KR102404430B1 - Crosslinkable organopolysiloxane composition, cured product thereof, and LED device - Google Patents

Abstract

Provided are a crosslinkable organopolysiloxane composition that is rapidly crosslinked by hydrosilylation reaction to form a cured product having corrosion gas resistance, a cured product thereof, and an LED device in which an LED element is sealed by the composition.
[Solutions] (A) an alkenyl-functional branched organopolysiloxane containing a biphenylyl group represented by the average unit formula, (B) an aryl group having at least three siloxane units represented by the general formula in one molecule An alkenyl-functional branched organopolysiloxane containing, (C) an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule, and (D) a cross-linkable organopolysiloxane comprising a catalyst for hydrosilylation reaction composition.

Description

Crosslinkable organopolysiloxane composition, cured product thereof, and LED device

The present invention relates to a crosslinkable organopolysiloxane composition, a cured product obtained by curing the composition, and an LED device having the cured product.

Silicone compositions are used for the purpose of protecting LED elements, electrodes, substrates, etc. in LED devices from the viewpoint of forming a cured product having excellent rubber properties such as weather resistance, heat resistance, hardness, and elongation. In particular, a high refractive index type additive silicone composition having little shrinkage during curing and good light extraction efficiency is frequently used. Further, in the LED device, silver or a silver-containing alloy having good conductivity is used as an electrode, and silver plating is sometimes applied to the substrate in order to improve the luminance. On the other hand, the silicone composition is a general name for a composition containing a compound having a chemical structure of organopolysiloxane, and is synonymous in the present technical field.

In general, a cured product made of a silicone composition has high gas permeability, and when it is used for a high-brightness LED with strong light intensity and high heat generation, discoloration of the encapsulant due to intrusion of corrosive gas or water vapor in the environment, or to an electrode or substrate There is a problem that a decrease in brightness and a decrease in adhesive strength occur due to corrosion of the plated silver.

In Patent Document 1, (A) a diorganopolysiloxane containing at least two alkenyl groups bonded to a silicon atom, (B) SiO _4/2 unit, Vi(R ² ) ₂ SiO _1/2 unit, and R ² ₃ SiO An organopolysiloxane having a resin structure consisting of _1/2 unit, (C) an organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule, and (D) an addition comprising a platinum group metal catalyst Curable silicone compositions have been proposed.

However, such an addition-curable silicone composition is very easy to permeate corrosive gas or water vapor in the environment, and the silver plated on the electrode or substrate easily corrodes, or the adhesive strength decreases and peeling occurs, thereby reducing the sealing effect.

In Patent Document 2, (A) an organopolysiloxane represented by the average unit formula, (B) a straight-chain organopolysiloxane having at least two alkenyl groups in one molecule and not having a silicon atom-bonded hydrogen atom, (C ) A curable silicone composition comprising at least an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule and (D) a catalyst for hydrosilylation reaction has been proposed.

The curable silicone composition described in Patent Document 2 has a high hydrosilylation reactivity and forms a cured product with low gas permeability, an organopolysiloxane, and a curable silicone composition that has high reactivity and forms a cured product with low gas permeability , it is said to provide a cured product with low gas permeability.

However, even if the LED substrate on which the electrode or the substrate is silver-plated is sealed with the curable silicone composition described in Patent Document 2, for example, it can be seen that the silver plating is corroded in an atmosphere of 80 ° C. in the presence of sulfur, and the LED emits light. There was a problem that the brightness of the light was lowered.

Japanese Patent Laid-Open No. 2000-198930 Japanese Patent Laid-Open No. 2014-84417

The present invention has been made in view of the above circumstances, and an object of the present invention is to maintain heat resistance and transparency and adhesion to LED substrates, and crosslinking properties in which silver plating does not corrode even in a harsh environment such as an atmosphere of 80° C. in which sulfur is present. It is to provide the LED device which has an organopolysiloxane composition, the hardened|cured material obtained by hardening|curing this composition, and this hardened|cured material.

The present invention is

(A) Average unit formula:

(R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c (SiO _4/2 ) _d (R ² O _1/2 ) _e (wherein, R ¹ is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one of these monovalent hydrocarbon groups is an alkenyl group having 2 to 6 carbon atoms, and at least one is an aryl group, at least one of these aryl groups dog is a biphenylyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a, b, c, d, and e are 0≤a≤0.1, 0.2≤b≤0.9, 0.1≤c ≤0.6, 0≤d≤0.2, 0≤e≤0.1, and a number satisfying a+b+c+d+e=1) ground organopolysiloxane,

(B) having at least two alkenyl groups and at least one aryl group in one molecule, and having at least three siloxane units represented by the following general formula (1) in one molecule (preferably having a viscosity at 25°C Alkenyl-functional branched organopolysiloxane containing an aryl group (having fluidity of 20 Pa·s or less) {Ratio of component (A) and component (B) is 1/100 to 100/1},

R ³ ₃ SiO _1/2 General formula (1)

(Wherein, R ³ represents a substituted or unsubstituted monovalent hydrocarbon group.)

