KR20190093137A - Infrared-transmitting curable composition, cured product thereof and optical semiconductor device - Google Patents

Abstract

Provided is an infrared-transmitting curable composition which has excellent compatibility with a dye and has high infrared ray penetration and visible ray shielding. The infrared-transmitting curable composition comprises the following components: (A) an addition reaction product of (a) a compound represented by chemical formula (1) and (b) a polycyclic hydrocarbon having two additional reactive carbon-carbon double bonds in one molecule, wherein the addition reaction product has two additional reactive carbon-carbon double bonds in one molecule (R^1 represents a monovalent hydrocarbon group having 1 to 12 carbon atoms, or the like and R^2 represents a divalent hydrocarbon group having 1 to 12 carbon atoms); (B) a dye having an absorption band in the region of wavelength 350 to 650 nm and transmitting at least a part of light having a wavelength of 800 to 900 nm; (C) an organosilicon compound having a hydrogen atom bonded to at least two silicon atoms in one molecule and having no additional reactive carbon-carbon double bond containing group, epoxy group, alkoxysilyl group, and carboxylic anhydride group; and (D) a hydrosilylation reaction catalyst.

Description

Infrared permeable curable composition, its cured product and optical semiconductor device {INFRARED-TRANSMITTING CURABLE COMPOSITION, CURED PRODUCT THEREOF AND OPTICAL SEMICONDUCTOR DEVICE}

The present invention relates to an infrared ray transmissive curable composition, a cured product thereof, and an optical semiconductor device.

In recent years, sensors have been installed in various electronic devices and devices, and light emitting diodes (LEDs) have been used as infrared light emitting devices of the sensors.

In such a sensor, malfunction occurs due to visible light. Therefore, it is necessary to use a filter, a coating agent, or the like as a light source to block visible light and to transmit only infrared light.

As an infrared ray permeable filter, the infrared ray permeable filter which added dye to polycarbonate resin and an epoxy resin, for example is disclosed (patent documents 1-4).

On the other hand, as a method which does not use process water, an expensive filter, etc., LED sealing material containing resin which added the dye which interrupts visible light is developed. As this resin, the epoxy resin has been used conventionally (patent document 5).

However, epoxy resins have a drawback in that they are less resistant to heat and light, and in recent years, due to high brightness of LEDs and an increase in heat generation associated with them, cracking and peeling are likely to occur, leading to reduced reliability of LEDs. there is a problem.

From such a background, although the development of the infrared ray permeable sealing material containing the silicone resin with favorable durability is advanced (patent document 6), the material which is more excellent in infrared ray permeability and visible light shielding property is calculated | required.

Japanese Patent Publication No. 2013-227565 Japanese Patent Publication No. 2008-9238 Japanese Patent Laid-Open No. 9-3311 Japanese Patent Laid-Open No. 11-273439 Japanese Patent Laid-Open No. 2008-101188 Japanese Patent Laid-Open No. 2010-121117

This invention is made | formed in view of the said situation, Since it is excellent in compatibility with dye, it is possible to suppress aggregation of dye, the infrared permeable curable composition, its hardened | cured material, and the optical semiconductor using the same which have high infrared transmittance and visible light shielding property. It is an object to provide a device.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining so that the said subject may be solved, the composition containing the following (A)-(D) component shows the outstanding compatibility with dye, the aggregation of dye does not occur, and infrared ray transmittance is high, It discovered that the hardened | cured material excellent in the shielding property of visible light was provided and completed this invention.

That is, the present invention

1. An infrared ray transmissive curable composition comprising the following (A) to (D) components,

(A) A polycyclic hydrocarbon having (a) a compound having two hydrogen atoms bonded to the silicon atom represented by the following formula (1) in one molecule, and (b) two additional reactive carbon-carbon double bonds in one molecule. Addition reaction product with and addition reaction product having two addition reactive carbon-carbon double bonds in one molecule

(In formula, R <^1> may respectively independently be substituted by the halogen atom, the cyano group, or the glycidoxy group, and represents the C1-C12 monovalent hydrocarbon group or the C1-C6 alkoxy group, and R ² represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms)

(B) A dye having an absorption band in a region of wavelength 350 to 650 nm and transmitting at least a part of light having a wavelength of 800 to 900 nm.

