TWI728074B - Addition curable silicone resin composition - Google Patents

Abstract

The subject of the present invention is to provide an addition curable polysiloxane resin composition that has low viscosity and good dispensing properties before curing, produces sufficient strength after curing, has good cutting properties, and does not stick to the cured product, especially Methyl polysiloxane resin composition.

The solution to the problem is an addition curable silicone resin composition containing: (A) a branched organopolysiloxane containing alkenyl groups (B) a linear organopolysiloxane containing alkenyl groups ( C) Cyclic vinylsiloxane: 3-7 parts by mass relative to 100 parts by mass of the total of components (A) and (B) (D) Organohydrogenpolysiloxane having at least two hydrosilyl groups in the molecule , And (E) Hydrosilylation catalyst.

Description

Addition curable silicone resin composition

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

The addition-curing silicone resin composition has excellent rapid curing properties, heat resistance of the cured product, weather resistance, etc., so it has been used in the past as a sealing material for sealing semiconductor elements such as LEDs. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2007-2234) proposes an addition-curing silicone resin composition that exhibits high adhesion to LED packages made of thermoplastic resins 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-curable silicone resin composition.

As such, addition-curing silicone resins are generally widely used as semiconductor sealing materials, but their characteristics are still unsatisfactory. Generally speaking, methyl polysiloxane resin has softness and poor cutting properties, and in most cases, it has disadvantages such as sticking. _{If the SiO 4/2} unit [Q unit] or RSiO _3/2 unit [T unit] is added in order to improve the cutting performance, although a hard and non-sticky hardened product can be produced, it will become low in strength and brittle. Of resin.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2007-2234 A

[Patent Document 2] JP 2006-93354 A

The present invention has been completed in view of the above-mentioned problems, and its purpose is to provide an addition-curing polysilicone which has a low viscosity and good dispensing performance before hardening, and produces a hardened substance with sufficient strength after hardening, good cutting performance, and non-sticking. Resin composition, especially methyl polysiloxane resin composition.

(式(3)中，R¹與上述式(1)中的R¹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 inventor of the present invention has studied and reviewed, and found that an addition curable silicone resin composition containing the following components (A) to (E), (A) branched as represented by the following formula (1) Organopolysiloxane (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 Independently of each other is a group selected from a substituted or unsubstituted monovalent saturated hydrocarbon group with 1 to 12 carbons and an alkenyl group with 2 to 6 carbons, but ^{at least two of R 1} are alkenyl groups, and r is 0-100 Integer, s is an integer from 0 to 300, t is an integer from 0 to 200, u is an integer from 0 to 200, but 1≦t+u≦400, 3≦r+s+t+u≦800); (B ) The linear organopolysiloxane represented by the following formula (2) (R ¹ ₃ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (2) (In formula (2), R ¹ Independently of each other are groups selected from substituted or unsubstituted monovalent saturated hydrocarbon groups with 1 to 12 carbons and alkenyl groups with 2 to 6 carbons, but ^{at least two of R 1} are alkenyl groups, and the alkenyl group is located Respectively 2 (R ¹ ₃ SiO _1/2 ) units instead of x (R ¹ ₂ SiO _2/2 ) units, x is 200~700 (but not including the integer of x=200); (C) Cyclic vinylsiloxane represented by the following formula (3): 2-7 parts by mass relative to 100 parts by mass of the total of components (A) and (B)

(In the formula (3), the same as R ¹ (1) R in the above Formula ^1, n is an integer of 3 to 6); (D) having an alkyl group of one molecule at least two silicon organohydrogen silicon hydrogen siloxane : Relative to 1 mol of alkenyl group in components (A) to (C), the amount of hydrosilyl group in component (D) is 0.4 to 4.0 mol, and (E) hydrosilylation catalyst: hydrogen silane The sufficient amount of chemical reaction has low viscosity and good dispensing performance before hardening, and after hardening, it produces a hardened product with sufficient strength, good cutting performance, and no sticking, and the present invention is completed.

That is, the present invention provides the following addition curable polysiloxane resin Lipid composition.