(C) Organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule and 12 to 70 mol% of silicon atom-bonded organic groups are aryl groups {to the sum of alkenyl groups in component (A) and component (B) An amount such that the molar ratio of silicon atom-bonded hydrogen atoms in this component is 0.5 to 2}, and

(D) a catalyst for hydrosilylation reaction {a sufficient amount to promote a hydrosilylation reaction between the alkenyl group of component (A) and component (B) and the silicon atom-bonded hydrogen atom of component (C)}; It is a crosslinkable organopolysiloxane composition which does not contain an alkenyl-functional linear organopolysiloxane.

The cured product of the present invention is characterized in that it is formed by curing the crosslinkable organopolysiloxane composition. It is preferable that the refractive index of this hardened|cured material is 1.58 or more in 25 degreeC, It is more preferable that it is 1.59 or more, It is especially preferable that it is 1.60 or more.

The LED device of this invention is formed by sealing an LED element with the hardened|cured material of the said crosslinkable organopolysiloxane composition, It is characterized by the above-mentioned.

In the crosslinkable organopolysiloxane composition of the present invention, in order to prevent the curing reaction from proceeding during storage, the component (D) and the component (C) should be stored separately. The crosslinkable organopolysiloxane composition of the present invention can be prepared by mixing, for example, a solution containing the component (A) and the component (C), and a solution containing the component (B) and the component (D). , can be prepared.

The crosslinkable organopolysiloxane composition of the present invention is characterized in that it forms a cured product having a high refractive index and excellent corrosive gas shielding properties (sulfurization resistance) while maintaining the heat resistance and transparency and excellent adhesion of the organopolysiloxane. useful. In addition, the LED device in which the LED element is encapsulated with the cured product of the crosslinkable organopolysiloxane composition of the present invention is excellent in reliability in an atmosphere in which sulfur is present. In addition, such an LED device can expect a high light extraction effect.

The meaning of each term described in this specification is as follows.

Siloxane: A compound having a Si-O-Si bond.

Polysiloxane: A compound having a plurality of Si-O-Si bonds.

Organopolysiloxane: Polysiloxane having a structure in which an organic group is bonded to Si atoms constituting a Si-O-Si bond.

Organopolysiloxane composition: A composition formulated for specific performance comprising at least an organopolysiloxane.

The straight-chain organopolysiloxane refers to an organopolysiloxane having no structure in which the siloxane chain is connected via an atom linking group on the Si atom with respect to the main chain (-Si-O-Si-O-chain) of the polysiloxane. Also called linear component.

The branched organopolysiloxane refers to an organopolysiloxane having at least one T-type or cross-shaped branching point.

First, the crosslinkable organopolysiloxane composition of the present invention will be described in detail.

Component (A) is an important component that determines the physical properties of the crosslinked organopolysiloxane composition in combination with component (B), and the average unit formula:

(R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c (SiO _4/2 ) _d (R ² O _1/2 ) _e at least It is an alkenyl-functional branched organopolysiloxane containing an aryl group containing one biphenylyl group. The present inventors discovered that corrosion gas resistance, refractive index, and dicing property could be improved because this (A) component contained the aryl group containing at least 1 piece(s) of biphenylyl group.

In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one of these monovalent hydrocarbon groups is an alkenyl group having 2 to 6 carbon atoms, and at least one is an aryl group, this aryl group Among them, at least one is a biphenylyl group. A plurality of R ¹ may be the same as or different from each other. Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, A propyl group, a butyl group, a pentyl group, a hexyl group, etc. are illustrated, Preferably they are a methyl group and an ethyl group. In addition, examples of the aryl group having 6 to 14 carbon atoms include a biphenylyl group as an essential component, and a substituted or unsubstituted phenyl group, a naphthyl group, and an anthracenyl group are exemplified. Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. In the formula, R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and preferably a methyl group and an ethyl group. A plurality of R ² may be the same as or different from each other.

