JP2011114147A - Optical device having sealing layer made of hardened curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical device that has a stress relaxation mechanism not depending on glass transition within an operating temperature range in order to support the long-term reliability of the optical device and also has a sealing layer featuring excellent heat resistance and light resistance. <P>SOLUTION: The present invention is based on the fact that the sealing layer having specific viscoelasticity behavior has an excellent property in thermal shock resistance. It is also characterized in that a hardened material made of specific organosiloxane composition is preferable for the sealing agent. The optical device of this invention has a structure where the sealing layer has one or more maximum loss tangent values measured at a frequency of 10 Hz in the temperature range of -40 to 100°C and the maximum value in the range of 0.01 to 0.5. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a sealing layer that realizes long-term use reliability of an optical device, and an optical device having these.

Many optical devices such as a light emitting diode (LED), a solar cell, and a light receiving element for an optical disk have a light emitting portion or a light receiving portion and one or more sealing layers for protecting them. The sealing layer is strictly required to have adhesiveness, light resistance, heat resistance, and thermal shock resistance in order to protect the optical element from the external environment and ensure long-term reliability of the optical device (for example, Patent Document 1). . Further, as the output of a device represented by a white LED is increased, the sealing material is required to have higher adhesiveness, light resistance, heat resistance, and thermal shock resistance.
On the other hand, as a sealing layer currently used as a sealing layer of an optical device, for example, in an optical semiconductor application such as an LED, an epoxy resin, a silicone resin, or the like has been used depending on a use environment, a purpose, and the like. (For example, Patent Document 2). However, when an epoxy resin is used, although the adhesiveness is excellent, there is a problem that light resistance and heat resistance are insufficient due to the presence of an organic component in the resin skeleton, resulting in yellowing. In addition, in the case of silicone resin, the resin skeleton does not contain organic components, so it has excellent light resistance and heat resistance, but it adheres to dust when used as a soft material, and adheres as well as thermal shock when used as a hard material. There are problems such as inadequate performance.
On the other hand, as a method for improving the characteristics of a resin, studies have been made focusing on a loss tangent (tan δ) in a specific temperature range for a thermoplastic resin (for example, Patent Document 3 and Non-Patent Document 1). There is no suggestion of improving the properties of a sealing material made of a curable composition used for the above.
In view of the above, in order to support the long-term reliability of optical devices that have been remarkably developed in recent years, it has been required to develop a sealing material excellent in heat resistance, light resistance, and thermal shock resistance, and an optical device using the same.

JP 2004-359933 A JP 2008-179811 A JP 2001-234083 A

New Energy and Industrial Technology Development Organization Result Report “2007 New Energy Technology Research and Development Solar Power System Future Technology Research and Development Research and Development of Highly Durable Dye-Sensitized Solar Cells Excellent in Cost Effectiveness” 4th page.

  The present invention has been made in view of the above situation, and relates to an optical device having a sealing layer excellent in thermal shock resistance. This optical device realizes the required long-term reliability.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that a sealing layer having a specific viscoelastic behavior exhibits excellent characteristics in thermal shock resistance, and completes the present invention. It came.

  1) A curable composition is cured, and there is at least one maximum value of loss tangent measured at a frequency of 10 Hz within a temperature range of −40 ° C. to 100 ° C., and the maximum value is 0.01 to 0.5. An optical device having a sealing layer in the range.

2) The optical device according to 1), wherein the temperature dependence ratio of the storage elastic modulus of the sealing layer represented by the following formula (1) is 50 or less.
Temperature dependence ratio of storage elastic modulus = E ′ (− 20) / E ′ (100) (1)
(E ′ (100) represents the storage elastic modulus at 100 ° C., and E ′ (−20) represents the storage elastic modulus at −20 ° C.)

  3) The optical device according to any one of 1) to 2), wherein a content of silicon atoms in the cured product which is the sealing material layer is 10 to 60% by weight.

  4) The optical device according to any one of 1) to 3), wherein the sealing layer contains silicone-based particles (A).

  5) Core-alkoxysilane condensate shell structure in which the silicone-based particles (A) are coated with a shell component (A-2) obtained by condensing the silicone-based particles (A-1) by adding alkoxysilane. 4. The optical device according to 4), wherein the optical device is a silicone-based particle.

  6) The shell component of the silicone-based particles (A) is a first shell component (A-2) obtained by adding and condensing alkoxysilane, and then the second shell obtained by adding and condensing alkoxysilane. 5. The optical device according to 5), which is a silicone-based particle having a shell structure of a silicone-based particle core-alkoxysilane condensate composed of a shell component (A-3).

7) The second shell layer comprising the alkoxysilane condensate which is the component (A-3) has the following component (a) as an essential component, and includes the following component (b), component (c) and component (d) below. 6. The optical device according to 6), wherein at least one kind is condensed.
(A) Component: General formula (2)

(Wherein R ¹² represents an alkyl group, and R ¹³ , R ^14, and R ¹⁵ represent the same or different monovalent organic groups) and / or a partial condensation thereof. object.
(B) Component: General formula (3)

(Wherein R ²² and R ²³ represent the same or different monovalent alkyl groups, and R ²⁴ and R ²⁵ represent the same or different monovalent organic groups) and / Or a partial condensate thereof.
(C) Component: General formula (4)

(Wherein R ³² , R ³³ , and R ³⁴ represent the same or different monovalent alkyl groups, and R ³⁵ represents a monovalent organic group) and / or The partial condensate.
(D) Component: General formula (5)

(Wherein R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ represent the same or different monovalent alkyl groups) and / or a partial condensate thereof.

8) The first shell layer comprising the alkoxysilane condensate as the component (A-2) is formed by condensing at least one of the following component (b), the following component (c) and the following component (d). The optical device according to 6) or 7), characterized in that
(B) Component: General formula (3)

(Wherein R ²² and R ²³ represent the same or different monovalent alkyl groups, and R ²⁴ and R ²⁵ represent the same or different monovalent organic groups) and / Or a partial condensate thereof.
(C) Component: General formula (4)

(Wherein R ³² , R ³³ , and R ³⁴ represent the same or different monovalent alkyl groups, and R ³⁵ represents a monovalent organic group) and / or The partial condensate.
(D) Component: General formula (5)

(Wherein R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ represent the same or different monovalent alkyl groups) and / or a partial condensate thereof.

  9) The first shell layer made of the alkoxysilane condensate as the component (A-2) is 1 to 40% by weight with respect to 40 to 98% by weight of the silicone-based particles as the component (A-1). 3) A polymer coated with 1 to 30% by weight of a second shell layer comprising an alkoxysilane condensate as a component (however, (A-1) component, (A-2) component and (A-3) component are: The optical device according to any one of 6) to 8), which is 100% by weight in total.

  10) The optical device according to any one of 1) to 9), wherein the sealing layer contains a silicone resin.

  11) The optical material according to any one of 1) to 10), wherein the sealing layer is obtained by curing a curable composition containing an organopolysiloxane (B) having at least two alkenyl groups. device.

  12) The sealing layer is obtained by curing a curable composition containing an organopolysiloxane (C) having at least two hydrosilyl groups. 1) to 11) Optical devices.

13) The component (B) is represented by the general formula (6)
SiO _4/2 (6)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (7) and (8).
R ^a1 R ^a2 ₂ SiO _1/2 (7)
R ^a2 ₃ SiO _1/2 (8)
(Wherein R ^a1 is an alkenyl group, and R ^a2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
At least 2 alkenyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by formula (II) and having a structure in which at least two ends of the main structure are blocked with the general formula (7) The optical device according to 11), which is an organopolysiloxane composition.

14) The component (C) is represented by the general formula (6)
SiO _4/2 (6)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (9) and (10).
R ^b1 R ^b2 ₂ SiO _1/2 (9)
R ^b2 ₃ SiO _1/2 (10)
(Wherein R ^b1 is a hydrogen atom, and R ^b2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
And having at least 2 hydrosilyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by formula (II) and having a structure in which at least two ends of the main structure are blocked with the general formula (9) The optical device according to 12), which is an organohydrogenpolysiloxane.