(式(3)中，R¹與上述式(1)中的R¹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) components (A) and a branched 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} independently selected from A substituted or unsubstituted monovalent saturated hydrocarbon group with 1 to 12 carbons and an alkenyl group with 2 to 6 carbons, but ^{at least two of R 1} are alkenyl groups, r is an integer from 0 to 100, and s is 0 to 300 is an integer, t is an integer from 0 to 200, u is an integer from 0 to 200, but 1≦t+u≦400, 3≦r+s+t+u≦800); (B) the following formula (2) ) Represented by linear organopolysiloxane (R ¹ ₃ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (2) (In formula (2), R ^{1 is} independently selected from A substituted or unsubstituted monovalent saturated hydrocarbon group with 1 to 12 carbons and an alkenyl group with 2 to 6 carbons, but ^{at least two of R 1} are alkenyl groups, and the alkenyl groups are located in two ( R ¹ ₃ SiO _1/2 ) unit instead of x (R ¹ ₂ SiO _2/2 ) unit, x is 200~700 (but not including the integer of x=200); (C) the following formula (3) Cyclic vinylsiloxane represented by: 2-7 parts by mass relative to 100 parts by mass of the total of components (A) and (B)

(In the formula (3), the same as R ¹ (1) R in the above Formula ^1, n is an integer of 3 to 6); (D) having an alkyl group of one molecule at least two silicon organohydrogen silicon hydrogen siloxane : Relative to 1 mol of alkenyl group in components (A) to (C), the amount of hydrosilyl group in component (D) is 0.4 to 4.0 mol, and (E) hydrosilylation catalyst: hydrogen silane The amount sufficient for the chemical reaction.

[2] The addition curable silicone resin composition as in [1], wherein the blending ratio of the aforementioned (A) component and (B) component is calculated by mass ratio as (A): (B)=1: 1~2:1.

[3] The addition curable silicone resin composition according to [1] or [2], wherein the aforementioned component (D) is an organohydrogen polysiloxane represented by the following formula (4) (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 a substituted or unsubstituted monovalent saturated hydrocarbon group with 1 to 12 carbon ^{atoms, at least two of R 2} are hydrogen atoms, r'is an integer from 0 to 100, s'is an integer from 0 to 300, and t'is 0 to An integer of 200, u'is an integer of 0~200, but 2≦r'+s'+t'+u'≦800).

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

According to the present invention, by adding a sufficient amount of cyclic vinyl silicone, it is possible to obtain low viscosity and good dispensing performance before curing, and produce It has sufficient strength, good cutting ability, and is an additive curable silicone resin composition that does not stick to the hardened material.

Hereinafter, each component of the present invention will be explained.

[(A) Branched (resin-like) organopolysiloxane]

The component (A) of the present invention is the 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} independent of each other A group consisting of a substituted or unsubstituted monovalent saturated hydrocarbon group with 1 to 12 carbons and an alkenyl group with 2 to 6 carbons, but ^{at least two of R 1} are alkenyl groups, r is an integer from 0 to 100, and s is 0 ~300 is an integer, t is an integer of 0~200, u is an integer of 0~200, 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 carbons, preferably 1 to 6, preferably 1 to 4, and an alkenyl group having 2 to 6 carbons. Examples of monovalent saturated hydrocarbon groups include, specifically, alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclopentyl and cyclohexyl, and those bonded to these groups A group in which part or all of the hydrogen atoms of the carbon atoms are replaced by halogen atoms such as fluorine, bromine, chlorine, cyano, (meth)acryloxy, glycidoxy, mercapto, and amino groups, such as three Halogenated monovalent saturated hydrocarbon groups such as fluoropropyl and chloropropyl; cyanoalkyl groups such as β-cyanoethyl and γ-cyanopropyl; 3-methacryloxypropyl, 3-glycidoxypropyl Group, 3-mercaptopropyl, 3-aminopropyl, etc. Examples of alkenyl groups include vinyl groups, allyl groups, propenyl groups, hexenyl groups, and styryl groups. Among them, methyl, cyclohexyl, etc. are preferred, and methyl is particularly preferred. However, ^{at least two of R 1} are alkenyl groups, and the alkenyl group is preferably a vinyl group.

In addition, the alkenyl group has at least two in one molecule, and the organopolysiloxane of component (A) preferably contains 0.005 to 0.5 mol/100g, especially 0.01 to 0.2 mol/100g.