In the formula, a represents a number representing the ratio of the siloxane unit represented by the general formula: R ¹ ₃ SiO _1/2 , and is a number satisfying 0≤a≤0.1, preferably 0≤a≤0.08. This is because, when a exceeds the upper limit of the above range, fluidity becomes too high, and sufficient strength and hardness at room temperature of the resulting cured product (in this specification, cured product is synonymous with crosslinked product) cannot be obtained. b represents a number representing the ratio of the siloxane unit represented by the general formula: R ¹ ₂ SiO _2/2 , and is a number satisfying 0.2≤b≤0.9, preferably 0.3≤b≤0.7. This is because, when b is less than the lower limit of the above range, the refractive index does not become a desirable high refractive index, and when the upper limit of the above range is exceeded, sufficient hardness at room temperature of the resulting cured product cannot be obtained. In the formula, c represents a number representing the ratio of the siloxane unit represented by the general formula: R ¹ SiO _3/2 , and is a number satisfying 0.1≤c≤0.6, preferably 0.2≤c≤0.6. This is because, when c is less than the lower limit of the above range, sufficient hardness at room temperature of the obtained cured product cannot be obtained. On the other hand, when the upper limit of the above range is exceeded, the flexibility of the obtained cured product becomes insufficient. In addition, d represents a number representing the ratio of the siloxane unit represented by the general formula: SiO _4/2 , and is a number satisfying 0≤d≤0.2, preferably 0≤d≤0.1. This is because, when d exceeds the upper limit of the above range, the resulting cured product has insufficient flexibility. In addition, e represents a number representing the ratio of the terminals of the branched organosiloxane represented by the general formula: R ² O _1/2 , and is a number satisfying 0≤e≤0.1. This is because, when e exceeds the upper limit of the above range, sufficient hardness at room temperature of the obtained cured product cannot be obtained. On the other hand, in the formula, the sum of a, b, c, d and e is 1. When a, d, and e each represent 0, (A) component is represented by average unit formula: (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c .

Component (B) is an important second component that, in combination with component (A), influences the physical properties of the crosslinked organopolysiloxane composition, has at least two alkenyl groups and at least one aryl group in one molecule, and has the general formula (1) : R ³ ₃ SiO _1/2 alkenyl-functional branched organo containing at least three terminal siloxane units of polysiloxane in one molecule and containing an aryl group having fluidity with a viscosity of 20 Pa·s or less at 25°C polysiloxane. (B) It is preferable that a component has fluidity|liquidity whose viscosity is 20 Pa*s or less in 25 degreeC. In the formula, R ³ represents a substituted or unsubstituted monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, A propyl group, a butyl group, a pentyl group, a hexyl group, etc. are illustrated, Preferably they are a methyl group and an ethyl group. Examples of the aryl group having 6 to 14 carbon atoms include a substituted or unsubstituted biphenylyl group, a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. A plurality of R ³ may be the same as or different from each other. Even if it is a branched organopolysiloxane, since it has at least three terminal siloxane units in one molecule of polysiloxane represented by the general formula: R ³ ₃ SiO _1/2 , the viscosity at 25° C. is 100 Pa·s (that is, 100000 mPa·s) or less It can be set as polysiloxane which has fluidity|liquidity of In addition, by controlling the manufacturing method of component (B), the molecular weight of the alkenyl-functional branched organopolysiloxane having a three-dimensional structure can be controlled within a preferred range, and the viscosity at 25° C. has fluidity below the preferred range. It can be set as polysiloxane. Since it has this branched structure and has fluidity at 25°C, it is possible to obtain a composition having a fast curing rate and no surface tack of the cured product.

On the other hand, if the viscosity is 100 Pa·s at 25°C, it is obvious to those skilled in the art that it has fluidity at 25°C.

(B) In 25 degreeC, it is preferable that a viscosity is 50000 mPa*s or less, It is more preferable that it is 30000 mPa*s or less, It is especially preferable that it is 20000 mPa*s or less.

As the component (B), the average unit formula:

Alkenyl-functional branched phase containing an aryl group, represented by (R ⁴ ₃ SiO _1/2 ) _f (R ⁴ ₂ SiO _2/2 ) _g (R ⁴ SiO _3/2 ) _h (SiO _4/2 ) _i Organopolysiloxanes are exemplified. Here, R ⁴ is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least two of these monovalent hydrocarbon groups are an alkenyl group having 2 to 6 carbon atoms, and at least one is an aryl group. Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, ethyl group, and propyl group A group, a butyl group, a pentyl group, a hexyl group etc. are illustrated, Preferably they are a methyl group and an ethyl group. Examples of the aryl group having 6 to 14 carbon atoms include a substituted or unsubstituted biphenylyl group, a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. A plurality of R ⁴ may be the same as or different from each other. where f, g, h, i are 0<f≤0.8, 0≤g≤0.96, 0<(h+i), 0.5≤f/(h+i)≤4, f+g+h+ It is a number that satisfies i = 1. Here, f is a number defining the amount of terminal siloxane units of polysiloxane represented by the general formula: R ⁴ ₃ SiO _1/2 for obtaining fluidity of 20 Pa·s or less at 25°C, h and i are organopolysiloxane divided As a number specifying the component for taking the ground structure, both f and h+I must be a number greater than 0. In addition, in order to obtain fluidity of 20 Pa·s or less at 25°C, the ratio f/(h+i) of the amount of terminal siloxane units of the polysiloxane represented by the general formula for branching points: R ³ ₃ SiO _1/2 is 0.5 must be greater than or equal to 4, and the maximum is 4. The linear component represented by the general formula: R ⁴ ₂ SiO _2/2 is not necessarily an essential component, but may be introduced as a component in the polymer to obtain the required viscosity, and may be in the range of 0≤g≤0.96, 0≤g It is preferred that ≤0.90.

(B) component is average composition formula (R ⁴ ₃ SiO(R ⁴ ₂ SiO) _m ) _e SiR ⁴ _(4-e) (wherein R ⁴ is a monovalent hydrocarbon group having 1 to 14 carbon atoms, this 1 Among the hydrocarbon groups, at least two are alkenyl groups having 2 to 6 carbon atoms, and at least one is an aryl group, m represents an integer of 0 or more and 200 or less, and e represents 3 or 4.) , an alkenyl-functional branched organopolysiloxane containing an aryl group is also preferred. In the formula, m represents the number of linear siloxane units, and is an integer satisfying 0≤m≤200, preferably 0≤m≤100. In the formula, e represents 3 or 4, and is a number defining a structure for forming a branch point of branched organopolysiloxane, and when e is 3, it becomes a T-type branch point, and when e is 4, It becomes a cross-shaped branch point.

Moreover, as an example of (B) component, _the linear organopolysiloxane which has an aryl group ^and an alkenyl group represented by ^Formula : ^R5R62SiO ₍ ^R62SiO _{) nSiR5R62} , ^Formula : (HR ⁷ ₂ SiO) _j SiR ⁷ _(4-j) (R ⁷ represents a monovalent hydrocarbon group having 1 to 14 carbon atoms, j represents 3 or 4), containing a silicon atom-bonded hydrogen atom and an alkenyl-functional branched organopolysiloxane containing at least three alkenyl groups in one molecule of the product, which is formed by a hydrosilylation reaction of a siloxane oligomer, which contains no hydrogen atom bonded to a silicon atom, and containing an aryl group. In the formula, R ⁵ represents an alkenyl group having 2 to 6 carbon atoms, exemplified by a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group, and R ⁶ is at least one aryl group having 1 to 14 carbon atoms A monovalent hydrocarbon group is shown, and examples of the monovalent hydrocarbon group include an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 14 carbon atoms, and examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and a propyl group , a butyl group, a pentyl group, a hexyl group, etc. are illustrated, and a methyl group and an ethyl group are preferable. Examples of the aryl group having 6 to 14 carbon atoms include a substituted or unsubstituted phenyl group, a biphenylyl group, a naphthyl group, and an anthracenyl group. A plurality of R ⁵ , R ⁶ and R ⁷ may be the same as or different from each other, respectively. In the formula, n represents the number of linear siloxane units, and is an integer satisfying 0≤n≤200, preferably 0≤n≤100. This is because, when n exceeds the upper limit of the above range, the viscosity of the branched organopolysiloxane obtained exceeds 20 Pa·s at 25°C. In the formula, R ⁷ represents a monovalent hydrocarbon group having 1 to 14 carbon atoms that does not contain an alkenyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a substituted or unsubstituted biphenylyl group; Aryl groups, such as a phenyl group, a naphthyl group, and anthracenyl group, are illustrated. In the formula, j represents 3 or 4 and is a number defining a structure for forming a branching point of branched organopolysiloxane, and when j is 3, it becomes a T-type branching point, and j is 4 days When, it becomes a cross-shaped branch point.

In order to exhibit the effect of the present invention, the mixing ratio of the component (A) and the component (B) is preferably 1/100 to 100/1, preferably 1/50 to 50/1 by weight of A/B, and 1 It is more preferable that it is /20-20/1.

In the Examples, the amounts of component (A) and component (B) are described in parts by weight, and it is apparent to those skilled in the art that the mixing ratio of component (A) and component (B) in the present specification is expressed as a weight ratio.

