TWI834881B - Addition-hardening polysilicone resin composition, method of manufacturing the composition, and optical semiconductor device - Google Patents

Abstract

The present invention provides an addition-hardened polysiloxane resin composition that can impart a low refractive index to a polysiloxane cured product that has high transparency and less hardness change and less mass loss even under high-temperature conditions. The addition-hardening polysiloxane resin composition contains (A) an organopolysiloxane having an alkenyl group and a fluoroalkyl group, (B) an organosilicon compound having a hydrogen atom, and (C) a platinum group in a specific proportion. Metal catalyst, and (D) i) organopolysiloxane with fluoroalkyl group, ii) carboxylate of rare earth elements containing cerium, and iii) (R ⁴ O) ₄ Ti (in the formula, R ⁴ is a reaction product of at least one of a compound represented by a homogeneous or heterogeneous monovalent hydrocarbon group) or a partial hydrolysis condensate thereof.

Description

Addition curable polysilicone resin composition, method of manufacturing the composition, and optical semiconductor device

The present invention relates to an addition-hardening polysiloxane resin composition, a manufacturing method of the composition, and an optical semiconductor device.

Recently, the use of polysilicone resin has been proposed as a die bonding material for light emitting diode (hereinafter referred to as "LED") elements (Patent Documents 1 to 3). Since polysilicone resin has better heat resistance, weather resistance, and discoloration resistance than conventional epoxy resins, it is recommended to use blue LEDs and white LEDs in the center.

However, these previous die-bonding materials made of polysilicone resin materials are mainly made of methyl-based polysilicone resin compositions, which do not fully satisfy the optical element performance, especially the light transmittance at 400 nm is not necessarily high. On the other hand, Patent Document 4 proposes addition hardening of an elastomer having a low refractive index, good transparency, and excellent light extraction efficiency by using a polysiloxane composition containing a perfluoroalkyl group bonded to a silicon atom. Type polysiloxane composition and sealing material for optical components made of the composition. However, the weight of fluoropolysiloxane resins with perfluoroalkyl groups decreases significantly at high temperatures, and the hardness increases accordingly. Reduced weight and increased hardness can cause serious errors such as cracks even in LEDs, and we hope to solve them.

Patent Document 5 reports a heat-resistant silicone rubber composition containing a rare earth salt mixture of 2-ethylhexanoic acid, and reports that the transmittance of a 2 mm thick sheet for light with a wavelength of 600 nm is 90% or more. However, this heat-resistant silicone rubber composition has a problem of poor light transmittance for short-wavelength light near a wavelength of 400 nm. In addition, these heat resistance-imparting agents are incompatible with fluoropolysiloxane resins having perfluoroalkyl groups, and may separate over time, resulting in the failure to exhibit the heat resistance of the cured product, or the transparency may be impaired. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 11-1619 [Patent Document 2] Japanese Patent Application Publication No. 2002-265787 [Patent Document 3] Japanese Patent Application Publication No. 2004-186168 [Patent Document 4] Japanese Patent Application Publication No. 2013-010881 [Patent Document 5] Japanese Patent No. 5422755

[Problem to be solved by the invention]

The present invention was completed in order to solve the above-mentioned problems, and its object is to provide an addition-cured polysiloxane cured material that can provide a low refractive index, has high transparency even when used under high-temperature conditions, and has less hardness change and less mass loss. Polysilicone resin composition. [Means used to solve problems]

In order to achieve the above object, the present invention provides an addition-hardening polysiloxy resin composition, which contains: (A) one molecule having two or more alkenyl groups bonded to silicon atoms and one or more alkenyl groups bonded to silicon Organopolysiloxane whose atoms are represented by CF ₃ -(CF ₂ ) _a -(CH ₂ ) _b - (but a is an integer of 3 or more and b is an integer of 1 or more), (B) in one molecule Organosilicon compounds having more than two hydrogen atoms bonded to silicon atoms: with respect to one alkenyl group bonded to a silicon atom in the component (A), one of the alkenyl groups bonded to a silicon atom in the component (B) above The amount of hydrogen atoms is 0.5 to 5.0, (C) Platinum group metal catalyst: relative to the total mass of the aforementioned component (A) and the aforementioned component (B), it is 1 to 500 ppm based on the mass of the platinum group metal. amount, and (D) the reaction product of the following components i), ii) and iii): 0.01 to 20 parts by mass relative to 100 parts by mass of the total of the component (A) and component (B), i) in The viscosity at 25℃ is 10~10,000mPa·s and one molecule has at least one group represented by CF ₃ -(CF ₂ ) _j -(CH ₂ ) _k - bonded to a silicon atom (but j is 3 The above integers, k is an integer above 1) organopolysiloxane, ii) Carboxylate of rare earth elements containing cerium: cerium is in an amount of 0.05 to 5 parts by mass relative to 100 parts by mass of the component i) above, iii) At least one of the compounds represented by (R ⁴ O) ₄ Ti (in the formula, R ⁴ is the same or different monovalent hydrocarbon group) or its partial hydrolysis condensate: relative to 100 parts by mass of the aforementioned i) component, titanium The amount is 0.05 to 5 parts by mass.

This addition-curable polysilicone resin composition can provide a low refractive index, and can be used as a polysiloxane cured product with excellent light transmittance near a wavelength of 400 nm and less hardness change and mass loss even under high-temperature conditions.

The aforementioned component (B) is preferably a group represented by CF ₃ -(CF ₂ ) _f -(CH ₂ ) _g - having one or more bonds to a silicon atom in one molecule (but f is an integer above 0, g is an integer above 1).