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

In addition, r is an integer of 0 to 100, preferably an integer of 0 to 75, preferably an integer of 0 to 50, but it is more preferable that r is 2 or more, especially 2 to 50, especially 3 to 40. It is preferably 3 to 35. In this case, when the R ¹ ₃ SiO _1/2 unit has an alkenyl group, ^{the r of the R 1} ₃ SiO _1/2 unit having the alkenyl group is preferably 2 to 50. 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 an integer from 0 to 100, more preferably an integer 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. The organopolysiloxane must have R ¹ SiO _3/2 units (T units) and/or SiO _4/2 units (Q units), so it has a branched (resin-like) structure.

[(B) Linear organopolysiloxane]

The component (B) of the present invention is also the main component of the addition curable polysiloxane resin composition of the present invention. By using it in combination with the branched organopolysiloxane of component (A), it can reduce the viscosity, even Improve the strength of the hardened product. This organopolysiloxane is an organopolysiloxane represented by the following formula (2).

(R ¹ ₃ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (2) (In the formula, ^{the definition of R 1} is the same as above, ^{at least 2 of R 1} are alkenyl groups, and x is 200~700 Integer).

R ¹ can exemplify the same groups as those exemplified in the specific examples of the component (A), and x is an integer of 200 to 700, preferably 300 to 600. If x is less than 200, the hardened product cannot obtain sufficient strength, and if x is greater than 700, the hardened product will become 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 the R ¹ ₃ SiO _1/2 unit, the R ¹ ₂ SiO _2/2 unit, or a plurality of these units, and the R ¹ ₃ SiO _1/2 unit preferably has an alkenyl group.

The blending amount of the (B) component is an amount that totals 100 parts by mass with the (A) component, and the blending ratio of the aforementioned (A) component and (B) component is calculated by mass ratio, which is based on (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 hardened material will not stick and the cutting performance is good, so it is suitable.

[(C) Cyclic Vinylsiloxane]

The (C) component of the present invention can be used together with the aforementioned (A) and (B) components to adjust the cross-linking density. As a result, the viscosity of the composition or the hardness and 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, n is an integer from 3 to 6)

R ¹ may be exemplified the same groups as specific examples of the component (A) of the recited groups, an alkyl group is suitably a methyl, ethyl, propyl, butyl, etc., preferably methyl. n is an integer from 3 to 6, preferably 3 or 4.

Specifically, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7 can be exemplified -Tetravinylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinylcyclopentasiloxane, etc.

The amount of (C) component added is 2 to 7 parts by mass relative to 100 parts by mass of the total of (A) and (B) components, preferably 2 to 6 parts by mass, and more preferably 3 to 6 parts by mass. In the case of less than 2 parts by mass, the viscosity cannot be sufficiently reduced, and the resulting hardened product may not have sufficient strength. In addition, it is also known that cyclic vinylsiloxane has an inhibitory effect on hydrosilylation. Therefore, if it is added more than 7 parts by mass, the curing time will become longer, and the crosslinking density will even become too large, which will result in brittleness.

[(D) Organohydrogen polysiloxane]

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

(D) The organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule is not particularly limited, and the organohydrogenpolysiloxane represented by the following formula (4) can be 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 is} mutually Independently is a hydrogen atom or a substituted or unsubstituted monovalent saturated hydrocarbon group with 1 to 12 carbons ^{, at least two of R 2} are hydrogen atoms, r'is an integer from 0 to 100, s'is an integer from 0 to 300, t'is an integer from 0 to 200, 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, examples of the monovalent saturated hydrocarbon group, specifically, methyl, ethyl, Alkyl groups such as propyl group and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and hydrogen atoms of carbon atoms bonded to these groups are partially or completely replaced by halogen atoms such as fluorine, bromine, and chlorine, Groups substituted by cyano groups, etc., 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, preferably an integer from 0 to 200, More preferably, it is an integer of 0-100, especially 1 or more, especially 2 or more. t'is an integer of 0~200, preferably an integer of 0~100, more preferably an integer of 0~50, u'is an integer of 0~200, preferably an integer of 0~100, more preferably an integer of 0~50 Integer, preferably in the range of 2≦r'+s'+t'+u'≦800, preferably in the range of 3≦r'+s'+t'+u'≦400, 4≦r'+s The range of'+t'+u'≦200 is more preferable.

In addition, there are at least two hydrogen atoms in one molecule, and the component (D) preferably contains 0.1-10 mol/100g, especially 0.5-5 mol/100g.