Component (C) is a crosslinking agent of the crosslinkable organopolysiloxane composition of the present invention (hereinafter also referred to as the present composition), has at least two silicon atom-bonded hydrogen atoms in one molecule, and contains 12 to 70 silicon atom-bonded organic groups It is an organopolysiloxane whose mole % is an aryl group. (C) The silicon atom-bonded hydrogen atom in a component is at least two. This is because, when the number of silicon atom-bonded hydrogen atoms is less than two in one molecule, sufficient mechanical strength at room temperature of the resulting cured product cannot be obtained. (C) As a silicon-atom bonding organic group in a component, Cycloalkyl groups, such as alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a tolyl group, a naphthyl group , an anthracenyl group, an aryl group such as a biphenylyl group, and the like are exemplified. (C) As for component, 12-70 mol% of a silicon-atom bond organic group is an aryl group. This is because, when content of an aryl group deviates from the said range, compatibility of the mixture of (A) component and (B) component will worsen, transparency of the hardened|cured material obtained will be lost, and mechanical properties will also worsen. A silicon atom-bonded hydrogen atom is synonymous with Si-H.

As such (C)component, General formula: (HR ⁸ ₂ SiO) ₂ SiR ⁸ ₂ , (HR ⁸ ₂ SiOSiR ⁸ ₂ ) ₂ O, (HR ⁸ ₂ SiO) ₃ SiR ⁸ , ((HR ⁸ ₂ SiO) ₂ SiR ⁸ ) The compound represented by ₂ O, etc. are illustrated. In the formula, R ⁸ is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one of these monovalent hydrocarbon groups is an aryl group, and the monovalent hydrocarbon group is an alkyl group having 1 to 6 carbon atoms, carbon atoms A 6-14 aryl group etc. are illustrated, A methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group etc. are illustrated as a C1-C6 alkyl group, Preferably they are a methyl group and an ethyl group. Examples of the aryl group having 6 to 14 carbon atoms include a substituted or unsubstituted biphenylyl group, a phenyl group, a naphthyl group, and an anthracenyl group. A plurality of R ⁸ may be the same as or different from each other. On the other hand, in R< ⁸ >, content of the aryl group is the range of 12-70 mol%.

This composition WHEREIN: Content of (C)component is an amount which becomes in the range of 0.5-2 molar ratio of the silicon atom-bonded hydrogen atom in this component with respect to the sum total of the alkenyl groups in (A) component and (B) component, Preferably, it is an amount used in the range of 0.5-1.5. This is because the mechanical strength at room temperature of the hardened|cured material obtained as content of (C)component is outside the said range becomes inadequate.

(D)component is a catalyst for hydrosilylation reaction for promoting the hydrosilylation reaction of the alkenyl group of (A)component and (B)component, and the silicon-atom bond hydrogen atom in (C)component. Although a platinum-type catalyst, a rhodium-type catalyst, and a palladium-type catalyst are illustrated as (D)component, a platinum-type catalyst is preferable at the point which can accelerate|stimulate the bridge|crosslinking of this composition remarkably. In particular, in view of high catalytic activity, a platinum-alkenylsiloxane complex is preferable, and in view of good stability of the complex, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane as a ligand Platinum complexes are preferred.

In this composition, content of (D)component WHEREIN: If content of (D)component is an amount sufficient to accelerate|stimulate the hydrosilylation reaction of the alkenyl group of (A) component and (B) component, and the silicon atom-bonded hydrogen atom of (C)component, especially not limited Preferably, with respect to this composition, it is preferable that the metal atom in (D)component is an amount in the range of 0.1 ppm - 100 ppm by weight (usually synonymous with mass) unit. This is because when the content of component (D) is less than the lower limit of the above range, the resulting composition is not sufficiently crosslinked or does not crosslink at a sufficient rate. Because it could cause problems.

Although the present composition contains the components (A) to (D), as other optional components, a reaction inhibitor may be added for the purpose of arbitrarily changing the curing rate. Examples of the reaction inhibitor include alkyne alcohols such as 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol and ethynylcyclohexanol, 1,3,5,7-tetramethyl- 1,3,5,7-tetravinylcyclotetrasiloxane, benzotriazole, etc. are illustrated. The content of these reaction inhibitors is not particularly limited, but is preferably within the range of 1 ppm to 1000 ppm based on the weight of the present composition.

In addition, in the case where adhesion with the substrate is required depending on the application, the composition may contain an adhesion promoter. Examples of the adhesion promoter include a trialkoxysilyl group (eg trimethoxysilyl group or triethoxysilyl group), a hydrosilyl group, an epoxy group (eg 3-glycidoxypropyl group), and an alkenyl group (eg For example, an organosilane having a vinyl group or an allyl group) in one molecule, an organosiloxane oligomer, etc. are mentioned.