  The present invention having a sealing layer having at least one maximum value of tan δ in a specific temperature range and having a maximum value in a specific value range provides an optical device having excellent thermal shock resistance.

  Hereinafter, the present invention will be described in detail.

<Sealing layer>
The sealing layer in the present invention exhibits a specific viscoelastic behavior, and is preferably a sealing material obtained by curing a curable composition.
The sealing layer in the present invention preferably has an aryl group content of 3 mol% or less, more preferably 1 mol% or less, and particularly preferably 0 mol%. The smaller the aryl group content, the better the heat resistance and light resistance, and the less the coloration or the like occurs.

<Dynamic mechanical properties of sealing layer>
In general, when a sinusoidal vibration stress (strain) having an angular frequency ω is applied, the complex elastic modulus in the strain and the stress is expressed by E * = E ′ + iE ″, where E ′ is the storage elastic modulus and E ″ is the loss elasticity. Rate. When the phase difference between stress and strain is δ, the loss tangent (tan δ) is expressed by E ″ / E ′.

  The sealing layer in the present invention has at least one maximum value of tan δ at −40 ° C. to 100 ° C., which is a general use environment temperature range of the optical device, and the maximum value is 0.01 to 0.5. It is the sealing layer which is in the range. The maximum value of tan δ is more preferably in the range of 0.01 to 0.4, and still more preferably in the range of 0.01 to 0.03. If it is less than 0.01, the stress dissipating ability of the sealing layer may not be sufficient, and if it exceeds 0.5, the temperature dependence of various properties such as elastic modulus may increase.

  In the sealing layer of the present invention, the temperature dependency ratio of the storage elastic modulus is preferably 50 or less, more preferably 40 or less, and further preferably 30 or less.

  The temperature dependence ratio of the storage elastic modulus in the present invention is calculated by the following formula (1).

Temperature dependence ratio of storage elastic modulus = E ′ (− 20) / E ′ (100) (1)
Here, E ′ (100) and E ′ (−20) are storage elastic moduli at 100 ° C. and −20 ° C., respectively.

  When the temperature dependence of the storage elastic modulus is within the above range, a favorable optical device can be obtained without any phenomenon such as softening of the sealing layer and lowering of heat resistance of the sealing layer that may occur in the manufacturing process of the optical device. . In addition, when the temperature dependency is within the above range, in an optical device using a sealing layer in which an additive such as spherical silica is dispersed, the additive is well dispersed and maintains desired optical characteristics. be able to.

  The sealing layer used in the present invention is a heat-resistant sealing material having a stress relaxation mechanism that does not depend on glass transition in the operating temperature range, and realizes an optical device having excellent heat resistance using the sealing material. .

<(A) Silicone particles>
The sealing layer having a specific viscoelastic behavior in the present invention preferably contains silicone-based particles (A). Silicone-based particles (A) are preferable in that they contribute to effective expression of the viscoelastic behavior of the sealing layer of the present invention and increase the stress relaxation ability of the sealing layer.
The structure of the silicone-based particle (A) is not particularly limited as long as it is a particle having a siloxane bond. Further, the shape thereof is not particularly limited. For example, in the case of a spherical shape, the volume average particle size is preferably 0.005 μm to 3.0 μm, more preferably 0.01 μm to 2.0 μm, and 0.05 μm to 0.5 μm. Is particularly preferred. When the volume average particle size is small, the viscosity of the composition containing the silicone-based particles (A) may increase, and when the volume average particle size is large, the transparency of the cured product may be deteriorated. The volume average particle size can be measured using, for example, a nanotrack particle size analyzer UPA150 (manufactured by Nikkiso Co., Ltd.).

  In addition, in order to control the dispersibility of the component (A) in the sealing layer, it is possible to introduce an organic group on the surface or inside of the silicone particles. Means such as inclusion using force. Examples of the organic group to be introduced include vinyl group, acrylic group, carboxyl group, ester group, ether group, thiol group, mercapto group, cyano group, and aryl group.

  The component (A) preferably has a core-shell structure, and the shell portion in the core-shell structure is more preferably formed from two or more layers. The core-shell structure in the present invention can be obtained, for example, by reacting a monomer component different from the monomer component forming the core in the presence of the core particles. It is possible to form a core-shell structure while absorbing the shell component into the core particles, or to form an inclined structure from the core portion to the shell portion, but a structure in which the shell structure is formed outside the core particles Particles having are preferred.

  Silicone particles (A) are silicones having a core-alkoxysilane condensate shell structure in which silicone particles (A-1) are coated with a shell component (A-2) obtained by condensation by adding alkoxysilane. System particles are preferred. The shell component of the silicone-based particles (A) is a first shell component (A-2) obtained by adding and condensing an alkoxysilane, and then a second shell obtained by adding and condensing an alkoxysilane condensate. It is more preferable that the silicone particles have a silicone particle core-alkoxysilane condensate shell structure composed of the component (A-3).

  By having a core-shell structure of (A-1) component-based silicone particles, (A-2) component first shell component, and (A-3) component second shell component, (A) Silanol groups on the surface of the component can be reduced. Thereby, for example, the affinity and compatibility with the matrix can be improved, and the viscosity of the composition when blended in the curable composition for obtaining the sealing layer of the present invention becomes too high. Can be prevented. Furthermore, it is possible to prevent changes in the composition over time, particularly an increase in viscosity.

  The sealing layer obtained by curing the curable composition containing the component (A) is preferable from the viewpoint of improving various characteristics such as thermal shock resistance of an optical device.

  In the silicone particles (A), the first shell layer made of the alkoxysilane condensate (A-2) is 1 to 40% with respect to 40 to 98% by weight of the silicone particles (A-1). % By weight of a polymer coated with 1 to 30% by weight of a second shell layer made of an alkoxysilane condensate as component (A-3) (however, (A-1) component, (A-2) component and (A -3) 100% by weight in total of the components).

  Furthermore, the first shell layer made of the alkoxysilane condensate as the component (A-2) is 2 to 37% by weight with respect to 35 to 96% by weight of the silicone particles as the component (A-1). 3) More preferably, the second shell layer made of an alkoxysilane condensate as a component is a polymer coated by 2 to 28% by weight.

  (A-1) When there are few components, since the softness | flexibility of particle | grains will be impaired, when the characteristics of the optical device which uses the hardened | cured material obtained from the curable composition which mix | blended (A) component as a sealing layer fall There is. When there are few (A-2) components, the (A) component cannot maintain the original particle shape and the (A) component flows out into the matrix, and the sealing layer obtained by curing the curable composition It may cause deterioration of physical properties such as lowering strength.

  Moreover, when there are few (A-3) components, the silanol group on the surface of (A) component cannot fully be reduced, for example, compatibility with (A) component and a matrix becomes inadequate, (A) The viscosity of the composition containing the component may increase, the viscosity may increase over time, or the strength of the sealing layer obtained from the curable composition containing the component (A) may decrease.

The component (A-1) may be silicone-based particles, but the general formula (11)
R ^a _m SiO _{(4-m) / 2} (11)
(Wherein, R ^a is a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or different, and m represents an integer of 0 to 3). It is preferable to consist of organosiloxane having

  In the component (A-1), the structural unit of m = 2 in the general formula (11) preferably accounts for 70 mol% or more of the component (A-1), more preferably 80 mol% or more. Preferably. When the amount of this component is small, the flexibility of the component (A-1) is impaired, and thus various characteristics of the optical device having a sealing layer formed by curing the curable composition containing the component (A) may be deteriorated. There is a case.

  Although the component (A-1) can be obtained by polymerization of organosiloxane, the organosiloxane may be any of linear, branched and cyclic structures, but from the viewpoint of availability and cost, It is preferable to use an organosiloxane having a cyclic structure.

  Specific examples of the organosiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and trimethyltriphenylcyclotrisiloxane. In addition to cyclic compounds such as these, linear or branched organosiloxanes can be mentioned. These organosiloxanes can be used alone or in combination of two or more.