When the component (B) has the perfluoroalkyl group, the addition-curable polysiloxane resin composition can be provided with a low refractive index, and can have excellent light transmittance and change in hardness even when used under high temperature conditions near a wavelength of 400 nm. and hardened materials with less mass loss.

Preferably, in the aforementioned component (A), a=5 and b=2, and in the aforementioned component (D), j=5 and k=2.

If the aforementioned component (A) uses a specific organopolysiloxane having the aforementioned fluoroalkyl group, and the aforementioned component (D) is produced using a specific organic polysiloxane having the aforementioned fluoroalkyl group, the addition curing type The polysilicone resin composition can be used to provide a low refractive index, excellent light transmittance near a wavelength of 400 nm, and less hardness change and mass loss even under high-temperature conditions.

The refractive index of the addition curable polysiloxy resin composition at 25° C. for light with a wavelength of 589 nm is 1.37 or less. If the addition-curing polysilicone resin composition exhibits a refractive index below the aforementioned specific value, the addition-curing polysilicone resin composition can provide a cured polysilicone product with a higher light extraction efficiency.

Furthermore, the present invention provides a method for manufacturing the above-mentioned addition curable polysiloxane resin composition, which includes reacting the above-mentioned i), ii) and iii) components at a temperature of 150°C or above while injecting oxygen-containing gas. The steps for component (D) mentioned above.

By this method of manufacturing the addition-hardening polysiloxane resin composition, it is possible to manufacture a composition that can be given a low refractive index, has excellent light transmittance near a wavelength of 400 nm, and has less hardness change and less mass loss even when used under high temperature conditions. An addition curable polysiloxane resin composition that is a cured product.

Furthermore, the present invention provides a polysilicone cured product, which is a cured product of the above-mentioned addition curable polysilicone resin composition.

The polysiloxane hardened material has a low refractive index, has excellent light transmittance at wavelengths near 400 nm, and has less hardness change and less mass loss even when used under high temperature conditions.

The polysiloxane hardened material preferably has a light transmittance of 80% or more at a wavelength of 400 nm with an optical path length of 2 mm.

The polysiloxane cured material exhibiting a light transmittance above the above-mentioned specific value is one that has better light transmittance even when used under high temperature conditions with a wavelength near 400 nm.

In addition, the present invention provides an optical semiconductor device in which an optical semiconductor element is bonded with the above-mentioned polysiloxane hardened material, and an optical semiconductor device in which an optical semiconductor element is sealed with the above-mentioned polysilicone hardened material. By.

These optical semiconductor devices are highly reliable. [Effects of the invention]

The addition-curable polysiloxy resin composition of the present invention can provide a low refractive index, excellent light transmittance around a wavelength of 400 nm even when used under high temperature conditions, and a cured product with less change in hardness and less loss in mass. Therefore, the addition curable polysiloxy resin composition of the present invention can be used as a material for protecting and sealing LED elements, a material for changing and adjusting wavelength, a crystal bonding material or a constituent material of a lens, or other optical devices or optical parts. The materials used are particularly useful.

As mentioned above, there is a demand for the development of an addition-hardening polysiloxane resin composition that has a low refractive index, has excellent light transmittance at a wavelength near 400 nm even when used under high temperature conditions, and has less hardness change and less mass loss.

As a result of repeated active examinations on the above-mentioned issues, the present inventors found that the above-mentioned issues can be achieved if the addition-curable polysiloxane resin composition includes the following (A) to (D) and is suitable as a material for LEDs. etc., thus completing the present invention.

That is, the present invention is an addition-hardening polysiloxy resin composition, which contains: (A) One molecule has more than two alkenyl groups bonded to silicon atoms and one or more alkenyl groups bonded to silicon atoms. Organopolysiloxane with a group represented by CF ₃ -(CF ₂ ) _a -(CH ₂ ) _b - (where a is an integer of 3 or more and b is an integer of 1 or more), (B) having 2 in one molecule Organosilicon compounds with more than one hydrogen atom bonded to a silicon atom: with respect to one alkenyl group bonded to a silicon atom in the component (A), the hydrogen atom bonded to a silicon atom in the component (B) The amount of atoms is 0.5 to 5.0. (C) Platinum group metal catalyst: The amount is 1 to 500 ppm based on the mass of the platinum group metal relative to the total mass of the aforementioned component (A) and the aforementioned component (B). and (D) the reaction product of the following components i), ii) and iii): 0.01 to 20 parts by mass relative to 100 parts by mass of the total of the component (A) and component (B), i) at 25°C The viscosity below is 10~10,000mPa·s and one molecule has at least one group represented by CF ₃ -(CF ₂ ) _j -(CH ₂ ) _k - bonded to the silicon atom (but j is 3 or more an integer, k is an integer above 1) organopolysiloxane, ii) carboxylate of rare earth elements containing cerium: cerium is in an amount of 0.05 to 5 parts by mass relative to 100 parts by mass of the component i) above, iii) At least one of the compounds represented by (R ⁴ O) ₄ Ti (in the formula, R ⁴ is the same or different monovalent hydrocarbon group) or its partial hydrolysis condensate: relative to 100 parts by mass of the aforementioned i) component, titanium becomes 0.05 ~5 parts by mass.