(C) an organosilicon having a hydrogen atom bonded to at least two silicon atoms in one molecule and not having a group selected from an addition reactive carbon-carbon double bond containing group, an epoxy group, an alkoxysilyl group, an amide group and a carboxylic anhydride group compound

(D) hydrosilylation reaction catalyst

2. The infrared permeable curable composition of 1, wherein the polycyclic hydrocarbon is at least one of 5-vinylbicyclo [2.2.1] hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene;

3. 1 or 2 infrared rays permeable curable composition in which said (A) component is represented by following formula (2),

(Wherein n represents an integer of 0 to 50)

4. The cured product of any of the infrared ray transmissive curable compositions according to any one of 1 to 3, wherein the average light transmittance at a wavelength of 350 to 650 nm is 40% or less, and the average light transmittance at a wavelength of 800 to 900 nm in both thicknesses of 2 mm and 0.4 mm. Hardened | cured material which is 60% or more,

5. Optical semiconductor device which has an optical semiconductor element sealed by the hardened | cured material of the infrared permeable curable composition in any one of 1-3.

To provide.

According to the curable composition of this invention, since the hardened | cured material excellent in infrared rays permeability and visible light shielding property can be obtained, it is suitable for the small apparatus which the thickness of a hardened | cured material layer is restrict | limited, and also applies also in the site | part to which the thickness of a hardened layer is needed. It is possible.

The infrared permeable curable composition of this invention which has such a characteristic is useful as an optical device use, especially an infrared light emitting device, the coating material for optical components, an adhesive agent, and also an optical semiconductor element sealing material.

1 is an ultraviolet visible transmission spectrum diagram in the cured product (film thickness 0.4mm) prepared in Example 2-1.
2 is an ultraviolet visible transmission spectrum diagram in the cured product (film thickness 2.0 mm) produced in Example 2-1.
3 is an ultraviolet visible transmission spectrum diagram in the cured product (film thickness 0.4mm) prepared in Example 2-2.
4 is an ultraviolet visible transmission spectrum diagram in the cured product (film thickness 2.0 mm) prepared in Example 2-2.
5 is an ultraviolet visible transmission spectrum diagram in the cured product (film thickness 2.0 mm) produced in Comparative Example 2-1.
6 is an ultraviolet visible transmission spectrum diagram in the cured product (film thickness 2.0 mm) produced in Comparative Example 2-2.
7 is an ultraviolet visible transmission spectrum diagram in the cured product (film thickness 0.4mm) prepared in Comparative Example 2-3.
8 is an ultraviolet visible transmission spectrum diagram in the cured product (film thickness 2.0 mm) produced in Comparative Example 2-3.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

The infrared permeable curable composition according to the present invention comprises (A) a compound having two hydrogen atoms bonded to a silicon atom represented by the following formula (1) in one molecule, and (b) an addition reactive carbon-carbon double bond. Is an addition reaction product with a polycyclic hydrocarbon having two in one molecule, and an addition reaction product having two addition reactive carbon-carbon double bonds in one molecule, (B) has an absorption band in a region of 350 to 650 nm wavelength, A dye that transmits at least a portion of light having a wavelength of 800 to 900 nm, (C) has a hydrogen atom bonded to at least two silicon atoms in one molecule, and has an addition reactive carbon-carbon double bond-containing group, an epoxy group, an alkoxysilyl group and a carboxyl An organosilicon compound having no acid anhydride group, and (D) a hydrosilylation reaction catalyst.

In addition, in this invention, "additional reactivity" means the property which can react with the hydrogen atom couple | bonded with the silicon atom (Hereinafter, it may be called "SiH") by hydrosilylation reaction.

(In formula, R <^1> may respectively independently be substituted by the halogen atom, the cyano group, or the glycidoxy group, and represents the C1-C12 monovalent hydrocarbon group or the C1-C6 alkoxy group, and R ² represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms)

[1] (A) component

Compound (a) which becomes a raw material of (A) component of this invention, the compound which has two hydrogen atoms couple | bonded with the silicon atom represented by said Formula (1) in 1 molecule, and (b) addition reactive carbon-carbon double bond is 1 It is an addition reaction product with two polycyclic hydrocarbons which have in a molecule | numerator, and it is an addition reaction product which has two addition reactive carbon-carbon double bonds in 1 molecule.