  Examples of the substituted or unsubstituted monovalent hydrocarbon group possessed by the organosiloxane include a methyl group, an ethyl group, a propyl group, a phenyl group, and a substituted hydrocarbon group obtained by substituting them with a cyano group. it can.

  Moreover, it is preferable that the terminal of the molecule | numerator of (A-1) component is a silanol group. By having a silanol group at the end of the molecule, a bond is formed by a condensation reaction with the later-described component (A-2), so that silicone particles having a stable core-shell structure are obtained. Can do.

  (A-1) Although there is no limitation in the manufacturing method of a component, it can be obtained also by normal emulsion polymerization, dispersion polymerization, solution polymerization, etc., and the point which can control distribution of a particle size, In view of the convenience of operation and the like, it is preferable to obtain by emulsion polymerization.

  The component (A-1) preferably uses seed polymerization from the viewpoint of obtaining particles having a smaller particle diameter and further reducing the particle diameter in the latex state. The seed polymer used for seed polymerization is not particularly limited, but rubber components such as butyl acrylate rubber, butadiene rubber, butadiene-styrene and butadiene-acrylonitrile rubber, butyl acrylate-styrene copolymer, styrene-acrylonitrile copolymer, etc. A polymer can be used.

  The component (A-1) can be produced, for example, by a normal emulsion polymerization method performed under acidic or basic conditions, but the reaction under acidic conditions is more than the reaction under basic conditions. This is advantageous because the condensation reaction of alkoxysilane proceeds rapidly. For example, various raw materials containing the above organosiloxane are made into an emulsion using a homomixer, a colloid mill, a homogenizer and the like together with an emulsifier and water, and then the pH of the system is adjusted to 5 or less, preferably 4 or less with an acid component, Polymerize by heating. As the acid component used in this case, it is preferable that the emulsion polymerization can proceed stably and also has an emulsifying ability itself, and examples thereof include alkylbenzenesulfonic acid, alkylsulfuric acid, alkylsulfosuccinic acid and the like. .

  After adding all of the raw materials at once, the pH may be adjusted to an arbitrary value after stirring for a certain period of time, or the remaining raw materials in an emulsion in which a part of the raw materials are charged and the pH is adjusted to an arbitrary value May be added sequentially. In the case of sequential addition, it may be added as it is or mixed with water and an emulsifier to form an emulsified liquid, but since the polymerization rate can be increased, a method of adding in an emulsified state is used. It is preferable. The reaction temperature and time are preferably from 0 to 100 ° C, more preferably from 50 to 95 ° C, because of easy reaction control. The reaction time is preferably 1 to 100 hours, more preferably 3 to 50 hours.

  When polymerization is performed under acidic conditions, the Si—O—Si bond forming the skeleton of the component (A-1) is usually in an equilibrium state between cleavage and bond formation. This equilibrium changes depending on the temperature, and the higher the temperature, the easier it is to produce the high molecular weight component (A-1). Therefore, in order to obtain a high molecular weight component (A-1), it is preferable to perform aging by polymerization after heating and then cooling to a polymerization temperature or lower.

  Specifically, the polymerization is carried out at 50 ° C. or higher, and the heating is stopped when the polymerization conversion rate reaches 75 to 90%, more preferably 82 to 89%, and the temperature is lower than the polymerization temperature, for example, 10 to 50 ° C., preferably Can be cooled to 20 to 45 ° C. and aged for about 5 to 100 hours. In addition, the polymerization conversion rate said here means the conversion rate to the (A-1) component of the organosiloxane of the low volatile content in a raw material.

  The amount of water used for the emulsion polymerization is not particularly limited, and may be any amount necessary to emulsify and disperse various raw materials. For example, a weight of 1 to 20 times the total amount of normal raw materials is used. It ’s fine.

  As the emulsifier used for the emulsion polymerization, any known emulsifier can be used without particular limitation as long as it does not lose the emulsifying ability in the pH range where the reaction is carried out. Examples of such emulsifiers include, for example, alkylbenzene sulfonic acid, sodium alkylbenzene sulfonate, sodium alkyl sulfate, sodium alkyl sulfosuccinate, sodium polyoxyethylene nonylphenyl ether sulfonate, and the like. Moreover, there is no limitation in particular in the usage-amount of this emulsifier, What is necessary is just to adjust suitably according to the particle diameter of the target (A-1) component.

  The use amount of the emulsifier is such that sufficient emulsification ability is obtained, and the physical properties of the obtained (A-1) component and the silicone particles that are the (A) component obtained therefrom are not adversely affected. If it dares to illustrate, it is preferable to use 0.005 to 20 weight% with respect to latex, and it is preferable to use 0.05 to 15 weight% especially.

  The volume average particle size of the latex-type silicone particles of the component (A-1) is preferably 0.005 μm to 3.0 μm, more preferably 0.01 μm to 2.0 μm, and particularly preferably 0.05 μm to 0.5 μm. preferable. If the volume average particle size is small, it is difficult to obtain stably, and if it is large, the transparency of the cured product may deteriorate. In addition, the measurement of a volume average particle diameter can be performed using nano track particle size analyzer UPA150 (made by Nikkiso Co., Ltd.), for example.

  When the component (A-1) used in the present invention is synthesized, what is called a cross-linking agent or a graft crossing agent can be used if necessary.

  Examples of the crosslinking agent that can be used for the synthesis of the component (A-1) of the present invention include three functional groups that can participate in the condensation reaction such as trimethoxymethylsilane, phenyltrimethoxysilane, and ethyltriethoxysilane. So-called trifunctional crosslinking agent, tetraethoxysilane, 1,3-bis [2- (dimethoxymethylsilyl) ethyl] benzene, 1,4-bis [2- (dimethoxymethylsilyl) ethyl] benzene, 1,3-bis [ 1- (dimethoxymethylsilyl) ethyl] benzene, 1,4-bis [1- (dimethoxymethylsilyl) ethyl] benzene, 1- [1- (dimethoxymethylsilyl) ethyl] -3- [2- (dimethoxymethylsilyl) ) Ethyl] benzene, 1- [1- (dimethoxymethylsilyl) ethyl] -4- [2-dimethoxymethylsilyl] Le] so-called four-functional crosslinking agent 4 containing a functional group capable of participating in condensation reactions such as benzene, more can be mentioned partial condensate obtained by condensation of alkoxy groups of these crosslinking agents.

  These crosslinking agents can be used alone or in combination of two or more as required. The amount of the crosslinking agent used is preferably 0.1 to 10% by weight of the component (A-1). When the use of the crosslinking agent is large, the flexibility of the component (A-1) is impaired, and therefore, when the component (A) is blended with the matrix, the low temperature thermal shock resistance of the organopolysiloxane composition is lowered. There is a case. Moreover, the elasticity of (A-1) component can be arbitrarily adjusted by changing the crosslinking degree by adjusting the usage-amount of a crosslinking agent.

  Examples of the grafting agent that can be used in the present invention include p-vinylphenylmethyldimethoxysilane, p-vinylphenylethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, and 3- (p-vinylbenzoate). Iloxy) propylmethyldimethoxysilane, vinylmethyldimethoxysilane, tetravinyltetramethylcyclosiloxane, allylmethyldimethoxysilane, mercaptopropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane and the like.

  By using the first shell component (A-2) in the present invention, it is possible to maintain the morphology of the component (A) as particles. For example, it is possible to suppress a decrease in luminous intensity of an optical device that is a sealing layer obtained from an organopolysiloxane composition.