The present invention will be described in detail below, but the present invention is not limited thereto. [Addition-curing polysilicone resin composition] The addition-curing polysilicone resin composition of the present invention contains the components (A) to (D) described below. (A) One molecule has more than two alkenyl groups bonded to silicon atoms and more than one group represented by CF ₃ -(CF ₂ ) _a -(CH ₂ ) _b - bonded to silicon atoms (but (a is an integer of 3 or more, b is an integer of 1 or more) organopolysiloxane, (B) Organosilicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule, (C) Platinum group Metal-based catalyst, (D) The reaction product of the following i), ii) and iii) components, i) has a viscosity of 10~10,000mPa·s at 25°C and has at least 1 bond in one molecule Organopolysiloxane with a silicon atom represented by CF ₃ -(CF ₂ ) _j -(CH ₂ ) _k - (but j is an integer above 3 and k is an integer above 1), ii) Cerium-containing rare earth Element-like carboxylates, iii) At least one of the compounds represented by (R ⁴ O) ₄ Ti (in the formula, R ⁴ is the same or different monovalent hydrocarbon group) or its partial hydrolysis condensate.

Each ingredient is explained in detail below. <(A) Component> (A) Component has two or more alkenyl groups bonded to silicon atoms and one or more CF ₃ -(CF ₂ ) _a -(CH _{2 )} bonded to silicon atoms in one molecule. ) Organopolysiloxane represented by _b - (but a is an integer of 3 or more, b is an integer of 1 or more), contributes to the low temperature of the addition-curable polysiloxane resin composition and the polysiloxane cured product Refractive index. (A) The component may be linear or branched, and may be liquid, waxy or solid.

Examples of the alkenyl group bonded to the silicon atom in component (A) include vinyl, allyl, butenyl, pentenyl, hexenyl, etc., and preferably have 2 to 10 carbon atoms, especially 2 to 6 alkenyl groups, more preferably vinyl groups. a is an integer of 3 or more, preferably an integer of 3 to 9, more preferably 5. When a is less than 3, there is a risk that the refractive index cannot be sufficiently low. b is an integer of 1 or more, preferably an integer of 1 to 5, and more preferably 2. When b is 0, the manufacturing quality is poor.

The group represented by CF ₃ -(CF ₂ ) _a -(CH ₂ ) _b - is preferably a group represented by CF ₃ -(CF ₂ ) ₃ -(CH ₂ ) ₂ -, a group represented by CF ₃ -( CF ₂ ) ₅ -(CH ₂ ) ₂ - represents the base.

In the component (A), in addition to the above-mentioned fluoroalkyl group, it may also have a group represented by CF ₃ -(CF ₂ ) _d -(CH ₂ ) _e - bonded to the silicon atom (but d is an integer from 0 to 2 , e is an integer from 1 to 5), based on raw material blending or synthesis, it is preferably a group represented by CF ₃ -(CH ₂ ) ₂ -.

The substituent other than the alkenyl group and fluoroalkyl group bonded to the silicon atom in component (A) is not particularly limited, but is preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl and butyl, cycloalkyl groups such as cyclohexyl and cyclopentyl, aryl groups such as phenyl, tolyl and xylyl, and benzyl. Aralkyl groups such as chloromethyl, phenylethyl, etc., halogenated alkyl groups such as chloromethyl, chloropropyl, chlorocyclohexyl, etc. An alkyl group is preferred, and a methyl group is more preferred.

Examples of the component (A) include linear organopolysiloxane represented by the following formula (1). (In the formula, R ₁ is the same or different alkenyl group, R ₂ is a substituted or unsubstituted monovalent hydrocarbon group with 1 to 8 carbon atoms other than the same or different alkenyl group, and R _f1 is the same or different fluorinated hydrocarbon group respectively. Alkyl group, at least one of R _f1 is a group represented by CF ₃ -(CF ₂ ) _a -(CH ₂ ) _b - (but a is an integer of 3 or more, and b is an integer of 1 or more). w is 1 to 3 are integers, x, y, and z are respectively the integers of x≧0, y≧1, and z≧0. The siloxane units in brackets with x, y, and z can be arranged in any order).

x is an integer above 0, preferably an integer between 0 and 10, and y is an integer above 1, preferably between 2 and 20, and more preferably between 5 and 10. z is an integer above 0, preferably 0 to 10, more preferably 0 to 5. x+y+z is preferably 1~30, more preferably 2~20, and more preferably 5~12. And the value of y/(x+y+z) is preferably in the range of 1/20~1/1, more preferably in the range of 1/10~1/1, and even more preferably in the range of 1/5~1/1.

Moreover, _{the component} (A ₎ may be a branched organopolysiloxane ( _R2 is the same as above). These branched organopolysiloxanes may further contain (R ₂ ) ₂ SiO _2/2 units (D units) such as methylvinylsiloxy units, dimethylsiloxy units, and dimethylethylene units. (R ₂ ) ₃ SiO _1/2 unit (M unit) (R ₂ is the same as above), and the total content of Q unit and T unit is preferably (A ) The total siloxane units in the component account for more than 5 mol%, more preferably 10 to 95 mol%, more preferably 20 to 80 mol%, particularly preferably 20 to 60 mol%.

From the viewpoint of ease of handling, the weight average molecular weight of component (A) is appropriately in the range of 500 to 100,000. Specific examples of the component (A) include organopolysiloxane represented by the following structural unit ratios. (In the above formula, the order of siloxane units is arbitrary).

＜(B)Component＞ Component (B) is an organic silicon compound having two or more hydrogen atoms bonded to silicon atoms (i.e., SiH groups) in one molecule. The component (B) functions as a cross-linking agent that cross-links by hydrosilylation reaction with the alkenyl group contained in the component (A). Component (B) is not particularly limited if it is an organosilicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule. Examples include organohydrogensilanes, organohydrogenpolysiloxanes, etc. However, organohydrogen polysiloxane is preferred. The molecular structure of organohydrogen polysiloxane is not particularly limited, and examples include linear, cyclic, branched chain, three-dimensional network structure (resin-like), and the like.