(a) In the compound which has two hydrogen atoms couple | bonded with the silicon atom represented by said Formula (1) in 1 molecule, As a specific example of the C1-C12 monovalent hydrocarbon group of R <^1> , Methyl, ethyl, 1 carbon atom such as n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, cyclopentyl, cyclohexyl group An alkyl group of 12 to 12; Alkenyl groups having 2 to 12 carbon atoms such as vinyl, 1-propenyl, allyl (2-propenyl), hexenyl, octenyl, cyclopentenyl, and cyclohexenyl groups; Aryl groups having 6 to 12 carbon atoms such as phenyl and naphthyl group; Alkylaryl groups having 7 to 12 carbon atoms such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, and hexylphenyl group; And aralkyl groups having 7 to 12 carbon atoms such as benzyl and phenethyl group.

Moreover, as a specific example of the C1-C6 alkoxy group, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t-butoxy, n-pentyloxy and n-hexyloxy, cyclopentyloxy, cyclohexyloxy group, etc. are mentioned.

Among these, as R ¹ , a monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an addition reactive carbon-carbon double bond is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and a methyl group is even more preferable. Do.

On the other hand, specific examples of the divalent hydrocarbon group having 1 to 12 carbon atoms of R ² include carbon such as methylene, ethylene, propylene, trimethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene and decamethylene groups Linear, branched or cyclic alkylene groups having 1 to 12 atoms; And aralkylene groups having 7 to 12 carbon atoms such as arylene groups having 6 to 12 carbon atoms such as phenylene, biphenylene, and naphthylene groups, and phenylene methylene and methylenephenylene methylene groups.

Among these, arylene groups having 6 to 12 carbon atoms are preferable, and a phenylene group is more preferable.

Although the thing represented by a following formula is mentioned as a specific example of a compound represented by said Formula (1), It is not limited to these. In addition, Me represents a methyl group.

In addition, the compound represented by Formula (1) may be used individually by 1 type, or may be used in combination of 2 or more type.

Moreover, (b) As a polycyclic hydrocarbon which has two addition reactive carbon-carbon double bonds in 1 molecule, (i) addition reactivity between two adjacent carbon atoms among the carbon atoms which form the backbone of a polycyclic hydrocarbon A carbon-carbon double bond being formed, (ii) a hydrogen atom bonded to a carbon atom forming a skeleton of a polycyclic hydrocarbon is substituted by an addition reactive carbon-carbon double bond-containing group, (iii) a polycyclic Among the carbon atoms forming the skeleton of the hydrocarbon, an additional reactive carbon-carbon double bond is formed between two adjacent carbon atoms, and the hydrogen atom bonded to the carbon atom forming the skeleton of the polycyclic hydrocarbon is added reactive carbon. -The thing substituted by the carbon double bond containing group, etc. can be used.

As a specific example of the said polycyclic hydrocarbon, 5-vinyl bicyclo [2.2.1] hept-2-ene represented by following formula (3) and 6-vinyl bicyclo [2.2.1] hept represented by Formula (4) 2-ene etc. are mentioned, These can also be used as a mixture (Hereinafter, when it is not necessary to distinguish these three characters, it may collectively be called "vinyl norbornene").

In addition, the substitution position of the vinyl group of the said vinylnorbornene may be either a cis arrangement (exo type) or a trans arrangement (endo type), and there is no special difference in the reactivity of a compound etc. by the difference of these arrangements. May be a combination of isomers of both configurations.

The addition reaction product of (A) component can be synthesize | combined by the method of Unexamined-Japanese-Patent No. 2005-133073, for example.

As an example, hydrosilylation of the (b) polycyclic hydrocarbon is carried out in an amount of more than 1 mol and 10 mol or less, preferably more than 1 mol and 5 mol or less with respect to 1 mol of the compound represented by (a) Formula (1). It can manufacture by addition reaction in presence of a reaction catalyst.