Furthermore, in this composition, as long as the object of the present invention is not impaired, as other optional components, organopolysiloxanes other than the components (A) to (C), inorganic fillers (eg, silica, glass, alumina) , zinc oxide, etc.), fine organic resin powder such as polymethacrylate resin, heat resistance agent, dye, pigment, phosphor, flame retardant imparting agent, solvent, etc. may be contained.

Although linear alkenyl functional organopolysiloxane is mentioned as organopolysiloxane other than the said (A) component - (C)component, the crosslinkable organopolysiloxane composition of this invention is an alkenyl functional linear organopolysiloxane It does not contain nopolysiloxane.

In the present invention, a crosslinkable organopolysiloxane composition having good properties can be obtained by using the component (B) even if the linear alkenyl-functional organopolysiloxane, which was conventionally regarded as an essential component, is not used.

The preferable range of the viscosity of this composition is the same as the preferable range of the viscosity of (B) component. The composition is rapidly cross-linked by heating, has no surface tack, and forms a cured product having sufficient flexibility, and preferably can form a hard cured product.

When the present composition is completely cured by heating, it can be made to a more preferable hardness depending on the use, and particularly high hardness can be obtained. The crosslinkable organopolysiloxane composition of the present invention preferably has a Type D durometer hardness of 45 or more as stipulated in JIS K 6253 when heated at 150° C. for 3 hours, and a Type D durometer hardness according to the desired use. may be 45 to 60, and the hardness of the Type D durometer may be 60 to 80 according to other desired uses. Conversely, when it is desired to obtain a rubber-like cured product, the present composition can have a type A durometer hardness of 30 to 60 specified in JIS K 6253 when fully cured by heating, and can be typed according to other desired uses. A Durometer hardness can be 60 to 90.

This composition can form a stable hardened|cured material which does not change mechanical properties, hardness, etc. by heating. As a heating temperature, it is preferable to carry out within the range of 80 degreeC - 200 degreeC. In addition, the present composition is not limited in the molding method, and can be used as an adhesive, film formation, potting agent, coating agent, and underfill agent by ordinary mixing and oven heating. In particular, since it has a high refractive index and high light transmittance, it is suitable for use as an optical lens material, a potting agent for semiconductor devices such as LEDs, a coating agent, a protective material, and the like.

Next, the hardened|cured material of this invention is demonstrated in detail.

The cured product of the present invention is characterized in that it is formed by curing the crosslinkable organopolysiloxane composition. The shape of hardened|cured material is not specifically limited, For example, it spans over many fields, such as a block form, a sheet form, and a film form. Although the hardened|cured material can also handle this alone, it is also possible to handle it in the state which coat|covered or sealed the optical semiconductor element etc.

Example

The crosslinkable organopolysiloxane composition of the present invention will be described in detail by way of Examples. In addition, a viscosity is a value in 25 degreeC. In the formula, Me, Ph, Vi, and BPP each represent a methyl group, a phenyl group, a vinyl group, and a biphenylyl group. On the other hand, the hardness of the cured product was measured with a type A and type D durometer prescribed in JIS K 6253 "Hardness test method for vulcanized rubber and thermoplastic rubber". JIS is an abbreviation for Japanese Industrial Standards. Furthermore, the refractive index of hardened|cured material was measured with the laser of wavelength 550nm using the Metricon company make, prism coupler model 2010.

[Example 1]

Average unit formula: 62 parts by weight of branched methylvinylbiphenylylphenylpolysiloxane represented by (MeViSiO _2/2 ) _0.3 (Ph ₂ SiO _2/2 ) _0.25 (BPPSiO _3/2 ) _0.25 (PhSiO _3/2 ) _0.2 ; Formula: (ViMe ₂ SiO(SiPhMeO) ₁₅ ) ₃ 17 parts by weight of branched methylvinylphenylpolysiloxane having a viscosity of 1200 mPa·s at 25° C., represented by 3 SiPh, and a tree represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂ After uniformly mixing 21 parts by weight of siloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum is mixed in an amount such that the amount of platinum is 5 ppm by weight with respect to the present composition 25 A crosslinkable organopolysiloxane composition having a viscosity at °C of 6000 mPa·s was prepared.

The composition obtained in Example 1 was cured for 3 hours when heated to 150° C., and a cured product having a Type D durometer hardness of 80 at 25° C. was obtained. There was no surface tack, and there was no change in hardness even after heating. The refractive index of the obtained cured product was 1.6024, and a high refractive index was obtained.