The number of SiH groups in component (B) is preferably 2 to 200 per molecule, more preferably 3 to 100. When the organosilicon compound of component (B) has a linear or branched chain structure, the SiH groups may be located at only one of the molecular chain terminals and the non-terminal portion of the molecular chain, or they may be located at both of them. The number of silicon atoms (degree of polymerization) in one molecule of the organosilicon compound of component (B) is preferably 2 to 1,000, more preferably 3 to 200, and still more preferably 4 to 100. Furthermore, the organosilicon compound of component (B) is preferably liquid at 25°C, and the kinematic viscosity at 25°C measured by a Cannon-Fenske viscometer is preferably 1 to 1,000 mm ² /s, more preferably 10 to 300 mm. ² /s.

In component (B), the substituent bonded to the silicon atom other than the SiH group is not particularly limited, but it is preferable that it does not have an aliphatic unsaturated group, and examples thereof include an unsubstituted monovalent hydrocarbon group, or a halogen atom (for example, Fluorine atom, chlorine atom, bromine atom), epoxy-containing group (such as epoxy group, glycidyl group, glycidoxy group), alkoxy group (such as methoxy group, ethoxy group, propoxy group, butyl group) Oxygen group) and other substituted monovalent hydrocarbon groups. Preferable examples of these substituted or unsubstituted monovalent hydrocarbon groups are alkyl groups with 1 to 6 carbon atoms, aryl groups with 6 to 10 carbon atoms, more preferably methyl or ethyl groups, or examples of these groups. A group substituted by the substituents exemplified above. Furthermore, having an epoxy group-containing group and/or an alkoxy group as a substituent of the monovalent hydrocarbon group can impart adhesiveness to the cured product of the addition-curable polysiloxy resin composition of the present invention.

The substituent bonded to silicon in the component (B) preferably has a group represented by CF ₃ -(CF ₂ ) _f -(CH ₂ ) _g - from the viewpoint of further lowering the refractive index (but f is 0 The above integers, g is an integer above 1). The group represented by CF ₃ -(CF ₂ ) _f -(CH ₂ ) _g - is preferably CF ₃ -(CH ₂ ) ₂ -, CF ₃ -(CF ₂ ) ₃ -(CH ₂ ) ₂ -, CF ₃ -(CF ₂ ) ₅ -(CH ₂ ) ₂ - represents the base.

Specific examples of component (B) include organohydrogen polysiloxane represented by the following formula (2). (In the formula, R ³ are the same or different respectively, and are substituted or unsubstituted monovalent hydrocarbon groups without alkenyl groups. h and i satisfy 0.7≦h≦2.1, 0.001≦i≦1.0 and 0.8≦h+i≦ 3.0, preferably a number satisfying 1.0≦h≦2.0, 0.01≦i≦1.0 and 1.5≦h+i≦2.5).

The substituted or unsubstituted monovalent hydrocarbon group as R ³ is not particularly limited as long as it does not have an alkenyl group, but it is preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl and butyl, cycloalkyl groups such as cyclohexyl and cyclopentyl, aryl groups such as phenyl, tolyl and xylyl, and benzyl groups. , aralkyl groups such as phenylethyl, chloromethyl, chloropropyl, chlorocyclohexyl, CF ₃ -(CF ₂ ) _e -(CH ₂ ) _f - (but e is an integer above 0, and f is 1 Integers above), etc.

Among these, R ³ is preferably an alkyl group or a halogenated alkyl group, more preferably a methyl group, and CF ₃ -(CH ₂ ) ₂ -, CF ₃ -(CF ₂ ) ₃ -(CH ₂ ) ₂ - , CF ₃ -(CF ₂ ) ₅ -(CH ₂ ) ₂ - represents the base.

The organohydrogensiloxane represented by the above-mentioned average composition formula (2) may also contain monoorganosiloxane units (M units), diorganosiloxane units (D units), and triorganosiloxane units that do not contain SiH groups. Units (T units) and/or SiO _4/2 units (Q units), among all organosiloxane units, preferably 30 to 70 mol% are methylhydrogensiloxane units.

Specific examples of component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(hydrodimethyl methylsiloxy)methylsiloxane, tris(hydrodimethylsiloxy)phenylsiloxane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane·dimethylsiloxane cyclic copolymer, Trimethylsiloxy-terminated methyl hydrogen polysiloxane at both ends of the molecular chain, trimethylsiloxy-terminated dimethylsiloxane/methylhydrogensiloxane copolymer at both ends of the molecular chain, molecular chain Copolymer of diphenylsiloxane and methylhydrogensiloxane terminated with trimethylsiloxy groups at both ends of the molecular chain, methylphenylsiloxane and methylhydrogensiloxane terminated with trimethylsiloxy groups at both ends of the molecular chain Oxane copolymer, trimethylsiloxy terminated dimethylsiloxane, methylhydrosiloxane, methylphenylsiloxane copolymer at both ends of the molecular chain, trimethylsiloxy terminated at both ends of the molecular chain Group-terminated dimethylsiloxane, methylhydrogensiloxane, diphenylsiloxane copolymer, dimethylhydrogensiloxy-terminated methylhydrogen polysiloxane at both ends of the molecular chain, Terminal dimethylhydrogensiloxy-terminated dimethylpolysiloxane, both terminal dimethylhydrogensiloxy-terminated dimethylsiloxane and methylhydrogensiloxane copolymers, both molecular chain terminals Terminal dimethylhydrosiloxy group-terminated dimethylsiloxane and methylphenylsiloxane copolymer, both terminal dimethylhydrosiloxy group-terminated dimethylsiloxane and diphenyl groups Siloxane copolymer, dimethylhydrogensiloxy-terminated methylphenyl polysiloxane at both ends of the molecular chain, dimethylhydrogensiloxy-terminated diphenyl polysiloxane at both ends of the molecular chain, molecule Dimethylhydrosiloxy-terminated diphenylsiloxane and methylhydrosiloxane copolymers at both ends of the chain. In each of these exemplary compounds, part or all of the methyl group is replaced by an ethyl group, a propyl group, etc. Other alkyl-substituted organohydrogen polysiloxanes, etc.