In this case, as a hydrosilylation reaction catalyst, a well-known thing can be used, As a specific example, The reaction product of carbon powder, platinum black, platinum chloride, platinum chloride, chloroplatinic acid, and monohydric alcohol which carry platinum metal, Platinum-based catalysts such as complexes of chloroplatinic acid and olefins and platinum bisacetoacetate; Platinum group metal catalysts, such as a palladium type catalyst and a rhodium type catalyst, etc. are mentioned. In addition, addition reaction conditions, use of a solvent, etc. are not specifically limited, What is necessary is just to be normal.

In the above reaction, an excess molar amount of the (b) polycyclic hydrocarbon is reacted with the compound represented by the formula (1) during the synthesis of the addition reaction product of the component (A). The addition reaction product has two addition reactive carbon-carbon double bonds derived from the polycyclic hydrocarbon (b) in one molecule.

Although it does not specifically limit as addition reaction product of (A) component, What is represented by following formula (5) is preferable, Especially it is more preferable that it is represented by following formula (2) whose R <^1> is a methyl group.

The addition reaction product containing such a polycyclic hydrocarbon and a phenylene group can be particularly suitably used because it provides excellent curability with dyes and gives a cured product excellent in hardness, crack resistance and heat resistance.

(In formula, R <^1> shows the same meaning as the above, Preferably it is a methyl group, n shows the integer of 0-50, Preferably it is an integer of 0-30, More preferably, it is an integer of 0-20. )

(Wherein n represents the same meaning as above)

[2] the component (B)

(B) component is a dye which has an absorption band in the area | region of wavelength 350-650 nm, and transmits at least one part of the light of wavelength 800-900 nm.

Examples of such dyes include anthraquinone-based, perinone-based, and quinophthalone-based dyes, which can be obtained as commercially available products.

As a commercial item, it is elixa black 850 (made by Orient Chemical Industries, Ltd.); SDO-12, SDO-2, Plast Black 8995, Plast Yellow 8005, Oil Green 5602, Plast Orange 8150, Plast Orange 8170, Plast Red 8370, Plast Black DA423, Plast Yellow 8005 (above, Arimoto Kagaku Kogyo Co., Ltd.) 1) etc. can be mentioned.

The dye of the component (B) may be used alone or in combination of two or more, and furthermore, a pigment, an inorganic material, or the like may be further used within the range of not impairing the visible light blocking property and infrared ray transmitting property of the present invention. .

Although the compounding quantity of (B) component can be adjusted suitably according to the thickness of the hardened | cured material obtained, Preferably it is 0.0001-20 mass parts, More preferably, it is 0.001-10 mass parts, with respect to 100 mass parts of (A) component. More preferably, it is 0.05-5.0 mass parts.

[3] (C) component

(C) component has a hydrogen atom (SiH) couple | bonded with at least 2, preferably 2-300 silicon atoms in 1 molecule, and an addition reactive carbon-carbon double bond containing group, an epoxy group, an alkoxy silyl group, an amide group And organosilicon compounds having no group selected from carboxylic anhydride groups.

The SiH group in this organosilicon compound reacts hydrosilylation with the addition-reactive carbon-carbon double bond of (A) component. When the organosilicon compound of (C) component has a linear structure or a branched structure, these SiH groups may exist only in either one of a molecular chain terminal and a molecular chain non-terminal part, or may exist in both of them.

The number (polymerization degree) of the silicon atoms in one molecule of the organosilicon compound of the component (C) is preferably 1 to 1,000, more preferably 1 to 200.

It is preferable that the organosilicon compound of (C) component is liquid at 25 degreeC, and the viscosity in 25 degreeC measured with the rotational viscometer becomes like this. Preferably it is 1-3,000 mPa * s, More preferably, it is 5-2,000 mPa * s.

As an organosilicon compound of (C) component, the compound represented by following formula (6) can be used, for example.