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

(D) An organohydrogen polysiloxane having at least two hydrosilyl groups in one molecule of the component, and its addition amount is 1 mol relative to the alkenyl group contained in the components (A) to (C), (D) The amount of hydrosilyl group in the composition is 0.4 to 4.0 mol, preferably 0.6 to 2.0 mol, more preferably 0.8 to 1.6 mol the amount. If it is less than 0.4 mol, the SiH group is insufficient and hardening is poor. If it exceeds 4.0 mol, the remaining SiH group is likely 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 the hydrosilylation reaction. In particular, it is preferably a catalyst selected from platinum group metal monomers and platinum group metal compounds. Examples include platinum (including platinum black), platinum chloride, chloroplatinic acid, platinum-divinylsiloxane complexes and other platinum-olefin complexes, platinum-carbonyl complexes and other platinum catalysts, Palladium catalyst, rhodium catalyst, etc. These catalysts can be used alone or in combination of two or more. Among them, particularly preferred are platinum-olefin complexes such as chloroplatinic acid and platinum-divinylsiloxane complexes.

(E) The blending amount of the component may be the amount of the catalyst. The amount of the catalyst may be any amount that allows the hydrosilylation reaction to proceed, and may be appropriately adjusted in accordance with the desired curing rate. For example, in the case of platinum group metal catalysts, from the viewpoint of the reaction rate, based on the mass basis of platinum group metal atoms, the above-mentioned total mass of the components (A) to (D) is 5-20 ppm The amount of is better, and even the amount of 5-10 ppm is better.

In addition to the above-mentioned (A) to (E) components, the curable composition of the present invention may contain phosphors, inorganic fillers, adhesives, curing inhibitors, etc. as necessary. The following is an explanation of each ingredient.

[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 the light-emitting layer, and converts it into light of different wavelengths is preferable. Such a phosphor is preferably selected from, for example, nitride-based phosphors, oxynitride-based phosphors that are mainly activated by lanthanide elements such as Eu, Ce, and lanthanides, Mn, etc. Alkaline earth metal halide phosphors activated by transition metal elements, alkaline earth metal borate halogen phosphors, alkaline earth metal aluminate phosphors, alkaline earth metal silicate phosphors, alkaline earth metal sulfides Phosphors, alkaline earth metal thiogallate phosphors, alkaline earth metal silicon nitride phosphors, germanate phosphors, or rare earth aluminates mainly activated by lanthanides such as Ce Phosphors, rare earth silicate phosphors, or organic complex phosphors mainly activated by lanthanides such as Eu, Ca-Al-Si-ON oxynitride glass phosphors, etc. More than one kind.

Nitride-based phosphors mainly activated by lanthanide elements such as Eu and Ce include M ₂ Si ₅ N ₈ : Eu (M is at least one selected from 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 Sr, Ca, Ba, Mg, Zn )Wait.

The oxynitride phosphors mainly activated by lanthanide elements such as Eu and Ce include MSi ₂ O ₂ N ₂ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, and Zn).

Alkaline earth metal halide apatite fluors mainly activated by transition metal elements such as Eu and other lanthanides, Mn, etc., include 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, including M ₂ B ₅ O ₉ X: R (M is at least one selected from Sr, Ca, Ba, Mg, Zn, and X is selected from F, Cl, Br, I At least one, R is any one or more of Eu, Mn, Eu, and Mn).

Alkaline earth metal aluminate phosphors 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 alkaline earth metal sulfide phosphors 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 lanthanide elements 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 : A YAG-based phosphor represented by the composition formula of Ce and (Y, Gd) ₃ (Al, Ga) ₅ O _{12. In addition, there are Tb 3} Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc. in which part or all of Y is substituted by Tb, Lu, and the like.

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

The above-mentioned phosphors may contain at least one selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, and Ti instead of or together with Eu as required.

Ca-Al-Si-ON-based oxynitride glass phosphor refers to a phosphor using oxynitride glass as a matrix material. In the oxynitride glass, it is expressed in mole %, and CaCO ₃ is CaO Converted to 20-50 mol%, Al ₂ O ₃ is 0-30 mol%, SiO is 25-60 mol%, AlN is 5-50 mol%, rare earth oxides or transition metal oxides are 0.1 ~20 mol%, the total of the five components is 100 mol%. In addition, in the phosphor with oxynitride glass as the matrix material, the nitrogen content is preferably 15 mol% or less, and in addition to the rare earth oxide ions, it is advisable to contain other rare earth element ions as a sensitizer As a co-activator, its content in the fluorescent glass is in the range of 0.1-10 mol% in terms of rare earth oxides.