As a preferred specific example of component (B), the structural unit ratio [CF ₃ -(CF ₂ ) ₅ -(CH ₂ ) ₂ SiO _3/2 ] _{is 0.25} [H(CH ₃ ) ₂ SiO _1/2 ]. Polysiloxane represented by _0.75 (in the above formula, the order of the siloxane units is arbitrary). (B) Component may be used individually by 1 type, or may use 2 or more types together.

The blending amount of component (B) is 0.5 to 5.0 based on the alkenyl group bonded to the silicon atom in component (A) and the hydrogen atom (Si-H group) bonded to the silicon atom in component (B). The number of hydrogen atoms (Si-H groups) bonded to silicon atoms in component (B) is 0.5 to 5.0 relative to the total number of alkenyl groups bonded to silicon atoms in component (A). times the amount. From the viewpoint of cross-linking balance, the amount is preferably 0.7 to 3.0 times. If it is less than 0.5 times, cross-linking will be insufficient. If it exceeds 5.0 times, cross-linking will be insufficient or excessive, and a cured polysiloxane material with excellent hardness will not be obtained.

＜(C)Component＞ The platinum group metal catalyst of component (C) is a component used to advance and accelerate the hydrosilylation reaction of component (A) and component (B). The platinum group metal catalyst is not particularly limited, and examples thereof include platinum group metals such as platinum, palladium, and rhodium; chlorinated platinic acid, alcohol-modified chlorinated platinic acid, chlorinated platinic acid and olefins, and vinyl silica Platinum compounds such as coordination compounds of alkane or acetylene compounds; platinum group metal compounds such as tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium, etc., but due to their differences with the aforementioned components (A) and (B) It has good compatibility and contains almost no chlorine impurities, so it is better to use chlorinated platinic acid modified with polysiloxane. (C) Component may be used individually by 1 type, or may use 2 or more types together.

The compounding amount of component (C) is 1 to 500 ppm, preferably 3 to 100 ppm, and more preferably 5 to 5 ppm based on the mass of the platinum group metal element relative to the total mass of component (A) and component (B). 40ppm. When the aforementioned blending amount of component (C) is less than 1 ppm, the resulting addition-curable polysiloxane resin composition is not sufficiently hardened. On the other hand, even if the aforementioned blending amount exceeds 500 ppm, the resulting addition-curable polysiloxane composition cannot be further improved. The curing speed of the silicone resin composition is uneconomical.

＜(D)Component＞ Component (D) is a reaction product of the following components i), ii) and iii). It shows high compatibility with the above-mentioned components (A) to (C) and is used to form an addition curable polysiloxane resin. Additive that imparts heat resistance.

i) The viscosity at 25°C is 10~10,000mPa·s and one molecule has at least one group represented by CF ₃ -(CF ₂ ) _j -(CH ₂ ) _k - bonded to a silicon atom (but j is an integer of 3 or more, k is an integer of 1 or more) organopolysiloxane, ii) Carboxylate of rare earth elements containing cerium: cerium is 0.05 to 5 parts by mass relative to 100 parts by mass of component i) Amount, iii) At least one of the compound represented by (R ⁴ O) ₄ Ti (in the formula, R ⁴ is the same or different monovalent hydrocarbon group) or its partial hydrolysis condensate: relative to 100 parts by mass of component i), Titanium is used in an amount of 0.05 to 5 parts by mass.

(i) The viscosity of the organopolysiloxane component at 25°C is 10~10,000 mPa·s, preferably 100~7000 mPa·s. If the viscosity is less than 10 mPa·s, it will volatilize during the reaction. If the viscosity exceeds 10,000 mPa·s, it will become highly viscous and become difficult to handle.

(i) Among the ingredients, in the base represented by CF ₃ -(CF ₂ ) _j -(CH ₂ ) _k -, j is an integer of 3 or more, preferably an integer of 3 to 9, and more preferably 5. When j is less than 3, the compatibility with component (A) is insufficient and the transparency of the addition-cured polysiloxane resin composition and the cured polysiloxane is impaired. k is an integer of 1 or more, preferably an integer of 1 to 5, and more preferably 2. If k is 0, it is not good in terms of manufacturing.

The group represented by CF ₃ -(CF ₂ ) _j -(CH ₂ ) _k - is preferably a group represented by CF ₃ -(CF ₂ ) ₃ -(CH ₂ ) ₂ -, a group represented by CF ₃ -( CF ₂ ) ₅ -(CH ₂ ) ₂ - represents the base.

As a specific example of component i), the structural unit ratio is [(CH ₃ ) ₃ SiO _1/2 ] _0.2 [(CH ₃ )SiO _3/2 ] _0.4 [CF ₃ -(CF ₂ ) ₅ -(CH ₂ ) ₂ SiO _3/2 ] _0.4 represents polysiloxane, etc.

Examples of the carboxylate of rare earth elements as component ii) include salts of cerium and 2-ethylhexanoic acid, naphthenic acid, oleic acid, lauric acid, stearic acid, and the like.

In the component iii), the monovalent hydrocarbon group of R ⁴ can be exemplified by the same ones as those exemplified as R ² in the aforementioned formula (1), preferably the carbon number of methyl, ethyl, propyl, butyl, etc. 1~4 alkyl groups. Examples of the titanium compound as the component iii) include titanium tetraalkoxides such as tetra-n-butyl titanate and hydrolysis condensates thereof.