(In formula, R <^3> respectively independently represents the C1-C12 monovalent hydrocarbon group which may be substituted by the hydrogen atom or the halogen atom, a shows the integer of 1-100, b is the integer of 0-100. , And the arrangement of siloxane units in parentheses with a and b appended may be random, alternate, or block)

Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms that may be substituted with the halogen atom of R ³ include an alkyl group having 1 to 12 carbon atoms or a haloalkyl group, an aryl group having 6 to 12 carbon atoms, and the like. As a specific example of these alkyl groups and aryl groups, the same thing as the group illustrated by said R <^1> can be mentioned. Among these, as R ¹ , a methyl group or a phenyl group is preferable.

In particular, it is preferable that 10 mol% or more of all the substituents directly bonded to the Si atom in (C) component are a phenyl group from a compatible viewpoint with dye, and it is more preferable that 20 mol% or more is a phenyl group.

Although the suitable example of the compound represented by said Formula (6) is shown below, it is not limited to these. In addition, in each formula, Ph represents a phenyl group (it is the same below).

Moreover, as an organosilicon compound of (C) component, the compound represented by following formula (7) or (8) can also be used.

In formula (7) and (8), R <^1> and R <^2> represents the same meaning as the above, R <^4> represents a C1-C12 divalent hydrocarbon group each independently, R <^5> respectively independently carbon A monovalent hydrocarbon group having 1 to 12 atoms is represented, X represents a divalent linking group, and m represents an integer of 2 or 3.

As a specific example of the bivalent hydrocarbon group of R <^4> , the thing similar to the group illustrated by said R <^2> can be mentioned, A C1-C6 alkylene group is preferable and ethylene and trimethylene group are more preferable.

As a specific example of the monovalent hydrocarbon group of R <^5> , the same thing as the group illustrated by said R <^1> is mentioned, However, a C1-C12 alkyl group or a C6-C12 aryl group is preferable, and a methyl group or a phenyl group is more preferable. desirable.

As a divalent linking group of X, More preferably, the C1-C12 bivalent hydrocarbon group by which the carbon-carbon bond in a chain may be substituted by the ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, or Linear, branched or cyclic divalent siloxane chains. Specific examples of the divalent hydrocarbon group include the same groups as those exemplified in the above R ² , but an alkylene group having 1 to 12 carbon atoms is preferable.

Although the suitable specific example of a compound represented by said Formula (7) and (8) is shown below, it is not limited to these.

The organosilicon compound of (C) component may be used individually by 1 type, or may be used in combination of 2 or more type.

The compounding quantity of (C) component is an amount whose molar ratio represented by {the sum of the SiH groups of (C) component} / {the sum of the addition reactive carbon-carbon double bond in (A) component} becomes 0.2-5.0, Preferably the amount is 0.5 to 2.0.

In addition, the organosilicon compound of the component (C) does not have a group selected from an addition-reactive carbon-carbon double bond-containing group, an epoxy group, an alkoxysilyl group, an amide group, and a carboxylic anhydride group. It is distinguished from the (F) component mentioned later which has at least 1 type of group.

[4] (D) component

(D) component is a catalyst which accelerates the hydrosilylation reaction of the addition reactive carbon-carbon double bond couple | bonded with the silicon atom in the addition reaction product of (A) component with the SiH group in the organosilicon compound of (C) component.

The catalyst is not particularly limited as long as it promotes the hydrosilylation reaction, and examples thereof include platinum group metals such as platinum, palladium and rhodium, platinum chloride, alcohol-modified platinum chloride, platinum chloride and olefins, vinylsiloxane or acetylene. Coordination compounds with compounds, platinum group metal compounds such as tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium, and the like, and the like, and these may be used alone or in combination of two or more thereof. You may also

Among these, platinum compounds such as cobalt chloride, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid and olefins, vinylsiloxane, or acetylene compounds are preferable, and these platinum compounds are supported on a carrier such as an inorganic oxide, a resin, or carbon. It may be used in the form.

The catalyst compounding amount of the component (D) may be an effective amount as a hydrosilylation catalyst, and is preferably in the range of 0.1 to 1,000 ppm in terms of mass of the platinum group metal element with respect to the total mass of the component (A) and the component (C). More preferably, it is the range of 1-500 ppm.