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

When the phosphor is blended, 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 cured product of the present invention is made into a phosphor-containing wavelength conversion film, the blending amount of the phosphor is preferably set at 10 to 2,000 parts by mass. 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 above-mentioned average particle size can be measured by a CILAS laser measuring device, etc., by a particle size distribution measurement by a laser light diffraction method.

[Inorganic Filler]

Inorganic fillers, for example, silica, fuming silica, Fuming titanium dioxide, aluminum oxide, calcium carbonate, calcium silicate, titanium dioxide, iron (III) oxide, zinc oxide, etc. These can be used individually by 1 type or in combination of 2 or more types. In the case of blending inorganic fillers, the blending amount is not particularly limited, as long as it is 20 parts by mass or less per 100 parts by mass of the total of components (A) to (D), preferably in the range of 0.1-10 parts by mass It is sufficient to blend appropriately.

[Adhesive agent]

In order to impart adhesiveness to the curable composition of the present invention, an adhesive auxiliary agent may be contained as necessary. The auxiliary agent may be, for example, an organosiloxane having 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, preferably three types of organosiloxanes Oligomer. In the organosiloxane oligomer, the number of silicon atoms is preferably 4-50, preferably 4-20. In addition, as an adhesive agent, an organooxysilyl-modified isocyanurate compound represented by the following general formula (5), and its hydrolysis condensate (organosiloxane-modified isocyanurate compound) can be used. ).

In the above 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 or ethyl group with a carbon number of 1 to 6, 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 which may have an oxygen atom for R 3} is preferably a linear or branched alkenyl group having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, For example, a vinyl group, an allyl group, a 1-butenyl group, a 1-hexenyl group, a 2-methpropenyl group, or a (meth)acrylic group can be mentioned.

In the case of blending an adhesive agent, the blending amount is preferably 10 parts by mass or less, preferably 0.1 to 8 parts by mass, and particularly preferably 0.2, relative to 100 parts by mass of the total of components (A) to (D). ~5 parts by mass. As long as the blending amount is below the above upper limit, the hardness of the hardened product will be high and the surface stickiness can also be suppressed.

In addition, when an adhesive agent is blended, the blending amount is such that the 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 The amount of 0.4 to 4 is preferable, the amount of 0.6 to 3 is more preferable, and the amount of 0.8 to 2 is more preferable.

[Sclerosis inhibitor]

The curable composition of the present invention may contain a curing inhibitor in order to control reactivity and improve storage stability. Hardening inhibitors can be selected from Triallyl isocyanurate, alkyl maleate, acetylene alcohols, and silane-modified products and siloxane-modified products, hydrogen peroxide, tetramethylethylenediamine, benzotriazole, and the like The compound of the group formed by the mixture. In the case of blending a hardening inhibitor, the blending amount is 5 to 100 times the effective amount of the catalyst in the hydrosilylation catalyst of component (E) in terms of molar ratio. Preferably, the amount is 5 to 50 times.

[Other additives]

In the curable composition of the present invention, in addition to the above-mentioned components, other additives may be blended. Other additives include, for example, anti-aging agents, free radical inhibitors, flame retardants, surfactants, ozone degradation inhibitors, light stabilizers, tackifiers, plasticizers, antioxidants, heat stabilizers, conductivity imparting agents , Antistatic agents, radiation shielding agents, nucleating agents, phosphorus peroxide decomposers, lubricants, pigments, metal deactivators, physical property regulators, organic solvents, 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. It is preferably a composition composed of (A) component, (B) component, (C) component, (D) component, (E) component, and phosphor. In particular, in order to obtain a cured product with high transparency, it is preferable not to contain inorganic fillers such as silicon dioxide. Examples of this inorganic filler are as described above.

The preparation method of 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 mixed and prepared by any method. Or as long as the (A), (B), (C), (D), (E) components and the phosphor, or (A), (B), (C), (D), (E) components, And any components may be mixed and prepared by any method. For example, it can be prepared by putting it in a commercially available mixer (THINKY CONDITIONING MIXER (manufactured by Thinky Co., Ltd.), etc.) and mixing uniformly for about 1 to 5 minutes.