Component (D) is a reaction product obtained by reacting the aforementioned components i), ii), and iii) at a temperature of 150° C. or higher while introducing oxygen-containing gas. The oxygen-containing gas preferably contains 5 volume % or more of oxygen relative to the entire gas supplied by bubbling. A mixed gas of an inert gas such as nitrogen or argon and oxygen, or air can be used.

The compounding amount of component (D) is 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the total of component (A) and component (B). If the blending amount of component (D) exceeds the aforementioned range, the resulting addition-curable polysiloxane resin composition may be colored or the hardness of the polysiloxane cured product may decrease. Furthermore, if the blending amount of component (C) is lower than the aforementioned range, sufficient heat discoloration resistance cannot be obtained.

＜Other ingredients＞ In addition to the aforementioned components (A) to (D), the addition curable polysiloxy resin composition of the present invention may also contain other components exemplified below.

(reaction inhibitor) In the addition curable polysiloxy resin composition of the present invention, a conventionally known reaction inhibitor (reaction control agent), which is a compound having a curing inhibitory effect on the addition reaction catalyst of component (C), can be used if necessary. Examples of the reaction inhibitor include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; sulfur-containing compounds; acetylene compounds; and hydrogen peroxide compounds. ; Maleic acid derivatives, etc. The degree of the hardening inhibitory effect of reaction inhibitors varies greatly depending on the chemical structure of the reaction inhibitors. Therefore, the amount of the reaction inhibitors is preferably adjusted to the optimal amount for each reaction inhibitor used. Usually, it is preferable that it is 0.001~5 parts by mass based on 100 parts by mass of the total of component (A), component (B), component (C) and component (D).

(Adhesion imparting agent) The addition curable polysiloxy resin composition of the present invention may also contain an adhesive agent for improving its adhesiveness. Examples of the adhesiveness-imparting agent include silane coupling agents and hydrolysis condensates thereof. Examples of the silane coupling agent include epoxy group-containing silane coupling agents, (meth)acrylic acid group-containing silane coupling agents, isocyanate group-containing silane coupling agents, isocyanurate group-containing silane coupling agents, and amine group-containing silane coupling agents. As for silane coupling agents, mercapto group-containing silane coupling agents, etc., it is generally known that 0.1 to 20 parts by mass is preferably used, and 0.3 to 10 parts by mass is more preferably used based on 100 parts by mass of the total of component (A) and component (B). In addition, although the adhesiveness-imparting agent has the above-mentioned adhesiveness functional group, it may also contain an alkenyl group or a hydrogen atom bonded to a silicon atom. In this case, a hydrosilylation reaction occurs with the component (A) and the component (B), and is incorporated into the reaction system.

(filler) The addition curable polysiloxy resin composition of the present invention can also be filled with inorganic fillers such as crystalline silica, hollow fillers, and sesquioxane, and these fillers are formed by organic alkoxysilane compounds. , fillers for surface hydrophobization of organosilicone compounds such as organochlorosilane compounds, organosilazane compounds, low molecular weight siloxane compounds, etc., polysilicone rubber powder, polysiloxane resin powder, etc. As this component, it is particularly preferable to use a filler that imparts thixotropy. By imparting thixotropy, a polysiloxane curing agent with excellent workability and mechanical properties can be obtained.

The addition curable polysiloxy resin composition of the present invention can be prepared by mixing the aforementioned components (A) to (D) and other components if necessary using a conventional method such as a planetary mixer. The addition curable polysiloxy resin composition of the present invention can also be prepared by separately preparing the first component consisting of the aforementioned component (A), component (C), component (D) and other components as needed, and A two-dose composition in which the first component and the second component are mixed before use. In addition, the first agent and the second agent may have components used in common. By using the addition-hardening polysiloxane resin composition as a two-part form, storage stability can be further ensured.

The refractive index (nD25) of light with a wavelength of 589 nm at 25° C. of the addition-hardening polysiloxy resin composition of the present invention is preferably 1.40 or less. If the addition-curing polysilicone resin composition exhibits a refractive index below the above-mentioned specific value, the addition-curing polysilicone resin composition can provide a cured polysilicone product with a higher light extraction efficiency.

[hardened material] Furthermore, the present invention provides a cured product (polysilicone cured product) of the addition-curable polysilicone resin composition. The polysiloxane hardened material is highly transparent even when used under high temperature conditions, has little hardness change and mass loss, and is particularly useful as a sealing material for LED components and the like. In particular, since the addition curable polysiloxane resin composition of the present invention contains a fluoroalkyl group, etc. in the components (A), (D), and optionally (B), it can obtain low refractive index and light transmittance. It is a polysiloxane hardened material that can improve light extraction efficiency and has excellent light extraction efficiency.

The light transmittance of the cured polysiloxane of the present invention at a wavelength of 400 nm under an optical path length of 2 mm is preferably more than 80%. The addition curable polysiloxane resin composition of the present invention can be cured under conventional conditions. For example, it can be cured at 100 to 180° C. for 10 minutes to 5 hours.

The addition curable polysiloxy resin composition of the present invention can be used as a coating material or sealing material for semiconductor components, especially semiconductor components for optical purposes such as LED components, crystal bonding materials, and protective coating materials for electrical and electronic applications. .

[Optical semiconductor device] Furthermore, the present invention provides an optical semiconductor device in which an optical semiconductor element is bonded or sealed using the polysiloxane cured material. The addition curable polysiloxane resin composition of the present invention can provide a polysiloxane cured product that is highly transparent and has less hardness change and less mass loss even when used under high temperature conditions. Therefore, an optical semiconductor device using the cured polysiloxane becomes highly reliable.