The alkoxysilane used for the component (A-2) of the present invention is a bifunctional alkoxysilane compound (b) represented by the following general formula (3), represented by the general formula (4) (c) ) Component trifunctional alkoxysilane compounds, tetrafunctional alkoxysilane compounds represented by general formula (5), and partial condensates thereof (partial condensates obtained by condensing alkoxy groups) can be used. (A-2) component is obtained by hydrolyzing and condensing these. These alkoxysilanes can be used alone or in combination of two or more.
(B) Component: General formula (3)

(Wherein R ²² and R ²³ represent the same or different monovalent alkyl groups, and R ²⁴ and R ²⁵ represent the same or different monovalent organic groups) and / Or a partial condensate thereof.
(C) Component: General formula (4)

(Wherein R ³² , R ³³ , and R ³⁴ represent the same or different monovalent alkyl groups, and R ³⁵ represents a monovalent organic group) and / or The partial condensate.
(D) Component: General formula (5)

(Wherein R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ represent the same or different monovalent alkyl groups) and / or a partial condensate thereof.

Examples of the alkoxy group mentioned in the general formulas (3) to (5) include methoxy, ethoxy, normal propoxy, isopropoxy, normal butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyloxy, hexyloxy and the like. These are alkoxy groups having 1 to 6 carbon atoms.
Examples of the organic group include hydrocarbon groups such as alkyl groups, alkenyl groups, allyl groups, and aralkyl groups.

  As a polymerization method for obtaining the component (A-2) using an alkoxysilane compound, emulsion polymerization can be used. Although general conditions can be applied for the emulsion polymerization, it is particularly preferable to pay attention to the polymerization temperature. It is preferable to apply 20-85 degreeC as the temperature in superposition | polymerization. Moreover, 1 to 50 hours of polymerization time can be applied.

  The component (A-2) can be produced by an ordinary emulsion polymerization method performed under acidic or basic conditions. However, the reaction under acidic conditions is more preferable than the reaction under basic conditions. This is advantageous for the reason that gelation is easily suppressed during the condensation reaction of alkoxysilane.

  With the alkoxysilane condensate (A-3) used in the present invention, many silanol groups present on the surfaces of the components (A-1) and (A-2) can be reduced. As a result, various problems derived from the silanol groups on the particle surface, such as the problem of lowering the compatibility and affinity between the component (A) and the matrix, for example, the viscosity of the compound when blended with silicone rubber or silicone resin Can be solved, and the problem that the viscosity of the compound gradually increases as the composition changes with time.

  Also, when blending such particles containing a large number of silanol groups, for example, the cured product may absorb moisture, and cracks may occur in the sealing layer during the cold test. Can also be solved.

As the component (A-3) of the present invention, a condensate of alkoxysilane is used. As the alkoxysilane, a monofunctional alkoxysilane compound (a) component represented by the following general formula (2) and a partial condensate thereof (partial condensate obtained by condensing an alkoxy group) are essential components. It is preferable. These can be used alone or in combination of two or more.
(A) Component: General formula (2)

(In General Formula (2), R ¹² represents an alkyl group, and R ¹³ , R ¹⁴ , and R ¹⁵ represent the same or different monovalent organic groups.)

  Examples of the alkoxy group mentioned in the general formula (3) include methoxy, ethoxy, normal propoxy, isopropoxy, normal butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyloxy, hexyloxy and the like. 1 to 6 alkoxy groups.

Examples of the organic group include hydrocarbon groups such as alkyl groups, alkenyl groups, allyl groups, and aralkyl groups.
Furthermore, the component (A-3) is preferably formed by condensing at least one of the component (b), the component (c) and the component (d). By combining the component (a) with at least one of the component (b), the component (c) and the component (d), the component (a) can be efficiently incorporated into the component (A). Become.

  In addition, when a component containing an alkenyl group is used in any of (a) to (d), the alkenyl group can be introduced into the component (A). When the alkenyl group is introduced into the component (A), the component (A) is mixed with the matrix component composed of the component (B) and the component (C) that are cured by the hydrosilylation reaction. In order to form a bond between them, the strength of the sealing layer obtained by curing the curable composition of the present invention can be improved, which is preferable.

  As a polymerization method for obtaining the component (A-3) using an alkoxysilane compound, emulsion polymerization can be used. Although general conditions can be applied for the emulsion polymerization, it is particularly preferable to pay attention to the polymerization temperature. It is preferable to apply 20-85 degreeC as the temperature in superposition | polymerization. Moreover, 1 to 50 hours of polymerization time can be applied.

  The component (A-3) can be produced by a usual emulsion polymerization method carried out under acidic or basic conditions, but the reaction under acidic conditions is more effective than the reaction under basic conditions. This is advantageous for the reason that gelation is easily suppressed during the condensation reaction of alkoxysilane.

  There is no particular limitation on the method for separating particles from the latex of the silicone particles that are the component (A) obtained by emulsion polymerization. For example, a metal salt such as calcium chloride, magnesium chloride, or magnesium sulfate is added to the latex. Examples of the method include coagulation, separation, washing with water, dehydration, and drying of the latex. A spray drying method can also be used.

  As a method for separating the particles from the latex, it is preferable to use a masterbatch method because the component (A) can be uniformly dispersed in the matrix resin and a transparent cured product can be obtained.

  Masterbatch methods include water-soluble or partially soluble organic solvents such as alcohols (methanol, ethanol, 2-propanol, etc.), ketones (methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), acetic acid. By adding esters (ethyl acetate, butyl acetate, methyl acetate), etc., the particles can be slowly aggregated, and then the aggregate can be recovered by centrifugal sedimentation or filtration. An example is a method of redispersing in a suitable solvent, mixing with a matrix resin, and distilling off the solvent.

  The obtained component (A) can be surface-treated within a range not impeding the characteristics of the present invention. By performing the surface treatment, the affinity between the component (A) and the matrix component can be improved.

  As the surface treating agent used at this time, for example, a silylating agent can be used. Examples of the silylating agent used here generally include alkylsilanes such as trimethylchlorosilane, dimethyldichlorosilane, and hexamethyl (di) silazane. These silylating agents can be used alone or in combination of two or more.

  In addition, during the surface treatment, by introducing a functional group having binding ability with the matrix component, such as an alkenyl group, an alkynyl group, an epoxy group, an amino group, a carboxyl group, etc. to the surface of the component (A), the component (A) A bond is formed between the matrix component and the strength of the entire curable composition.

  Examples of the silylating agent used when introducing a functional group having a binding ability with the matrix component onto the polymer surface include alkenylsilanes such as chlorodimethylvinylsilane, dichloromethylvinylsilane, dichlorodivinylsilane, and trichlorovinylsilane. . These silylating agents can be used alone or in combination of two or more.

<Silicon content>
The sealing layer in the present invention preferably has a silicon content of 10 to 60% by weight, more preferably 20 to 50% by weight, and even more preferably 30 to 40% by weight. The silicon content is the content (% by weight) of silicon atoms per unit weight of the sealing layer, and can be analyzed by a generally known method.

<Curable composition>
The structure of the curable resin used in the present invention is not particularly limited, and examples thereof include an epoxy resin, a phenol resin, a melamine resin, a urea resin, an alkyd resin, a polyurethane resin, a thermosetting polyimide, and a silicone resin. In particular, when the silicone-based particles (A) are added, an epoxy resin or a silicone resin is preferable from the viewpoint of compatibility with the silicone particles (A), and an addition-type silicone resin is more preferable.

  From the viewpoint of obtaining a sealing layer having excellent weather resistance and heat resistance, an addition-type silicone resin is more preferable.

  In the present invention, when an organosiloxane composition is used as the curable resin, the structure is not particularly limited, but any structure having a siloxane bond and having an organic group or a hydrogen atom bonded to a silicon atom may be used. ) Silicone-based particles, (B) an organopolysiloxane composition having at least two alkenyl groups in one molecule, (C) an organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule, and (D) hydrosilylation. The curable composition containing a catalyst is mentioned.

  (A) component, (B) component, and the compounding quantity of (C) component are 50-1 weight of (A) component with respect to a total of 100 weight part of (A) component, (B) component, and (C) component. Parts, (B) component 98 to 1 part by weight, (C) component 98 to 1 part by weight, and preferably. (A) 40 to 3 parts by weight, (B) 94 to 3 parts by weight, (C) 94 to 3 parts by weight with respect to 100 parts by weight of component (A), (B) and (C) More preferably, it is 45 to 3 parts by weight of component (A) and component (A).