[5] (E) component

The infrared ray permeable curable composition of the present invention may include a reaction control agent of component (E) as an optional component in order not to cause thickening or gelation before heat curing of the composition.

Specific examples of the reaction control agent include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentin-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclo Hexanol, ethynylmethyldecylcarbinol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentin, 3,5-dimethyl-3-trimethylsiloxy- 1-hexyn, 1-ethynyl-1-trimethylsiloxycyclohexane, bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5 , 7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, and the like, and these may be used alone or in combination of two or more thereof. .

Among them, 1-ethynylcyclohexanol, ethynylmethyldecylcarbinol, and 3-methyl-3-trimethylsiloxy-1-butyne are preferable.

The compounding quantity of (E) component becomes like this. Preferably it is 0.01-2.0 mass parts with respect to a total of 100 mass parts of (A) component and (C) component, More preferably, it is 0.01-0.1 mass part. If it is this range, the effect of reaction control will fully be exhibited.

[6] (F) components

In order to provide the adhesiveness of the composition to a base material, the infrared rays permeable curable composition of this invention may contain the adhesion | attachment adjuvant of (F) component as an arbitrary component.

As an adhesion | attachment adjuvant, it is an organic compound containing at least 1 or several of the functional group which consists of one or more (meth) acryl group, an epoxy group, an alkoxy silyl group, an amide group, and a carboxylic anhydride group in 1 molecule, A specific example is the following Same as

In addition, (F) component is distinguished from (C) component in the point which has the said functional group.

As an adhesion | attachment adjuvant, what contains organosiloxane skeleton can be used, As a specific example, Vinyl trimethoxysilane (brand name: KBM-1003, Shin-Etsu Chemical Co., Ltd. make), (gamma)-(glycidyl) Oxypropyl) trimethoxysilane (brand name: KBM-403, Shin-Etsu Chemical Co., Ltd.), (gamma)-(methacryloxypropyl) trimethoxysilane (brand name: KBM-503, Shin-Etsu Chemical Co., Ltd.) High School Co., Ltd.) etc. are mentioned.

Moreover, the siloxane compound represented by each structural formula shown below can also be used suitably as an adhesion | attachment adjuvant.

Moreover, the adhesion | attachment adjuvant which does not contain the organosiloxane skeleton can also be used, As a specific example, allyl glycidyl ether, vinylcyclohexene monooxide, 2-ethyl allyl malonate, allyl benzoate, diallyl phthalate, pyromellitic acid Tetraallyl ester (brand name: TRIAM805, Wako Junyaku Chemical Industries, Ltd.), triallyl isocyanurate, etc. are mentioned.

In addition, the adhesion | attachment adjuvant of (F) component may be used individually by 1 type, or may be used in combination of 2 or more type.

The compounding quantity of (F) component becomes like this. Preferably it is 0.05-10 mass parts, More preferably, it is 0.05-5 mass parts with respect to a total of 100 mass parts of (A) component and (C) component.

[7] (G) components

In order to suppress the oxidative deterioration of a composition and hardened | cured material, the infrared ray permeable curable composition of this invention may contain antioxidant of (G) component as an arbitrary component.

As antioxidant, it can select from a well-known thing suitably, and can use, for example, a hindered phenol compound and a hindered amine compound can be used.

Specific examples thereof include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone and 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butyl Phenol), 1,3,5-tris [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione, N ', N', N '', N '' '-tetrakis [4,6-bis [(1,2,2,6,6-pentamethylpiperidine -4-yl) (butyl) amino] -1,3,5-triazin-2-yl] [N ', N' '-ethylenebis (propane-1,3-diamine)], N-N'- N ''-N '' '-tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazine-2- 1) -4,7- diazadecan-1,10-diamine), These can be used even if single 1 type also combines 2 or more types.

The compounding quantity of (G) component becomes like this. Preferably it is 0.05-10 mass parts, More preferably, it is 0.05-5 mass parts with respect to a total of 100 mass parts of (A) component and (C) component.

In addition, the infrared permeable curable composition of this invention is a component other than the said (A)-(D) component and (E)-(G) component used as needed, unless the objective of this invention is impaired. You may contain it.