As an example of a method for die bonding an optical semiconductor element using the addition-curing polysilicone resin composition of the present invention, the addition-curing polysilicone resin composition of the present invention is filled in a syringe, applied to a substrate such as a package using a dispenser in a manner such that the thickness in a dry state becomes 5 to 100 μm, and then an optical semiconductor element (e.g., a light-emitting diode) is arranged on the applied addition-curing polysilicone resin composition, and the composition is cured to thereby die bond the optical semiconductor element to the substrate. Alternatively, the addition-curing polysilicone resin composition may be placed on a rubber roller, applied to a substrate in a dry state to a thickness of 5 to 100 μm by squeezing and punching, and then an optical semiconductor element is arranged on the applied addition-curing polysilicone resin composition to cure the composition, thereby bonding the optical semiconductor element to the substrate. The curing conditions of the addition-curing polysilicone resin composition are as described above. In this way, a highly reliable optical semiconductor device can be obtained in which the optical semiconductor element is bonded to the substrate using the polysilicone cured material of the present invention. [Example]

The present invention will be described in detail below using Examples and Comparative Examples, but the present invention is not limited to these. In addition, in the following, the viscosity is the value measured at 25°C using a rotational viscometer, and the dynamic viscosity is the value measured at 25°C using a Cannon-Fenske viscometer. In addition, the abbreviations of each siloxane unit have the following meanings.

[Synthesis Example 1] Into a 3L 4-neck flask equipped with a stirring device, a cooling tube, a dropping funnel and a thermometer, (3,3,4,4,5,5,6,6,7,7,8,8 , 2340.0g of 8-tridecafluorooctyl)trimethoxysilane, 202.5g of hexamethyldisiloxane, 680g of methyltrimethoxysilane, and 52g of methanol. While stirring, 6.6g of methanesulfonic acid was dropped, and then water was dropped. 80.3g. 500 g of hexafluoro-m-xylene was added, and the reaction was carried out at 65° C. for 5 hours, and then 10.7 g of a 50% potassium hydroxide aqueous solution was dropped. Methanol was distilled off by heating, and the reaction was carried out at 120°C for 5 hours. Furthermore, 3.4 g of methane sulfonic acid was added, and neutralization reaction was performed at 110° C. for 2 hours. Then, 6.9 g of KYOWAAD 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25° C. The resulting solution was filtered and concentrated under reduced pressure at 120°C to remove the solvent and obtain an organopolysiloxane with a viscosity of 5,300 mPa·s and a refractive index of 1.35. The structural unit ratio of the NMR spectrum analysis of the obtained organopolysiloxane is M _0.2 T _0.4 T ^F13 _0.4 .

[Synthesis example 2] To 130 parts by weight of the organopolysiloxane obtained in Synthesis Example 1, 13 parts by mass of a turpentine solution of 2-ethylhexanoate containing a cerium rare earth element mixture (rare earth element content 6% by mass) was added with stirring. A mixture of 0.55 parts by mass (based on the amount of cerium) and 2.7 parts by mass of tetra-n-butyl titanate (the mass of titanium is 0.85 times the mass of cerium in the aforementioned 2-ethylhexanoate) was used to obtain a yellow-white dispersion. Air was introduced into the dispersion liquid at a pressure of 0.1 MPa (flow rate: 0.3 L/min), and the dispersion was heated while circulating nitrogen gas in the reaction vessel to remove turpentine. Next, the mixture was heated at 300° C. for 1 hour to obtain a reddish-brown and transparent composition (D-1).

[Comparative Synthesis Example 1] In 130 parts by weight of organopolysiloxane represented by the average formula M ₂ D ^F3 (refractive index 1.38, viscosity 450 mPa·s), 2-ethylhexyl containing a cerium rare earth element mixture was 13 parts by mass of turpentine solution of acid salt (rare earth element content 6% by mass) (0.55 parts in terms of cerium content) and 2.7 parts by mass of tetra-n-butyl titanate (the mass of titanium is 0.55 parts by mass in the aforementioned 2-ethylhexanoate) 0.85 times the mass of cerium), add it while stirring thoroughly to obtain a yellow-white dispersion. Air was introduced into the dispersion liquid at a pressure of 0.1 MPa (flow rate: 0.3 L/min), and the dispersion was heated while circulating nitrogen gas in the reaction vessel to remove turpentine. Next, the mixture was heated at 300° C. for 1 hour to obtain a reddish-brown and transparent composition (D-2).

[Synthesis example 3] The reaction product of platinum hexachloride and 1,3-divinyltetramethyldisiloxane was diluted with an ethanol solution so that the platinum content became 3% by mass, and a platinum catalyst (C-1) was prepared.

[Examples 1 and 2, Comparative Examples 1 and 2] The following components were mixed in the amounts (parts by mass) shown in Table 1 to prepare an addition curable polysilicone resin composition. (A) Ingredients: (A-1) Organopolysiloxane (refractive index 1.36, viscosity 49 Pa・s) expressed by the structural unit ratio T ^F13 _0.35 T _0.53 D ^Vi _0.12

(B) Ingredients: (B-1) Organohydrogen polysiloxane (kinematic viscosity 2.5 mm ² /s) expressed in terms of constituent unit ratio T ^F13 _0.25 M ^H _0.75 (B-2) In terms of constituent unit ratio D ^F13 _0.17 D ^F3 _0.5 M ^H _0.33 represents organohydrogen polysiloxane (dynamic viscosity 230mm ² /s)

(C)Ingredients: (C-1) Platinum catalyst obtained in Synthesis Example 3 (D)Ingredients: (D-1) Composition obtained in Synthesis Example 2 (D-2) Comparative composition obtained in Synthesis Example 1

Other ingredients: (E-1) Compounds represented by the following structural formulas

[Si-H group]/[alkenyl group]: (B) The number of SiH groups in the component relative to one alkenyl group bonded to the silicon atom in the component (A)

The following evaluation was performed on the addition curable polysiloxy resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2, and the results are shown in Table 2. [Appearance] The appearance of each composition was visually observed.