  When there are many compounding quantities of (A) component, it may thicken at the time of mixing | blending or the transparency of hardened | cured material may fall. If the amount is too small, the thermal shock resistance may be insufficient. If the amount of the component (B) is large, a cured product with sufficient hardness may not be obtained or the cured product may be colored. If the amount is too small, a cured product having sufficient hardness may not be obtained. When the blending amount of component (C) is large, a cured product with sufficient hardness may not be obtained, or foaming may occur during the curing and bubbles may remain in the cured product. If the amount is too small, a cured product having sufficient hardness may not be obtained.

About the usage-amount of (D) component, it is preferable to use in the range of 10 ^{< -1} > ^-10-10 mol as a platinum atom with respect to 1 mol of alkenyl groups of (B) component, 10 ^<-4 > ^-10 <^-8> mol. It is more preferable to use within a range. If the platinum catalyst is too much, light having a short wavelength is absorbed, and thus the light resistance of the obtained cured product may be lowered. If it is too little, the matrix may not be cured.

  The viscosity of the organopolysiloxane composition may gradually increase from the viscosity immediately after compounding, but this increase is preferably small from the viewpoint of ease of handling and quality stability. The range of increase in the viscosity is preferably within 20%, more preferably within 10% of the value after standing for 24 hours at 25 ° C. compared to the value immediately after blending.

<(B) Organopolysiloxane composition having at least two alkenyl groups in one molecule>
The component (B) in the present invention is an organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule, which is a component (C) described later, and is cured by a hydrosilylation reaction to form a silicone matrix. is there. Therefore, any organopolysiloxane containing two or more alkenyl groups in one molecule is not particularly limited, and widely known ones can be used. The structure may be any of linear, branched, cyclic and three-dimensional cross-linked structures.

  Examples of the linear component (B) include polysiloxanes whose ends are blocked with dimethylvinylsilyl groups, copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units.

  Examples of the cyclic component (B) include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1 3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, and the like.

Further, examples of the component (B) having a three-dimensional crosslinked structure are not particularly limited, but the general formula (6)
SiO _4/2 (6)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (7) and (8).
R ^a1 R ^a2 ₂ SiO _1/2 (7)
R ^a2 ₃ SiO _1/2 (8)
(Wherein R ^a1 is an alkenyl group, and R ^a2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
And a structure having a structure in which at least two terminals of the main structure are blocked by the general formula (7).
The cured product obtained from the organopolysiloxane composition containing the component (A) represented by the general formula (6), the general formula (7), and the general formula (8) has a high cross-linking density, and thus has high hardness. This is preferable because a high-strength cured product is obtained.

  The alkenyl group is preferably a vinyl group, an allyl group, a butenyl group, or a hexenyl group, and more preferably a vinyl group from the viewpoints of availability, heat resistance, and light resistance.

  Examples of substituted or unsubstituted monovalent hydrocarbon groups other than alkenyl groups include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, phenyl groups, and tolyl groups. The same or different aryl groups or the same or different selected from chloromethyl group, trifluoropropyl group, cyanoethyl group, etc. in which part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. Of these, preferred are unsubstituted or substituted monovalent hydrocarbon groups having preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Among these, a methyl group is more preferable from the viewpoint of heat resistance and light resistance.

  Furthermore, the component (B) is preferably liquid at room temperature because it is easy to handle. The viscosity at room temperature is preferably 1000 Pa · s or less, and more preferably 100 Pa · s or less. .

<(C) Organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule>
In the present invention, the component (C) is cured by a hydrosilylation reaction with the component (B) to form a silicone matrix. For this reason, there is no particular limitation as long as it is an organohydrogenpolysiloxane containing two or more hydrosilyl groups in one molecule, and widely known ones can be used. The structure may be any of linear, branched, cyclic and three-dimensional cross-linked structures.

  Examples of the linear component (C) include polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups, and copolymers of dimethylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units. sell.

  Examples of the cyclic component (C) include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydro Examples include Gen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane.

Examples of the component (C) having a three-dimensional crosslinked structure are not particularly limited,
SiO _4/2 (6)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (9) and (10).
R ^b1 R ^b2 ₂ SiO _1/2 (9)
R ^b2 ₃ SiO _1/2 (10)
(Wherein R ^b1 is a hydrogen atom, and R ^b2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
And those having a structure in which at least two terminals of the main structure are blocked by the general formula (9) are exemplified.

  The cured product obtained from the organopolysiloxane composition containing the component (C) represented by the general formula (6), the general formula (9), and the general formula (10) has a high crosslink density, and thus has high hardness. This is preferable because a high-strength cured product can be obtained.

  Examples of substituted or unsubstituted monovalent hydrocarbon groups other than alkenyl groups include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, phenyl groups, and tolyl groups. The same or different aryl groups or the same or different selected from chloromethyl group, trifluoropropyl group, cyanoethyl group, etc. in which part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. Of these, preferred are unsubstituted or substituted monovalent hydrocarbon groups having preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Among these, a methyl group is more preferable from the viewpoint of heat resistance and light resistance.

  The addition amount of the organohydrogenpolysiloxane is such that the hydrosilyl group of the component (C) is 30 to 500 mol%, preferably 40 to 200 mol% with respect to the alkenyl group of the component (B) described above. Is desirable.

  Furthermore, the component (C) is preferably liquid at room temperature because it is easy to handle. The viscosity at room temperature is preferably 1000 Pa · s or less, and more preferably 100 Pa · s or less. .

<(D) Hydrosilylation catalyst>
As the hydrosilylation catalyst as component (D) in the present invention, for example, a platinum-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst can be added. Known platinum-based catalysts can be used. Specifically, platinum element alone, platinum compounds, platinum complexes, chloroplatinic acid, chloroplatinic acid alcohol compounds, aldehyde compounds, ether compounds, various olefins and vinyl Examples include complexes with siloxane. The addition amount of the platinum-based catalyst is preferably in the range of 10 ⁻¹ to 10 ⁻¹⁰ mol as a platinum atom per 1 mol of the alkenyl group of the component (B), and in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. More preferably it is used. If the platinum catalyst is too much, light having a short wavelength is absorbed, and thus the light resistance of the obtained cured product may be lowered. If it is too little, the matrix may not be cured.

<Adhesive agent>
In the present invention, an adhesion-imparting agent can be added to the curable composition as necessary.
As the adhesion-imparting agent in the present invention, a silane coupling agent, a boron-based coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, or the like can be preferably used.

  Examples of the silane coupling agent include at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group in the molecule, and a silicon atom-bonded alkoxy group. A silane coupling agent having a group is preferred. About the said functional group, an epoxy group, a methacryl group, and an acryl group are especially preferable in a molecule | numerator from the point of sclerosis | hardenability and adhesiveness especially.

  Specifically, as the organosilicon compound having an epoxy functional group and a silicon atom-bonded alkoxy group, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxy) And cyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

  Examples of the organosilicon compound having a methacryl group or an acryl group and a silicon atom-bonded alkoxy group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acrylonitrile. Examples include, but are not limited to, loxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

  Examples of boron coupling agents include trimethyl borate, triethyl borate, tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, triborate triborate. Examples include, but are not limited to, normal butyl, tri-sec-butyl borate, tri-tert-butyl borate, triisopropyl borate, trinormal propyl borate, triallyl borate, and boron methoxyethoxide.

  Examples of titanium coupling agents include tetra (n-butoxy) titanium, tetra (i-propoxy) titanium, tetra (stearoxy) titanium, di-i-propoxy-bis (acetylacetonate) titanium, i-propoxy ( 2-ethylhexanediolate) titanium, di-i-propoxy-diethylacetoacetate titanium, hydroxy-bis (lactate) titanium, i-propyltriisostearoyl titanate, i-propyl-tris (dioctylpyrophosphate) titanate, tetra- i-propyl) -bis (dioctyl phosphite) titanate, tetraoctyl-bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene Taneto, i- propyl trioctanoyl titanate, but i- propyl dimethacrylate -i- stearoyl titanate is exemplified, but not limited thereto.