[Example 2]

Average unit formula: (MeViSiO _2/2 ) _0.3 (PhBPPSiO _2/2 ) _0.25 (PhSiO _3/2 ) 62 parts by weight of branched methylvinylbiphenylylphenylpolysiloxane represented by _0.45 , Formula: (ViMe ₂ SiO (SiPhMeO) ₁₅ ) After uniformly mixing 17 parts by weight of branched methylvinylphenylpolysiloxane having a viscosity of ₃ SiPh of 6000 mPa·s at 25° C. and 21 parts by weight of trisiloxane represented by Formula: (HMe ₂ SiO) ₂ SiPh ₂ , Platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is mixed in an amount such that the amount of platinum is 5 ppm by weight with respect to the present composition, and the viscosity at 25°C is 15000 mPa·s An organic polysiloxane composition was prepared.

The composition obtained in Example 2 was cured for 3 hours when heated to 150° C., and a cured product having a Type D durometer hardness of 80 at 25° C. was obtained. There was no surface tack, and there was no change in hardness even after heating. The refractive index of the obtained cured product was 1.5901, and a high refractive index was obtained.

[Comparative Example 1]

Average unit formula: (MeViSiO _2/2 ) _0.3 (Ph ₂ SiO _2/2 ) _0.25 (PhSiO _3/2 ) 62 parts by weight of branched methylvinylphenylpolysiloxane represented by _0.45 , Formula: (ViMe ₂ SiO(SiPhMeO) ₁₅ ) ₃ 17 parts by weight of branched methylvinylphenylpolysiloxane having a viscosity of 1200 mPa·s at 25° C. represented by 3 SiPh, and 21 parts by weight of trisiloxane represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂ After uniformly mixing, A 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum is mixed in an amount such that the amount of platinum is 5 ppm by weight with respect to the present composition, and the viscosity at 25°C is 8000 mPa·s. An organopolysiloxane composition was prepared.

The composition obtained in Comparative Example 1 was cured for 3 hours when heated to 150° C., and a cured product having a Type D durometer hardness of 30 at 25° C. was obtained. There was no surface tack, and there was no change in hardness even after heating. The refractive index of the obtained hardened|cured material was 1.5681.

[Comparative Example 2]

Average unit formula: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.3 (PhSiO _3/2 ) 63 parts by weight of branched methylvinylphenylpolysiloxane represented by _0.45 , Formula: ViMe ₂ SiO (PhMeSiO) ₃₈ SiMe ₂ 17 parts by weight of a linear organopolysiloxane represented by Vi (which does not have a siloxane unit represented by the general formula (1)), and 20 parts by weight of a trisiloxane represented by the formula: (HMe ₂ SiO) ₂ SiPh ₂ uniformly After mixing, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum is mixed in an amount such that the amount of platinum is 25 ppm by weight with respect to the composition, and the viscosity at 25°C is 2500 mPa·s A phosphorus crosslinkable organopolysiloxane composition was prepared.

The composition obtained in Comparative Example 2 was cured for 3 hours when heated to 150° C., and a cured product having a Type D durometer hardness of 40 at 25° C. was obtained. There was no surface tack, and there was no change in hardness even after heating. The refractive index of the obtained hardened|cured material was 1.5580.

(sulfation resistance test)

The compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were coated on an LED substrate having a silver-plated electrode and an LED element, and heated in an oven at 150° C. for 3 hours, and the cured product of the composition An LED device in which the LED element was sealed was manufactured. The produced LED device was placed in an oven at 80° C. under a sulfur atmosphere, and after 24 hours, the silver-plated electrode was observed under a microscope. A case in which discoloration was not observed in the silver-plated electrode was judged as “○”, and a case in which the silver-plated electrode changed to black was determined as “x”, and the results are shown in Table 1.

(dicing test)

On a glass substrate, the compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were applied to a film thickness of 0.5 mm, 1.0 mm, 2.0 mm and 3.0 mm, and heated in an oven at 150° C. for 3 hours After curing the composition, the entire glass substrate was cut using a dicing saw. The case where the glass substrate could be cut without cracks or the like in the cured product was judged as “○”, and the case where the glass substrate could not be cut due to cracks in the cured product was judged as “×”, The results are shown in Table 1.

[Table 1]

The crosslinkable organopolysiloxane composition of the present invention has fast crosslinking, no surface tack of the cured product, and sufficient flexibility, so it can be used as a material from which stress is relieved. It can be used as an underfill agent. In particular, when the cured product of the composition is a material having a high refractive index and a high light transmittance, it is suitable for use as a lens material for optical use, a potting agent for semiconductor devices, coating agent, protective material, and the like. In addition, since the cured product of the composition has excellent corrosion resistance, it is particularly suitable for LED devices used outdoors or in environments that are easily affected by exhaust gas.