[Refractive index] For each composition, the refractive index (nD50) of light with a wavelength of 589 nm at 25°C was measured using a refractometer (RX-5000 manufactured by ATAGO).

[Light transmittance] The addition-curable polysiloxane resin composition was poured into a mold to a thickness of 2 mm, and the resulting polysiloxane cured product was heated and cured at 150° C. for 2 hours. A spectrophotometer U-3900 (manufactured by Hitachi High-tech Scientific Co., Ltd. ) Measure the light transmittance of straight light with a wavelength of 400 nm at 25°C immediately after the polysiloxane cured product is produced and after the polysiloxane cured product is stored in an environment of 250°C for 250 hours.

[hardness] For the polysiloxane cured product obtained by heating and curing the addition-curable polysiloxane resin composition at 150°C for 2 hours, measurements were made immediately after the polysiloxane cured product was produced and after the polysiloxane cured product was stored in an environment of 250°C. Type A hardness of polysiloxane hardened material at 25°C after 250 hours. The hardness change rate is calculated based on the following formula. (Change rate %) = ((hardness after 250°C, 250 hours) ÷ (hardness just after production) × 100) - 100

[Quality survival rate after heat resistance test] The mass of the cured polysiloxane used for the measurement of the light transmittance was measured after being stored in an environment of 250° C. for 250 hours when the initial mass was set to 100.

As shown in Table 2, it can be seen that the cured products obtained from the addition curable polysiloxane resin compositions of Examples 1 and 2 have excellent transparency and have little change in physical properties in the heat resistance test. On the other hand, since Comparative Example 1 does not contain component (D), the hardness change and mass change in the heat resistance test are large, and the heat resistance is poor. Furthermore, the composition (D-2) of Comparative Example 2 using an organopolysiloxane having a CF ₃ -CH ₂ -CH ₂ - group as a fluoroalkyl group as a reaction component, for the components (A) to (C) The compatibility of the addition-hardened polysiloxane composition is poor, and the transparency of the hardened polysiloxane is also poor, with less changes in hardness and quality.

Furthermore, the present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are illustrative only, and any embodiments having substantially the same structure and exerting the same effects as the technical concept described in the patent application scope of the present invention are included in the technical scope of the present invention.

Claims (8)

An addition-hardening polysiloxy resin composition, characterized by containing: (A) one molecule having more than two alkenyl groups bonded to silicon atoms and more than one CF ₃ - bonded to silicon atoms (CF ₂ ) _a -(CH ₂ ) _b - (but a is an integer from 3 to 9, b is an integer above 1), (B) has 2 or more in one molecule Organosilicon compound with a hydrogen atom bonded to a silicon atom: With respect to the alkenyl group bonded to a silicon atom in component (A), the hydrogen atom bonded to a silicon atom in component (B) is 0.5 to 5.0 The amount of (C) platinum group metal catalyst: relative to the total mass of the aforementioned component (A) and the aforementioned component (B), converted into an amount of 1 to 500 ppm based on the mass of the platinum group metal, and (D) the following The reaction product of the above-mentioned components i), ii) and iii): 0.01 to 20 parts by mass relative to 100 parts by mass of the total of the above-mentioned component (A) and the above-mentioned component (B), i) has a viscosity of 10 at 25°C ~10,000mPa‧s and one molecule has at least 1 base represented by CF ₃ -(CF ₂ ) _j -(CH ₂ ) _k - bonded to a silicon atom (but j is an integer from 3 to 9, and k is An integer above 1) organopolysiloxane, ii) carboxylate of rare earth elements containing cerium: cerium is in an amount of 0.05 to 5 parts by mass relative to 100 parts by mass of the component i) above, iii) (R ⁴ O) ₄ Ti (in the formula, R ⁴ is a monovalent hydrocarbon group of the same or different species) or at least one of its partial hydrolysis condensates: titanium is 0.05 to 5 parts by mass relative to 100 parts by mass of the aforementioned i) component The aforementioned (B) component is a group represented by CF ₃ -(CF ₂ ) _f -(CH ₂ ) _g - which has more than one bond to a silicon atom in one molecule (but f is 0 to 5 Integer, g is an integer above 1). For example, the addition curable polysiloxy resin composition of claim 1, wherein in the aforementioned component (A), a=5 and b=2, and in the aforementioned component (D), j=5 and k=2. As claimed in claim 1, the addition curable polysiloxane resin composition has a refractive index of 1.37 or less at a wavelength of 589 nm at 25°C. A method for manufacturing an addition-hardening polysiloxy resin composition according to claim 1, which is characterized by including reacting the aforementioned i), ii) and iii) components at a temperature of 150°C or above while introducing oxygen-containing gas. Steps to produce the aforementioned component (D). A polysilicone cured product characterized by being a cured product of the addition-curable polysiloxane resin composition according to any one of claims 1 to 3. For example, the polysiloxane hardened material of claim 5 has a light transmittance of more than 80% at a wavelength of 400 nm with an optical path length of 2 mm. An optical semiconductor device, characterized in that the optical semiconductor element is bonded with the polysiloxane hardened material as claimed in claim 5 or 6. An optical semiconductor device, characterized in that an optical semiconductor element is sealed with the polysiloxane cured material according to claim 5 or 6.