  Examples of the aluminum coupling agent include, but are not limited to, aluminum butoxide, aluminum isopropoxide, aluminum acetylacetonate, aluminum ethylacetoacetonate, and acetoalkoxyaluminum diisopropylate.

  The adhesiveness imparting agent in the present invention may be used alone or in combination of two or more. The addition amount is preferably 0.05 to 30% by weight of the total weight of the component (B) and the component (C). In addition, depending on the type or amount of the adhesion-imparting agent, there are those that inhibit the hydrosilylation reaction of the matrix resin, so the influence on the hydrosilylation reaction must be considered.

  A curing retarder can be used for the purpose of improving the storage stability of the curable composition used in the present invention or adjusting the reactivity of the hydrosilylation reaction during the curing process. Known curing retarders can be used, and specific examples include compounds containing aliphatic unsaturated bonds, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, and organic peroxides. . These may be used alone or in combination of two or more.

  Examples of the compound containing an aliphatic unsaturated bond include 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 3 -Methyl-1-hexyn-3-ol, 3-ethyl-1-pentyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, en-in Examples thereof include compounds, maleic esters such as maleic anhydride and dimethyl maleate.

  Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, and the like.

  Nitrogen-containing compounds include N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, N, N-dibutyl-1,3 -Propanediamine, N, N-dimethyl-1,3-propanediamine, N, N, N ', N'-tetraethylethylenediamine, N, N-dibutyl-1,4-butanediamine, 2,2'-bipyridine, etc. Is mentioned.

  Examples of tin compounds include stannous halide dihydrate, stannous carboxylate, and the like. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

Although the addition amount of a curing retarder is not particularly limited, it is preferably used in the range of 10 ⁻¹ to 10 ⁴ mol, preferably in the range of 1 to 10 ³ mol, per 1 mol of the hydrosilylation catalyst. More preferred. Moreover, these hardening retarders may be used independently and may be used in combination of 2 or more types.

  In the organopolysiloxane composition used in the present invention, fillers such as pulverized quartz, calcium carbonate, and carbon may be added as a bulking agent as needed within a range not impeding the effects of the present invention.

  In addition, the organopolysiloxane composition used in the present invention has various additives such as a colorant and a heat resistance improver, a reaction control agent, a mold release agent, or a filler as necessary, as long as the effects of the present invention are not hindered. A dispersant for the agent can be optionally added.

  Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like.

In order to make the organopolysiloxane composition of the present invention flame-retardant and fire-resistant, known additives such as titanium dioxide, manganese carbonate, Fe ₂ O ₃ , ferrite, mica, glass fiber, glass flakes and the like are used. It may be added. In addition, it is preferable to stop these arbitrary components to the minimum addition amount so that the effect of this invention may not be impaired.

  The organopolysiloxane composition used in the present invention mixes the above-mentioned components uniformly using a kneader such as a two-roll, Banbury mixer, or kneader, or using a planetary stirring and deaerator, and heat treatment as necessary. It can obtain by giving.

  The method for curing the organopolysiloxane composition used in the present invention is not particularly limited, but it can be reacted by simply mixing the components, or can be reacted by heating. From the viewpoint that the reaction is fast and generally a material having high heat resistance is easily obtained, a method of heating and reacting is preferable.

  Although various reaction temperatures can be set, a temperature range of 25 ° C to 300 ° C is preferable, 30 ° C to 280 ° C is more preferable, and 35 ° C to 260 ° C is more preferable. When the reaction temperature is lower than 25 ° C, the reaction time for sufficient reaction tends to be long, and when the reaction temperature is higher than 300 ° C, the product tends to be thermally deteriorated.

  The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Rather than carrying out the reaction at a constant temperature, the reaction is preferably carried out while raising the temperature in a multistage manner or continuously in that a uniform cured product without distortion can be easily obtained.

  The pressure during the reaction can be variously set as required, and the reaction can be carried out at normal pressure, high pressure or reduced pressure.

  The optical device in the present invention is a light receiving element for an optical recording disk such as a CD or DVD, an LED, a line sensor or area sensor that is a solid-state image sensor, a solar cell, an optical system device for a mobile phone, an optical system device for a digital camera, Optical thin film products, laser beam printer optical system devices, liquid crystal display devices, plasma display devices, optical filters, optical system devices using nonlinear optical materials, optical devices for projectors / rear pro TVs, spatial light modulators, spatial phase modulators, An optical isolator and the like can be mentioned, but the optical device is not limited to these.

  The present invention will be described in more detail based on the following examples, but the present invention is not limited only to these examples.

(Creation of cured material for dynamic viscoelasticity measurement)
The mold is filled with a curable resin composition for forming a sealing layer, and is thermally cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours, and has a length of 35 mm, a width of 5 mm, A document with a thickness of 2 mm was prepared.

(Dynamic viscoelasticity measurement)
The dynamic viscoelasticity of the cured material for measurement prepared as described above was measured using a dynamic viscoelasticity measuring device Reogel E4000 manufactured by UBM, measurement temperature -20 ° C to 100 ° C, heating rate 4 ° C per minute, strain 4 µm, Measurement was performed at a frequency of 10 Hz, a gap between chucks of 25 mm, and a tensile mode.

From the measurement results, the temperature dependence of the storage elastic modulus was calculated according to the following formula using the temperature at which the loss tangent shows the maximum value and the storage elastic modulus at −20 ° C. and 100 ° C.
Temperature dependence ratio of storage elastic modulus = E ′ (− 20) / E ′ (100) (2) where E ′ (100) is the storage elastic modulus at 100 ° C., and E ′ (− 20) is −20. The storage elastic modulus at ° C is shown.

(Creation of cured product for evaluation)
Enomoto Co., Ltd. LED package (product name: TOP LED 1-IN-1), 0.4mm x 0.4mm x 0.2mm single crystal silicon chip, Henkel Japan Co., Ltd. epoxy adhesive (product name) : LOCTITE 348), and fixed in an oven at 150 ° C. for 30 minutes. Here, a curable resin composition for forming a sealing layer was injected, and a sample was prepared by thermosetting in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours.

(Long-term reliability evaluation at operating environment temperature)
Long-term reliability was evaluated by the following two tests.
Evaluation 1 ... Thermal shock test The cured product for evaluation prepared as described above was cycled at a high temperature of 100 ° C for 5 minutes and at a low temperature of -40 ° C for 5 minutes using a thermal shock tester (TSA-71H-W manufactured by ESPEC). After 100 cycles, the sample was observed. After the test, if there was no change visually, it was rated as “C”, and if it cracked or peeled off or colored with the package, it was marked “X”.
Evaluation 2 ... Heat test The cured product for evaluation prepared as described above was allowed to stand at 200 ° C. for 100 hours in a convection oven (SPHH-101 manufactured by Espec Corp.), and then a sample was observed. After the test, when there was no change visually, it was evaluated as “◯”, and when cracks occurred, peeling from the package, or coloring occurred, it was evaluated as “X”.

(Synthesis Example 1)
After mixing 400 parts by weight of pure water and 12 parts by weight of sodium dodecylbenzenesulfonate (solid content) in a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer The temperature was raised to 50 ° C. in a nitrogen atmosphere. Thereafter, 10 parts by weight of butyl acrylate (BA), 3 parts by weight of t-dodecyl mercaptan and 0.01 part by weight of paramentane hydroperoxide (solid content) were added.

  After 30 minutes, 0.18 part of sodium formaldehyde sulfoxylate (SFS), 0.019 part by weight of ethylenediaminetetraacetic acid (EDTA) and 0.019 part by weight of ferrous sulfate were added and stirred for 1 hour. A mixed solution of 90 parts by weight of BA, 27 parts by weight of t-dodecyl mercaptan and 0.18 parts by weight of paramentane hydroperoxide (solid content) was continuously added over 3 hours. Further, post-polymerization was performed for 1 hour to obtain a latex containing a seed polymer (volume average particle size 0.020 μm).