As an example of another component, inorganic fillers, such as fumed silica, a flame retardant, a pigment, etc. for improving strength are mentioned.

As a hardening method and hardening conditions of the infrared rays permeable curable composition of this invention demonstrated above, a well-known method and conditions can be employ | adopted. For example, it can harden on the conditions of 10 minutes-5 hours at 100-180 degreeC.

As for the hardened | cured material of the infrared permeable curable composition of this invention, it is preferable that the average light transmittance of wavelength 350-650 nm is 40% or less, and the average light transmittance of wavelength 800-900 nm or more is 60% or more, and the average light transmittance of wavelength 350-650 nm. As for this 20% or less, it is more preferable that the average light transmittance of wavelength 800-900 nm is 70% or more.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.

[1] Synthesis of Addition Reaction Products of Component (A)

Synthesis Example 1

To a 5 L four-necked flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, vinylnorbornene (trade name: V0062, manufactured by Tokyo Chemical Industries, Ltd .; 5-vinylbicyclo [2.2.1] hept-2 1,785 g (14.88 moles) of toluene and approximately 455 g of toluene were added and the 455 g of toluene was heated to 85 ° C. using an oil bath. .

3.6 g of carbon powder carrying 5 mass% platinum metal was added thereto, and 1,698 g (8.75 mol) of 1,4-bis (dimethylsilyl) benzene was added dropwise over 180 minutes while stirring. After completion | finish of dripping, after stirring at 110 degreeC for 24 hours, it cooled to 25 degreeC. Thereafter, the platinum metal-carrying carbon was removed by filtration, and toluene and excess vinylnorbornene were distilled off under reduced pressure to obtain a colorless transparent oily product (A-1) (viscosity at 25 ° C: 12,820 mPa · s) 3,362 g was obtained.

As a result of FT-IR, NMR and GPC analysis of the reaction product, about 41 mol% of the compound of n = 0, about 32 mol% of the compound of n = 1, and about 27 mol% of the compound of n = 2 in the following formula Was a mixture of. In addition, the content of the addition reactive carbon-carbon double bond in the mixture was 0.36 mol / 100 g.

[2] production of infrared transmissive curable composition

[Examples 1-1, 1-2 and Comparative Examples 1-1, 1-2]

The following (A)-(G) component was mixed with the compounding quantity (mass part) shown in Table 1, and the composition was produced.

(A) component

(A-1) Addition reaction product (mixture) obtained in synthesis example 1

(B) component

(B-1) Plast Black 8995 (product made by Arimoto Kagaku Kogyo Co., Ltd.)

(B-2) SDO-2 (made by Arimoto Kagaku Kogyo Co., Ltd.)

(B-3) Plast Orange 8150-2 (made by Arimoto Kagaku Kogyo Co., Ltd.)

(C) component

(C-1) Organohydrogenpolysiloxane represented by following formula (9)

(C-2) Organohydrogenpolysiloxane represented by following formula (10)

Where the arrangement of siloxane units in parentheses is random, alternating, or block)

(C-3) The compound represented by following formula (11).

(C-4) The compound represented by following formula (12).

(D) component

(D-1) Toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane (0.5 mass% in terms of platinum)

(D-2) Diluting platinum hexachloride 1,3-divinyl tetramethyldisiloxane with linear dimethylpolysiloxane represented by following formula (13) (1 mass% in platinum conversion, viscosity 600mPa * s)

(E) component

(E-1) ethynylmethyldecylcarbinol

(E-2) The compound represented by following formula (14).

(F) component

(F-1) The compound represented by following formula (15).

(G) component

(G-1) SABOSTAB UV 119 (product made in SABO company)

(G-2) IRGANOX 3114 (product of BASF Corporation)

*): {Sum of the number of SiH groups of component (C)} / {sum of the number of addition-reactive carbon-carbon double bonds of component (A)}

Comparative Example 1-3

Formula 75 organopolysiloxane represented by 16 parts by mass of the _{(CH 2 = CH (CH 3} ) 2 SiO 1/2) 1.2 ((CH 3) Si 1/2) 7.4 (SiO 2/2) 10 25 mass parts of branched silicone resin whose vinyl group amount is 0.085 mol / 100g, 0.15 mass part of said (B-1), 0.04 mass part of (B-3), and organohydrogen represented by following formula (17) 2.6 mass parts of siloxane compounds, 0.05 mass part of said (D-2), and 0.04 mass part of said (E-1) were mixed, and the composition was manufactured ({the sum of the number of SiH groups in the said composition} / {addition reactive carbon- Molar ratio of the sum of the number of carbon double bonds is 1.5).