The method of 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 cured at 60~180℃ for about 1~12 hours. Particularly, it is better to harden it by stepwise hardening at 60~180℃, preferably 60~150℃. In the stage hardening, it is better to go 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 fully defoam. Next, the curable composition is heat-cured at a temperature of 120 to 180°C for 1 to 10 hours. By going through these stages, even when the hardened material is thick, it can be cured sufficiently, bubbles will not occur, and it is colorless and transparent. In addition, the colorless and transparent cured product in the present invention means a cured product having a light transmittance at 450 nm of 80% or more at a thickness of 1 mm, preferably 85% or more, and particularly preferably 90% or more. The measurement of the light transmittance will be described later.

The curable composition of the present invention can produce a cured product with high optical transmittance. Therefore, the curable composition of the present invention is useful in LED device sealing applications, especially in blue LED or ultraviolet LED device sealing applications. The method of sealing LED elements and the like with the curable composition of the present invention may be in accordance with a conventionally known method. For example, it can be performed by a dispensing method, a compression molding method, or the like.

In other respects, the curable composition and cured product of the present invention have excellent characteristics such as crack resistance, heat resistance, light resistance, transparency, etc., and are therefore used in display materials, optical recording media materials, optical device materials, Optical component materials, optical fiber materials, photoelectric energy organic materials, semiconductor integrated circuit peripheral materials, etc. are also very useful.

[Example]

The following examples and comparative examples are disclosed to illustrate the present invention in more detail, but 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 disclosed below.

[GPC measurement conditions]

Developing 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)

(Any one is manufactured by Tosoh Corporation)

Column temperature: 40℃

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

The Vi (vinyl) valence (mole/100g) and SiH valence (mole/100g) shown in the following examples are measured by ¹ H-NMR spectrum of the compound at 400 MHz, and dimethyl sulfide 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 component (C) used in Examples and Comparative Examples is disclosed as follows. In addition, in the following formula, Me represents a methyl group.

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

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

(C-1') Vinyl dimethyl polysiloxane oil at both ends represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., Vi value = 0.217 mol/100g)

(C-2') Two-terminal vinyl (dimethyl) (methyl vinyl) polysiloxane oil represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., Vi price = 1.14 mol/100g)

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

The (A) component, (B) component, (D) component, and (E) component used in the Example and the comparative example are shown below. In addition, in the following formula, Me represents a methyl group.

(A) Methyl silicone resin represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., Vi price = 9.12×10 ^-2 mol/100g)

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

(D) The SiH group-containing linear polysiloxane oil represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., SiH value=1.63 mol/100g)

(E) Divinylsiloxane complex of chloroplatinic acid

[Example 1]

Mix 53 parts by mass of (A), 36 parts by mass (B), 4 parts by mass (C), and 7 parts by mass (D), and add 5 ppm of (E) chloroplatinic acid based on the amount of platinum The divinylsiloxane complex compound is mixed to prepare a curable composition.

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

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

Prepared for the above examples 1 to 4 and comparative examples 1 to 5 The curable composition obtained was subjected to the test shown below.

[Viscosity of curable composition]

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

[Hardness of hardened material]

Pour the prepared curable composition in a 50mm diameter×10mm thick aluminum pan, and perform segmental curing in the order of 60°C×1 hour, 100°C×1 hour, and 150°C×4 hours to produce samples . The hardness (Shore A or Shore D) of the obtained hardened product was measured in accordance with the method described in JIS K 6253-3: 2012. The results are shown in Table 1.

[Light transmittance of hardened material]

A recessed 1mm thick Teflon (registered trademark) spacer is sandwiched between two glass slides of 50mm×20mm×1mm thickness. After fixing these, the hardenable composition is poured in, and the temperature is 60°C. The stepwise curing was performed in the order of ×1 hour, 100°C ×1 hour, and 150°C ×4 hours to prepare transmittance measurement samples. The light transmittance of the obtained sample at 450 nm was measured with a spectrophotometer U-4100 (manufactured by Hitachi High Technologies Co., Ltd.). The results are shown in Table 1.