  Next, in a five-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port, and a thermometer, 2.0 parts by weight (solid content) of the above seed polymer (10 wt% aqueous solution dodecylbenzene) After charging 1.5 parts by weight of sulfonic acid (solid content) and 300 parts by weight of pure water (including the carry-in from the latex containing the seed polymer), the mixture was stirred for 10 minutes and then the system was heated to 80 ° C. under a nitrogen atmosphere. The temperature was raised to. Separately, a mixture of 150 parts by weight of pure water, 0.5 parts by weight of 5% by weight aqueous sodium dodecylbenzenesulfonate (solid content), 97 parts by weight of octamethylcyclotetrasiloxane, and 3 parts by weight of trimethoxymethylsilane was homogenized. After forcedly emulsifying with a mixer at 8000 rpm for 5 minutes, this mixed solution was continuously added over 3.5 hours. Further, after 2.5 hours of post-polymerization, cooled to 25 ° C. and allowed to stand for 20 hours to complete the polymerization, and latex containing silicone-based particles (volume average particle size 0.110 μm) as component (A-1) Got.

(Synthesis Example 2)
In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer, 90 parts by weight (solid content) of silicone-based particles as component (A-1) obtained in Synthesis Example 1 , And 0.45 parts by weight (solid content) of 10% by weight aqueous solution of dodecylbenzenesulfonic acid were added, and the temperature was raised to 40 ° C. in a nitrogen atmosphere.

Separately, 40 parts by weight of pure water, 0.1 part by weight (solid content) of 15% by weight aqueous solution of sodium dodecylbenzenesulfonate, 7.30 parts by weight of dimethoxydimethylsilane ((CH ₃ ) ₂ SiO _2/2 Equivalent to 4.5 parts by weight in terms of a complete condensate of the structural unit represented by the formula: ethyl silicate condensate (manufactured by Tama Chemical Industry Co., Ltd., trade name: ethyl silicate 40, SiO ₂ content: 39.0 to 42) 0.0 wt%) 11.16 parts by weight (corresponding to 4.5 parts by weight in terms of the complete condensate of the structural unit represented by SiO ₂ ) was forcibly emulsified with a homomixer at 5000 rpm for 5 minutes. Later, it was added dropwise over 20 minutes. (A-2) component was formed by stirring this solution for 5 hours, keeping at 40 degreeC.

Next, 27 parts by weight of pure water and 0.03 part by weight (solid content) of a 15% by weight aqueous solution of sodium dodecylbenzenesulfonate were added to this solution, and 6.42 parts by weight ((CH ₃ ) ₃ SiO _{1 / 2} equivalent to 5.0 parts by weight in terms of the complete condensate of the structural unit represented by ₂ ), 1.40 parts by weight of ethoxydimethylvinylsilane (Vi (CH ₃ ) ₂ SiO _1/2 Equivalent to 1.0 part by weight in terms of a complete condensate), 0.81 part by weight of dimethoxydimethylsilane (corresponding to a complete condensate of a structural unit represented by (CH ₃ ) ₂ SiO _2/2 . Equivalent to 5 parts by weight), ethyl silicate condensate (manufactured by Tama Chemical Industry Co., Ltd., trade name ethyl silicate 40, SiO ₂ content: 39.0 to 42.0% by weight) 1.24 parts by weight (expressed as SiO ₂ Structural unit A mixture of equivalent) to 0.5 parts by weight in terms of after 5 minutes forced emulsification at 5000rpm homomixer to complete condensate, was added dropwise over 10 minutes.

  (A-3) component was formed by stirring this solution for 4.5 hours, keeping at 40 degreeC. This system was cooled to 25 ° C. and allowed to stand for 20 hours to complete the polymerization, and a latex containing silicone particles (volume average particle size 0.112 μm) as component (A) was obtained.

Example 1
A mixed solvent comprising ethyl acetate / methanol = 6/4 (vol / vol) with respect to 35 parts by weight of the resin solid content of the latex (resin solid content concentration 16% by weight) containing the component (A) obtained in Synthesis Example 2. After adding 200 parts by weight to agglomerate the particles, they were spun down at 2000 rpm for 5 minutes in a centrifuge. The obtained precipitate was dispersed and washed in 200 parts by weight of a mixed solvent of ethyl acetate / methanol = 3/7 (vol / vol), and then centrifuged with a centrifuge at 2000 rpm for 5 minutes. The obtained precipitate was dispersed in 200 parts by weight of a mixed solvent of ethyl acetate / methanol = 4/6 (vol / vol) and washed, and then the solvent was distilled off by centrifugation at 2000 rpm for 5 minutes using a centrifuge. Repeated three more times. Thereafter, 350 parts by weight of ethyl acetate was added to 35 parts by weight of the resulting precipitate to obtain an ethyl acetate solution of component (A).

  With respect to 30 parts by weight of the resin solid content of the silicone particles as the component (A) thus obtained, a vinyl group-containing polysiloxane having a three-dimensional structure as the component (B) (manufactured by Clariant, trade name MQV-7) , Vinyl group content 3.5 mol / kg) 36.2 parts by weight, component (C) hydrosilyl group-containing polysiloxane having a three-dimensional structure (manufactured by Clariant, trade name MQH-5, hydrosilyl group content 2.3 mol / kg) and 57.9 parts by weight of hydrosilyl group-containing polysiloxane having the same three-dimensional structure as component (C, manufactured by Clariant, trade name MQH-8, hydrosilyl group content 7.5 Mol / kg) was blended in an amount of 5.9 parts by weight, and the mixture was concentrated by a rotary evaporator to distill off ethyl acetate.

Thereafter, 5.0 parts by weight of 3-glycidoxypropyltrimethoxysilane, 1.0 part by weight of trimethyl borate, 0.0011 part by weight of 1% xylene solution of 1-ethynyl-1-cyclohexanol, N, N, N ′ , N'-tetramethylethylenediamine 1% xylene solution 0.0010 parts by weight and (D) component platinum vinylsiloxane complex xylene solution (containing 3% by weight platinum) 0.0062 parts by weight, Stirring and defoaming were carried out with a type stirring deaerator to obtain a liquid mixture.
The obtained liquid mixture was hardened according to each test-cured material preparation method, LED which has a sealing material and the said sealing material was created, and each test was done.

(Example 2)
Cured according to each test cured product preparation method as in Example 1 except that 8.40 parts by weight of ethoxydimethylvinylsilane in Synthesis Example 2 and 20 parts by weight of component (A) in Example 1 were used. Then, an LED having a sealing material and the sealing material was prepared, and each test was performed.

(Example 3)
In Example 2 above, except that 30 parts by weight of the component (A) is used, the cured product for test is cured according to the method for creating a cured product for each test in the same manner as in Example 2 to produce a sealing material and an LED having the sealing material. Each test was conducted.

Example 4
In Example 2 above, except that 40 parts by weight of component (A) is used, curing is performed according to each test cured material creation method in the same manner as in Example 2 to create a sealing material and an LED having the sealing material. Each test was conducted.

(Comparative Example 1)
36.2 parts by weight of (B) component, vinyl group-containing polysiloxane having a three-dimensional structure (manufactured by Clariant, trade name MQV-7, vinyl group content 3.5 mol / kg) 57.9 parts by weight of a hydrosilyl group-containing polysiloxane having a certain three-dimensional structure (manufactured by Clariant, trade name MQH-5, hydrosilyl group content 2.3 mol / kg) is also a component (C). 5.9 parts by weight of hydrosilyl group-containing polysiloxane having a structure (manufactured by Clariant, trade name MQH-8, hydrosilyl group content 7.5 mol / kg) was blended.

Thereafter, 5.0 parts by weight of 3-glycidoxypropyltrimethoxysilane, 1.0 part by weight of trimethyl borate, 0.0011 part by weight of 1% xylene solution of 1-ethynyl-1-cyclohexanol, N, N, N ′ , N'-tetramethylethylenediamine 1% xylene solution 0.0010 parts by weight and (D) component platinum vinylsiloxane complex xylene solution (containing 3% by weight platinum) 0.0062 parts by weight, Stirring and defoaming were carried out with a type stirring deaerator to obtain a liquid mixture.
The obtained liquid mixture was cured in accordance with the preparation of each test cured product, and a long-term reliability test was conducted.