[3] cured products

[Examples 2-1, 2-2 and Comparative Examples 2-1 to 2-3]

The compositions prepared in Examples 1-1 and 1-2 and Comparative Examples 1-1 to 1-3 were introduced into molds to have a thickness of 2 mm and 0.4 mm, respectively, at 150 ° C. for 4 hours. Cured.

About the obtained hardened | cured material, linear light transmittance was measured using the U-3310 type spectrophotometer (made by Hitachi Seisakusho Co., Ltd.), and the average light transmittance of wavelength 350-650 nm and the average light transmittance of 800-900 nm wavelength are measured. Each was obtained. The results are shown in Table 2. Moreover, each hardened | cured material of Example 2-1, the hardened | cured material of film thickness 0.4mm of Example 2-2, the hardened | cured material of film thickness 2.0mm of Comparative Example 2-1, and the film thickness of 2.0mm of Comparative Example 2-1 The ultraviolet visible transmission spectrum of hardened | cured material of is shown to FIGS. 1-5, respectively.

As shown in Table 2, in the cured products produced in Examples 2-1 and 2-2, light of wavelength 350 to 650 nm was blocked even in a thin film (0.4 mm thickness), and in a thick film (2 mm thickness). It was confirmed that the transmittance of near infrared rays of 800 to 900 nm was excellent.

On the other hand, in the hardened | cured material produced by the comparative examples 2-1 and 2-2 which do not add dye, it turned out that visible light cannot be blocked.

In addition, in the hardened | cured material of the comparative example 2-3 which does not use the (A) component and (C) component of this invention, although the addition amount of dye is significantly small compared with an Example, of the dye in hardened | cured material In view of the aggregate observed, it was suggested that the compatibility with the dye is insufficient. In particular, in the case where the cured product is a thin film (0.4 mm thick), it was confirmed that the visible light blocking property significantly decreased.

Claims (5)

The following (A)-(D) component is included, The infrared permeable curable composition characterized by the above-mentioned.
(A) A polycyclic hydrocarbon having (a) a compound having two hydrogen atoms bonded to the silicon atom represented by the following formula (1) in one molecule, and (b) two additional reactive carbon-carbon double bonds in one molecule. Addition reaction product with and addition reaction product having two addition reactive carbon-carbon double bonds in one molecule

(In formula, R <^1> may respectively independently be substituted by the halogen atom, the cyano group, or the glycidoxy group, and represents the C1-C12 monovalent hydrocarbon group or the C1-C6 alkoxy group, and R ² represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms)
(B) A dye having an absorption band in a region of wavelength 350 to 650 nm and transmitting at least a part of light having a wavelength of 800 to 900 nm.
(C) an organosilicon having a hydrogen atom bonded to at least two silicon atoms in one molecule and not having a group selected from an addition reactive carbon-carbon double bond containing group, an epoxy group, an alkoxysilyl group, an amide group and a carboxylic anhydride group compound
(D) hydrosilylation reaction catalyst The infrared transmissive curable type according to claim 1, wherein the polycyclic hydrocarbon is at least one of 5-vinylbicyclo [2.2.1] hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene. Composition, The infrared rays permeable curable composition according to claim 1 or 2, wherein the component (A) is represented by the following formula (2).

(Wherein n represents an integer of 0 to 50) As a hardened | cured material of the infrared rays permeable curable composition of Claim 1 or 2,
Hardened | cured material of both thickness 2mm and 0.4mm whose average light transmittance of wavelength 350-650 nm is 40% or less, and the average light transmittance of wavelength 800-900 nm is 60% or more. The optical semiconductor device which has an optical semiconductor element sealed by the hardened | cured material of the infrared rays permeable curable composition of Claim 1 or 2.

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