition using the cyclic vinyl siloxane of the present invention in an appropriate amount can produce a hardened material having sufficient strength, good cutting properties, and no stickiness. In addition, the viscosity of the resin composition can be reduced, and an improvement in work efficiency can be expected.

The present invention is not limited to the embodiments described above. The above embodiment is an example, and any article having substantially the same structure and exhibiting the same effect as the technical idea described in the patent application scope of the present invention is included in the technical scope of the present invention.

Claims (4)

An addition-curable polysiloxane resin composition characterized by containing the following components (A) to (E) and (A) a branched organic polysiloxane (R ¹ ) represented by the following formula (1) ₃ SiO _1/2 ) _r (R ¹ ₂ SiO _2/2 ) _s (R ¹ SiO _3/2 ) _t (SiO _4/2 ) _u (1) (wherein R ^{1 is} independently selected from the carbon number 1 to 12 substituted or unsubstituted monovalent saturated hydrocarbon groups and alkenyl groups having 2 to 6 carbon atoms, but at least 2 of R ¹ are alkenyl groups, r is an integer of 0 to 100, and s is 0 to 300 Integer, t is an integer from 0 to 200, and u is an integer from 0 to 200, but 1 ≦ t + u ≦ 400, 3 ≦ r + s + t + u ≦ 800); (B) The following formula (2) Linear organic polysiloxane (R ¹ ₃ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (2) (where R ¹ is the same as above, but at least two of R ¹ Is an alkenyl group, and x is an integer of 200 to 700); (C) a cyclic vinyl siloxane represented by the following formula (3): 2 with respect to 100 parts by mass of the total of the components (A) and (B); ~ 7 parts by mass

(In the formula, R ¹ is the same as above, and n is an integer of 3 to 6); (D) an organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule: relative to the components (A) to (C) The alkenyl group in the compound is 1 mole, the amount of the hydrosilyl group in the component (D) is 0.4 to 4.0 moles, and (E) the hydrosilylation catalyst: an amount sufficient for the hydrosilylation reaction. For example, the addition-curable polysiloxane resin composition of the first patent application range, wherein the blending ratio of the aforementioned (A) component and (B) component is calculated by mass ratio as (A): (B) = 1: 1 ~ 2: 1. For example, the addition-curable polysiloxane resin composition according to item 1 or 2 of the patent application range, wherein the (D) component is an organohydrogenpolysiloxane (R ² ₃ SiO _{1 / 2} ) _{r '} (R ² ₂ SiO _2/2 ) _s' (R ² SiO _3/2 ) _{t '} (SiO _4/2 ) _u' (4) (where R ^{2 is} independently a hydrogen atom or carbon A substituted or unsubstituted monovalent saturated hydrocarbon group of the number 1 to 12, at least two of R ² are hydrogen atoms, r 'is an integer of 0 to 100, s' is an integer of 0 to 300, and t' is an integer of 0 to 200 Integer and u 'are integers from 0 to 200, but 2 ≦ r' + s' + t '+ u' ≦ 800). For example, the addition-curable polysiloxane resin composition according to any one of claims 1 to 3, wherein the blending amount of the component (E) is 5 relative to the total mass of the components (A) to (D) ~ 20ppm amount.