(Comparative Example 2)
In a four-necked flask equipped with a stirrer, a reflux condenser, and a monomer blowing port, 20 parts by weight of 1,1,3,3-tetramethyldisiloxane (manufactured by Gerest), 3-vinyl-7-oxabicyclo [4.1 0.0] -heptane (manufactured by Union Carbide) 18.5 parts by weight, 20 ml of dehydrated toluene (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.013 part by weight of Wilkinson catalyst (manufactured by Aldrich) were added. After stirring at 4 ° C. for 4 hours, 22 parts by weight of vinyltrimethoxysilane (manufactured by Gerest) was added, the temperature was raised to 90 ° C., and the mixture was further stirred for 6 hours. After distilling off the solvent under reduced pressure at room temperature, 54.6 parts by weight of 1- [2- (3 {7-oxabicyclo [4.1.0] heptyl} ethyl] -3- [2-trimethoxysilylethyl] -1,1,3,3-tetramethyldisiloxane was obtained as a solid content.

  Furthermore, 1- [2- (3 {7-oxabicyclo [4.1.0] heptyl} ethyl] -3- [] obtained above was added to a four-necked flask equipped with a stirrer, reflux condenser, and monomer inlet. 2-trimethoxysilylethyl] -1,1,3,3-tetramethyldisiloxane 10 parts by weight, deionized water 10 parts by weight, ion exchange resin 0.4 parts by weight (product name Amberlite IRA-400, Rohm And Haus) and 5 parts by weight of 2-propanol were added and stirred for 12 hours at 150 ° C. After the ion exchange resin was removed by silica gel column chromatography using ethyl acetate (manufactured by Wako Pure Chemical Industries) as a solvent, By distilling off the solvent under reduced pressure, 8 parts by weight of 1- [2- (3 {7-oxabicyclo [4.1.0] heptyl} ethyl] -3- [2-trimethoxysilylethyl] -1,1 , 3,3-Tetrame A sol-gel condensate of tildisiloxane was obtained.

  The sol-gel condensate obtained above was cured according to the preparation of each test cured product, and a long-term reliability test was performed.

Various test results are shown in Table 1.

As shown in Table 1, in Example 1, the loss tangent has a maximum at 67 ° C., but the temperature dependence of the storage elastic modulus is very small as 8.7, and changes in the thermal shock test and the thermal test. You can see that there is no. On the other hand, the maximum loss tangent does not exist between −40 ° C. and 100 ° C. in Comparative Example 1, cracks occur in the thermal shock test, and the loss tangent peak exists at 48 ° C. in Comparative Example 2. However, the temperature dependence of the storage elastic modulus was as large as 95, and coloring occurred in the heat resistance test. From the above, it can be seen that the LED sealing material of Example 1 is excellent in adhesiveness, light resistance, heat resistance, and thermal shock resistance, and the LED having this as a sealing layer is excellent in long-term reliability.

Claims (14)

A curable composition is cured and has at least one maximum value of loss tangent measured at a frequency of 10 Hz within a temperature range of −40 ° C. to 100 ° C. and a maximum value of 0.01 to 0.5. An optical device having an encapsulating layer therein. 2. The optical device according to claim 1, wherein the temperature dependence ratio of the storage elastic modulus of the sealing layer represented by the following formula (1) is 50 or less.
Temperature dependence ratio of storage elastic modulus = E ′ (− 20) / E ′ (100) (1)
(E ′ (100) represents the storage elastic modulus at 100 ° C., and E ′ (−20) represents the storage elastic modulus at −20 ° C.) 3. The optical device according to claim 1, wherein a content of silicon atoms in the cured material that is the sealing material layer is 10 to 60 wt%. The optical device according to claim 1, wherein the sealing layer contains silicone-based particles (A). The silicone-based particle (A) has a core-alkoxysilane condensate shell structure in which the silicone-based particle (A-1) is coated with a shell component (A-2) obtained by adding and condensing an alkoxysilane. The optical device according to claim 4, wherein the optical device is a silicone-based particle. The shell component of the silicone-based particles (A) is a first shell component (A-2) obtained by adding and condensing alkoxysilane, and then a second shell component obtained by adding and condensing alkoxysilane. The optical device according to claim 5, wherein the optical device is a silicone-based particle having a silicone-based particle core-alkoxysilane condensate shell structure made of (A-3). The second shell layer comprising the alkoxysilane condensate as component (A-3) has the following component (a) as an essential component, and at least one of the following component (b), the following component (c), and the following component (d). The optical device according to claim 6, wherein the optical device is obtained by condensing seeds.
(A) Component: General formula (2)

(Wherein R ¹² represents an alkyl group, and R ¹³ , R ^14, and R ¹⁵ represent the same or different monovalent organic groups) and / or a partial condensation thereof. object.
(B) Component: General formula (3)

(Wherein R ²² and R ²³ represent the same or different monovalent alkyl groups, and R ²⁴ and R ²⁵ represent the same or different monovalent organic groups) and / Or a partial condensate thereof.
(C) Component: General formula (4)

(Wherein R ³² , R ³³ , and R ³⁴ represent the same or different monovalent alkyl groups, and R ³⁵ represents a monovalent organic group) and / or The partial condensate.
(D) Component: General formula (5)

(Wherein R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ represent the same or different monovalent alkyl groups) and / or a partial condensate thereof. The first shell layer comprising the alkoxysilane condensate as the component (A-2) is formed by condensing at least one of the following component (b), the following component (c) and the following component (d). The optical device according to claim 6 or 7.
(B) Component: General formula (3)

(Wherein R ²² and R ²³ represent the same or different monovalent alkyl groups, and R ²⁴ and R ²⁵ represent the same or different monovalent organic groups) and / Or a partial condensate thereof.
(C) Component: General formula (4)

(Wherein R ³² , R ³³ , and R ³⁴ represent the same or different monovalent alkyl groups, and R ³⁵ represents a monovalent organic group) and / or The partial condensate.
(D) Component: General formula (5)

(Wherein R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ represent the same or different monovalent alkyl groups) and / or a partial condensate thereof. The first shell layer made of the alkoxysilane condensate as the component (A-2) is 1 to 40% by weight with respect to 40 to 98% by weight of the silicone particles as the component (A-1), (A-3) A polymer coated with 1 to 30% by weight of a second shell layer composed of an alkoxysilane condensate as a component (however, the components (A-1), (A-2) and (A-3) are combined) The optical device according to claim 6, wherein the optical device is 100% by weight. The optical device according to claim 1, wherein the sealing layer contains a silicone resin. 11. The optical according to claim 1, wherein the sealing layer is obtained by curing a curable composition containing an organopolysiloxane (B) having at least two alkenyl groups. device. The optical component according to any one of claims 1 to 11, wherein the sealing layer is obtained by curing a curable composition containing an organopolysiloxane (C) having at least two hydrosilyl groups. device. The component (B) is represented by the general formula (6)
SiO _4/2 (6)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (7) and (8).
R ^a1 R ^a2 ₂ SiO _1/2 (7)
R ^a2 ₃ SiO _1/2 (8)
(Wherein R ^a1 is an alkenyl group, and R ^a2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
At least 2 alkenyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by formula (II) and having a structure in which at least two ends of the main structure are blocked with the general formula (7) The optical device according to claim 11, wherein the optical device is an organopolysiloxane composition. The component (C) is represented by the general formula (6)
SiO _4/2 (6)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (9) and (10).
R ^b1 R ^b2 ₂ SiO _1/2 (9)
R ^b2 ₃ SiO _1/2 (10)
(Wherein R ^b1 is a hydrogen atom, and R ^b2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
And having at least 2 hydrosilyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by formula (II) and having a structure in which at least two ends of the main structure are blocked with the general formula (9) The optical device according to claim 12, wherein the optical device is an organohydrogenpolysiloxane.