[Tensile strength of hardened product and elongation when cut]

In a concave Teflon (registered trademark) gold with a thickness of 150mm×200mm×2mm The prepared curable composition is poured into the mold, and the test samples are made by stepwise curing in the order of 60°C×1 hour, 100°C×1 hour, and 150°C×4 hours. According to JIS K 6251:2010, using EZ TEST (EZ-L, manufactured by Shimadzu Corporation), the tensile strength of the sample is measured under the conditions of a test speed of 500 mm/min, a distance between clamps of 80 mm, and a distance between marks of 40 mm. Elongation at cutting. The results are shown in Table 1.

[Adhesiveness of hardened material]

Press the thumb on the surface of the hardened object for 1 second, and perform a sensory evaluation of the resistance when pulling it apart. The situation that felt resistance was rated as "Yes", and the situation that did not feel resistance was rated as "None". The results are shown in Table 1.

[Cutability of hardened material]

Pour the prepared curable composition into a concave Teflon (registered trademark) metal mold, and perform segmental hardening in the order of 60°C×1 hour, 100°C×1 hour, and 150°C×4 hours to produce 100mm ×100mm×2mm thick hardened material sheet. For the obtained flakes, blade cutting was performed with a blade of ZP07-SD2000-F1B333NBC-ZB1050 (DISCO Co., Ltd.) for evaluation. In the evaluation, the case where there is no dent in the cut part is rated as "good", and the case where the part is dented after cutting is rated as "bad". The results are shown in Table 1.

As shown in Table 1, an appropriate amount of the curable silicone resin composition of the cyclic vinylsiloxane of the present invention can produce a cured product with sufficient strength, good cutting properties, and non-sticking. In addition, the viscosity of the resin composition can be reduced, and an improvement in work efficiency can be expected.

In addition, the present invention is not limited to the above-mentioned embodiment. The above-mentioned embodiment is an example, and any article that has substantially the same structure and exerts the same effect as the technical idea described in the scope of the patent application of the present invention is included in the technical scope of the present invention.

Claims (4)

An addition-curing polysiloxane resin composition characterized by containing the following components (A) to (E), (A) a branched 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} independently selected from the carbon number 1-12 substituted or unsubstituted monovalent saturated hydrocarbon groups and carbon 2-6 alkenyl groups, but ^{at least two of R 1} are alkenyl groups, r is an integer from 0 to 100, and s is from 0 to 300 Integer, t is an integer from 0 to 200, u is an integer from 0 to 200, but 1≦t+u≦400, 3≦r+s+t+u≦800); (B) the following formula (2) The linear organopolysiloxane represented by (R ¹ ₃ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (2) (In formula (2), R ^{1 is} independently selected from the carbon number 1-12 substituted or unsubstituted monovalent saturated hydrocarbon groups and carbon 2-6 alkenyl groups, but ^{at least two of R 1} are alkenyl groups, and the alkenyl groups are located in the two (R ¹ ₃ SiO _1/2 ) unit, instead of x (R ¹ ₂ SiO _2/2 ) units, x is 200~700 (but not including the integer of x=200); (C) the following formula (3 Cyclic vinylsiloxane represented by ): 2-7 parts by mass relative to 100 parts by mass of the total of components (A) and (B)

(In the formula (3), the same as R ¹ (1) R in the above Formula ^1, n is an integer of 3 to 6); (D) having an alkyl group of one molecule at least two silicon organohydrogen silicon hydrogen siloxane : Relative to 1 mol of alkenyl group in components (A) to (C), the amount of hydrosilyl group in component (D) is 0.4 to 4.0 mol, and (E) hydrosilylation catalyst: hydrogen silane The amount sufficient for the chemical reaction. For example, the addition curable silicone resin composition of item 1 in the scope of patent application, 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 silicone resin composition of item 1 or 2 of the scope of patent application, wherein the aforementioned (D) component is an organohydrogen polysiloxane represented by the following formula (4) (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 with a number of 1-12, ^{at least two of R 2} are hydrogen atoms, r'is an integer from 0 to 100, s'is an integer from 0 to 300, and t'is from 0 to 200 Integer, u'is an integer from 0 to 200, but 2≦r'+s'+t'+u'≦800). For example, the addition curable silicone resin composition of item 1 or 2 of the scope of patent application, wherein the blending amount of the aforementioned (E) component is 5-20 ppm relative to the total mass of the (A) ~ (D) components .