Claims (9)

(A) Average unit formula:
(R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c (SiO _4/2 ) _d (R ² O _1/2 ) _e (wherein, R ¹ is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one of these monovalent hydrocarbon groups is an alkenyl group having 2 to 6 carbon atoms, and at least one is an aryl group, at least one of these aryl groups dog is a biphenylyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a, b, c, d, and e are 0≤a≤0.1, 0.2≤b≤0.9, 0.1≤c ≤0.6, 0≤d≤0.2, 0≤e≤0.1, and a number satisfying a+b+c+d+e=1) ground organopolysiloxane,
(B) an alkenyl-functional branched phase containing at least two alkenyl groups and at least one aryl group in one molecule, and having at least three siloxane units represented by the following general formula (1) in one molecule, and an aryl group Organopolysiloxane {The weight ratio of component (A) and component (B) is 1/100 to 100/1, and component (A) and component (B) are different from each other},
R ³ ₃ SiO _1/2 General formula (1)
(Wherein, R ³ represents a substituted or unsubstituted monovalent hydrocarbon group.)
(C) Organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule and 12 to 70 mol% of silicon atom-bonded organic groups are aryl groups {to the sum of alkenyl groups in component (A) and component (B) An amount such that the molar ratio of silicon atom-bonded hydrogen atoms in this component is 0.5 to 2}, and
(D) A crosslinkable organopolysiloxane composition comprising a catalyst for hydrosilylation reaction and not containing an alkenyl-functional linear organopolysiloxane. According to claim 1,
The component (A) is an average unit formula: (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c (wherein, R ¹ , b and c have the same meaning as in paragraph 1.) A crosslinkable organopolysiloxane composition, which is an alkenyl-functional branched organopolysiloxane containing a biphenylyl group. 3. The method of claim 1 or 2,
The component (B) is an average unit formula:
(R ⁴ ₃ SiO _1/2 ) _f (R ⁴ ₂ SiO _2/2 ) _g (R ⁴ SiO _3/2 ) _h (SiO _4/2 ) _i (wherein R ⁴ is 1 of 1 to 14 carbon atoms) a hydrocarbon group, and among these monovalent hydrocarbon groups, at least two are alkenyl groups having 2 to 6 carbon atoms, and at least one is an aryl group, and f, g, h, i are 0<f≤0.8, 0 ≤g≤0.96, 0<(h+i), 0.5≤f/(h+i)≤4, f+g+h+i=1) A crosslinkable organopolysiloxane composition which is an alkenyl-functional branched organopolysiloxane. 3. The method of claim 1 or 2,
The component (B) is a formula: R ⁵ R ⁶ ₂ SiO(R ⁶ ₂ SiO) _n SiR ⁵ R ⁶ ₂ (wherein, R ⁵ represents an alkenyl group having 2 to 6 carbon atoms, and R ⁶ is the number of carbon atoms) 1 to 14 monovalent hydrocarbon groups, at least one of these monovalent hydrocarbon groups is an aryl group, and n represents an integer of 0 or more and 200 or less.) chain organopolysiloxane,
A hydrogen atom bonded to a silicon atom represented by the formula: (HR ⁷ ₂ SiO) _j SiR ⁷ _(4-j) (R ⁷ is a monovalent hydrocarbon group having 1 to 14 carbon atoms, and j represents 3 or 4) A crosslinkable organo which is an alkenyl-functional branched organopolysiloxane containing at least three alkenyl groups in one molecule of the product, which is formed by hydrosilylation reaction of a siloxane oligomer containing an aryl group, and which has no silicon atom-bonded hydrogen atom. Polysiloxane composition. 3. The method of claim 1 or 2,
The crosslinkable organopolysiloxane composition in which the said (B) component has fluidity|liquidity whose viscosity is 20 Pa.s or less at 25 degreeC. A cured product obtained by curing the crosslinkable organopolysiloxane composition according to claim 1 or 2. 7. The method of claim 6,
Hardened|cured material whose refractive index is 1.58 or more in 25 degreeC. The LED device by which the LED element was sealed by the hardened|cured material of Claim 6. A method for preparing the crosslinkable organopolysiloxane composition according to claim 1 or 2, comprising: a solution containing the component (A) and the component (C); and the component (B) and the component (D). A method for preparing the crosslinkable organopolysiloxane composition according to claim 1 or 2, comprising mixing a solution comprising: