KR20180127174A - Curable organopolysiloxane composition and reflective materials for optical semiconductor compring the same - Google Patents

Curable organopolysiloxane composition and reflective materials for optical semiconductor compring the same Download PDF

Info

Publication number
KR20180127174A
KR20180127174A KR1020180030964A KR20180030964A KR20180127174A KR 20180127174 A KR20180127174 A KR 20180127174A KR 1020180030964 A KR1020180030964 A KR 1020180030964A KR 20180030964 A KR20180030964 A KR 20180030964A KR 20180127174 A KR20180127174 A KR 20180127174A
Authority
KR
South Korea
Prior art keywords
organopolysiloxane
sio
group
carbon atoms
number
Prior art date
Application number
KR1020180030964A
Other languages
Korean (ko)
Other versions
KR102007490B1 (en
Inventor
안정모
강승현
정인홍
정명석
최태훈
김민섭
Original Assignee
주식회사 케이씨씨
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to KR1020170062367 priority Critical
Priority to KR20170062367 priority
Application filed by 주식회사 케이씨씨 filed Critical 주식회사 케이씨씨
Publication of KR20180127174A publication Critical patent/KR20180127174A/en
Application granted granted Critical
Publication of KR102007490B1 publication Critical patent/KR102007490B1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/06Preparatory processes
    • C08G77/08Preparatory processes characterised by the catalysts used
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/12Polysiloxanes containing silicon bound to hydrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/20Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes

Abstract

The present invention relates to a curable organopolysiloxane composition and a reflective material for an optical semiconductor including the same. The curable organopolysiloxane composition comprises: an organopolysiloxane mixture which includes a first organopolysiloxane including at least one alkenyl group and at least one SiO_2 unit within one molecule, a second organopolysiloxane in the normal chain including at least two vinyl groups within one molecule, and a third organopolysiloxane including a hydrogen group directly combined with at least two silicones within one molecule; a pigment; and a hydrosilylation catalyst. In addition, the curable organopolysiloxane composition comprises: 40-60 wt% of the first organopolysiloxane; 20-50 wt% of the second organopolysiloxane; and the remaining amount of the third organopolysiloxane, for a total weight (100 wt%) of organopolysiloxane mixture. Therefore, the curable organopolysiloxane composition and a reflective material for an optical semiconductor including the same can provide excellent heat resistance.

Description

TECHNICAL FIELD The present invention relates to a curable organopolysiloxane composition and a reflective material for optical semiconductors including the curable organopolysiloxane composition,

The present invention relates to a curable organopolysiloxane composition and a reflective material for optical semiconductors comprising the same.

A conventional package (PKG) of a surface mount type (SMT) type package is generally formed by bonding an electrode at the upper end portion of the chip and an electrode at the lower end portion of the PKG with a wire. The frame is made of a material having a high reflectance to serve as a reflector.

However, since the flip chip having a structure having an electrode only at the lower end of the chip has been commercialized according to the demand for miniaturization of optical semiconductor PKG, there is a demand for a chip-scale package (CPS) in which frames are omitted, Is increasing.

The gap between the chips is changed by a method of dispensing or molding with silicone having a high reflectance and then cutting into a single chip to produce PKG.

Therefore, there is a growing demand for materials having high reflectance in a visible light region and excellent heat resistance in a fine molding process and a thin film state.

JP 2009-021394A JP 2011-140550A JP 2009-155415A

An object of the present invention is to provide a curable organopolysiloxane composition excellent in heat resistance and a reflective material for optical semiconductor comprising the same.

In order to achieve the above object, one aspect of the invention, at least one alkenyl group and at least one SiO 2 in one molecule , A second organopolysiloxane having a straight chain containing at least two vinyl groups in one molecule and a third organopolysiloxane having a hydrogen group directly bonded to at least two silicon atoms in one molecule Wherein the organopolysiloxane mixture comprises 40 to 60% by weight of the first organopolysiloxane, 20 to 50% by weight of the second organogens, based on 100% by weight of the organopolysiloxane mixture, A polysiloxane, and a third organopolysiloxane in the remainder of the composition.

Another aspect of the present invention provides a reflective material for optical semiconductors comprising the curable organopolysiloxane composition.

The curable organopolysiloxane composition of the present invention is easy to handle during injection molding molding at a room temperature in a liquid state and can be made into a complicated molded product, has a high hardness of a molded product and is excellent in cutting workability, has low tackiness and excellent heat resistance, It has a high reflectance and can be effectively used as a reflective material for optical semiconductors.

Hereinafter, the present invention will be described in detail.

1. Hardenability Organo Polysiloxane  Composition

One aspect of the invention provides a curable organopolysiloxane composition.

The curable organopolysiloxane compositions of the present invention comprise an organopolysiloxane mixture, a pigment, and a hydrosilylation catalyst.

The organopolysiloxane mixture comprises a first organopolysiloxane, a second organopolysiloxane, and a third organopolysiloxane.

Specifically, the first organopolysiloxane is a main component of the curable organopolysiloxane composition, and contains at least one alkenyl group and at least one SiO 2 unit in one molecule, and may be represented by the following formula (1).

[Chemical Formula 1]

(R 1 3 SiO 1/2 ) a (R 2 3 SiO 1/2 ) b (SiO 2 ) c

Wherein R 1 is independently an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, at least one of R 1 is an alkenyl group having 2 to 6 carbon atoms, R 2 each independently may be an alkyl group having 1 to 6 carbon atoms. The alkyl or alkenyl group of R < 1 > or R < 2 > may be a straight chain or branched chain.

The alkyl group may be selected from the group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group and a cyclohexyl group. The alkenyl group may be selected from the group consisting of a vinyl group, a butenyl group, a pentenyl group, and a hexenyl group, and among these, the vinyl group may be used.

In the formula (1), a is preferably in the range of 0.05 to 0.25, and if a is less than 0.05, the crosslinking density of the first organopolysiloxane is lowered, and if it exceeds 0.25, the density of the curable organopolysiloxane composition is increased, Cracks may occur. The number b is preferably in the range of 0.1 to 0.5, and if b is less than 0.1, the viscosity of the curable organopolysiloxane composition is increased, and the flowability is low, so that mold workability may not be easy. If c is less than 0.4, the hardness of the cured product of the curable organopolysiloxane composition can not be secured. If c is more than 0.5, the viscosity of the curable organopolysiloxane composition becomes high, The mold workability may not be easy.

In the above formula (1), SiO 2 If the SiO 2 unit is contained in an amount of 40 wt% or more, it is possible to form a cured product having a high hardness at room temperature without introducing an allyl group (without modification of the phenyl group), and even when used at a high temperature for a long time It is possible to secure excellent heat resistance because the reflectance is not lowered due to discoloration. In addition, since a hard cured product can be formed, a curable organopolysiloxane composition that is liquid at room temperature can be provided without using an excessive amount of an inorganic filler, thereby providing excellent mold workability. If SiO 2 When the content of the unit is less than 40% by weight, the viscosity of the curable organopolysiloxane is lowered and the workability of the mold may be deteriorated.

For example, the first organopolysiloxane may be a silicate resin having a vinyldimethylsiloxy group and a trimethylsiloxy group at both ends, or a silicate resin having a divinylmethylsiloxy group and a trimethylsiloxy group at both ends, siloxy and trimethyl siloxy silicate, the resin (ViMe 2 SiO 1/2) 0.15 ( Me 3 SiO 1/2) 0.35 (SiO 2) 0.5, (ViMe 2 SiO 1/2) 0.10 (Me 3 SiO 1/2 ) 0 .40 (SiO 2) 0.5 , (ViMe 2 SiO 1/2) 0.2 (Me 3 SiO 1/2) 0.3 (SiO 2) 0.5, (ViMe 2 SiO 1/2) 0.15 (Me 3 SiO 1/2 ) 0 .45 (SiO 2) 0.4 , (ViMe 2 SiO 1/2) 0.10 (Me 3 SiO 1/2) 0.50 (SiO 2) 0.4, (ViMe 2 SiO 1/2) 0.2 (Me 3 SiO 1/2 ) 0 .4 (SiO 2) 0.4 , (ViMe 2 SiO 1/2) 0.15 (Me 3 SiO 1/2) 0.35 (SiO 2) 0.5, (ViMe 2 SiO 1/2) 0.10 (Me 3 SiO 1/2 ) 0 .20 (SiO 2) 0.7 or (ViMe 2 SiO 1/2) 0.2 ( Me 3 SiO 1/2) 0.2 (SiO 2) may be 0.6 days, the terminal divinyl methyl siloxy group and tray Methyl siloxy groups of the silicate resin (Vi 2 MeSiO 1/2) 0.15 (Me 3 SiO 1/2) 0 .35 (SiO 2) 0.5, (Vi 2 MeSiO 1/2) 0.10 (Me 3 SiO 1/2) 0.40 (SiO 2) 0.5, ( Vi 2 MeSiO 1/2) 0.2 (Me 3 SiO 1/2) 0 .3 (SiO 2) 0.5, (Vi 2 MeSiO 1/2) 0.15 (Me 3 SiO 1/2) 0.45 (SiO 2) 0.4, ( Vi 2 MeSiO 1/2) 0.10 (Me 3 SiO 1/2) 0 .50 (SiO 2) 0.4, (Vi 2 MeSiO 1/2) 0.2 (Me 3 SiO 1/2) 0.4 (SiO 2) 0.4, ( Vi 2 MeSiO 1/2) 0.15 (Me 3 SiO 1/2) 0 .35 (SiO 2) 0.5, (Vi 2 MeSiO 1/2) 0.10 (Me 3 SiO 1/2) 0.20 (SiO 2) 0.7 or (Vi 2 MeSiO 1/2) 0.2 (Me 3 SiO 1/2) 0 .2 (SiO 2) may be 0.6 days.

The second organopolysiloxane is a component that modulates the viscosity of the curable organopolysiloxane composition to impart flowability and modulates the modulus. The second organopolysiloxane contains at least two alkenyl groups in one molecule and can be represented by the following formula .

(2)

(R 3 3 SiO 1/2 ) 2 (R 3 R 4 SiO) d (R 4 2 SiO) e

Wherein R 3 is independently an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms and R 4 is each independently an alkyl group having 1 to 6 carbon atoms, An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and at least two of R 3 and R 4 are alkenyl groups having 2 to 6 carbon atoms. The alkyl group or alkenyl group of R 3 or R 4 may be a straight chain or branched chain.

The alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group and a cyclohexyl group. Examples of the alkenyl group include a vinyl group, a butenyl group, a pentenyl group and a hexenyl group, and among these, a vinyl group is preferable. The aryl group includes a phenyl group, a tolyl group, a xylyl group, a naphthyl group and a biphenylene group, and among these, a phenyl group is preferable.

D and e are each independently 0 or an integer of 1 or more, d + e is an integer of 10 to 10,000, and d / (d + e) is 0 to 0.1. If d + e is less than an integer of 10, the curable organopolysiloxane composition is volatilized during curing and voids are generated and mold workability is deteriorated. If it exceeds 10,000, the flowability of the curable organopolysiloxane composition is lowered, A sufficient amount of pigment can not be added, and mold workability may be deteriorated.

On the other hand, when d / e is an integer of 1 or more, when d / (d + e) exceeds 0.1, the reactivity is lowered and the density of the curable organopolysiloxane composition is high, so that cracks due to a change in hardness over time can be generated.

For example, the second organopolysiloxane may be a vinyldimethylsiloxy-terminated dimethylsiloxane polymer, a vinyldimethylsiloxy-terminated methylvinylsiloxane-dimethylsiloxane block polymer, a trimethylsiloxy-terminated methylvinylsiloxane-dimethylsiloxane block polymer, a vinyldimethylsiloxy- Terminal methylphenylsiloxane-dimethylsiloxane block polymer, or vinyldimethylsiloxy terminated diphenylsiloxane dimethylsiloxane block polymer.

The vinyldimethylsiloxy terminated dimethylsiloxane polymer may be (ViMe 2 SiO 1/2 ) (Me 2 SiO) e (ViMe 2 SiO 1/2 ). Specifically, (ViMe 2 SiO 1/2) ( Me 2 SiO) 500 (ViMe 2 SiO 1/2), (ViMe 2 SiO 1/2) (Me 2 SiO) 1000 (ViMe 2 SiO 1/2) or ( ViMe 2 SiO 1/2 ) (Me 2 SiO) 1250 (ViMe 2 SiO 1/2 ).

The vinyldimethylsiloxy terminated methylvinylsiloxane-dimethylsiloxane block polymer may be (ViMe 2 SiO 1/2 ) (Me 2 SiO) e (ViMeSiO) d (ViMe 2 SiO 1/2 ). Specifically, (ViMe 2 SiO 1/2) ( Me 2 SiO) 400 (ViMeSiO) 30 (ViMe 2 SiO 1/2) or (ViMe 2 SiO 1/2) (Me 2 SiO) 1000 (ViMeSiO) 50 (ViMe 2 SiO 1/2 ).

The trimethylsiloxy terminated methylvinylsiloxane-dimethylsiloxane block polymer may be (Me 3 SiO 1/2 ) (Me 2 SiO) e (ViMeSiO) d (Me 3 SiO 1/2 ). Specifically, (Me 3 SiO 1/2 ) (Me 2 SiO) 400 (ViMeSiO) 30 (Me 3 SiO 1/2 ), (Me 3 SiO 1/2 ) (Me 2 SiO) 540 (ViMeSiO) 5 3 SiO 1/2), (Me 3 SiO 1/2) (Me 2 SiO) 1000 (ViMeSiO) 50 (Me 3 SiO 1/2) or (Me 3 SiO 1/2) (Me 2 SiO) 60 (ViMeSiO ) may be 7 (Me 3 SiO 1/2)

The second organopolysiloxane may have a viscosity of 10 to 70 Pa · s at 25 ° C. If the viscosity of the second organopolysiloxane at 25 캜 is out of the above range, there is a problem that the mold workability is markedly poor.

Wherein the third organopolysiloxane serves as a crosslinking agent between the first organopolysiloxane and the second organopolysiloxane to form a cured product and includes a hydrogen group directly bonded to at least two silicon atoms in one molecule, 3 < / RTI >

(3)

H f R 5 g SiO (4-fg) / 2

In Formula 3, R 5 may each independently be an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group and a cyclohexyl group. The aryl group includes a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenylyl group, among which a phenyl group is preferable.

In the above formula (3), f and g represent the ratio of a hydrogen atom to an organic atom when the Si atom contained in the third organopolysiloxane is taken as 1, f is a number of 0.001 to 2, g is a number of 0.7 to 2 And f + g is a number of 0.8 to 3. If f is less than 0.001, the crosslinking density of the curable organopolysiloxane is lowered and the reactivity is lowered. If the value of f is more than 2, the crosslinking density is increased, so that cracks are easily generated in the cured product and voids are formed due to the generation of hydrogen gas during curing, The workability is deteriorated. If the g is less than 0.7, the crosslinking density becomes high, so that cracks easily occur in the cured product, voids are formed due to the generation of hydrogen gas during curing, and mold workability is deteriorated. When the value exceeds 2, the reactivity is lowered, Volatiles are easily volatilized and voids are formed during curing, thereby deteriorating mold workability. On the other hand, when f + g is less than 0.8, the viscosity is high and the flowability is deteriorated to deteriorate the mold workability. When the ratio is more than 3, the reactivity is low and the curing is slow and the molecular weight is small. do.

For example, the third organopolysiloxane includes (HMe 2 SiO 1/2 ) (Me 2 SiO) n (HMe 2 SiO 1/2 ) hydrogendimethylsiloxy end dimethylsiloxane polymer, (Me 3 SiO 1/2 ) (HMeSiO) n (Me 3 SiO 1/2) of trimethyl siloxy terminated methyl hydrogen siloxane polymer, (Me 3 SiO 1/2) ( Me 2 SiO) n (HMeSiO) m (Me 3 SiO 1/2) Trimethylsiloxy terminated methylhydrogensiloxane-dimethylsiloxane block polymer, (HMe 2 SiO 1/2 ) (Me 2 SiO) n (HMeSiO) m (HMe 2 SiO 1/2 ) hydrogendimethylsiloxy terminated dimethylsiloxane -Hydrogenmethylsiloxane block polymer, (HMe 2 SiO 1/2 ) n (Me 3 SiO 1/2 ) m (SiO 2 ) q hydrogendimethylsiloxy-trimethylsiloxy terminated silicate resin, aryl group containing oligomers (N, m, or q is an integer of 1 or more).

The dimethyl hydrogen siloxy terminated dimethyl siloxane polymer (HMe 2 SiO 1/2) (Me 2 SiO) 25 (HMe 2 SiO 1/2), (HMe 2 SiO 1/2) (Me 2 SiO) 45 (HMe 2 SiO 1/2 ) or (HMe 2 SiO 1/2 ) (Me 2 SiO) 125 (HMe 2 SiO 1/2 ).

It said trimethyl siloxy terminated methyl hydrogen siloxane polymer is (Me 3 SiO 1/2) (HMeSiO ) 20 (Me 3 SiO 1/2) or (Me 3 SiO 1/2) (HMeSiO ) 40 (Me 3 SiO 1 / 2 ).

Said trimethyl siloxy terminated methyl hydrogen siloxane-dimethyl siloxane block polymer is (Me 3 SiO 1/2) (Me 2 SiO) 20 (HMeSiO) 20 (Me 3 SiO 1/2), (Me 3 SiO 1/2) (Me 2 SiO) 25 (HMeSiO ) 12 (Me 3 SiO 1/2), (Me 3 SiO 1/2) (Me 2 SiO) 46 (HMeSiO) 20 (Me 3 SiO 1/2), (Me 3 SiO 1/2) (Me 2 SiO) 100 (HMeSiO) 10 (Me 3 SiO 1/2) or (Me 3 SiO 1/2) (Me 2 SiO) 7 (HMeSiO) 3 (Me 3 SiO 1/2) days .

The hydrogendimethylsiloxy terminated dimethylsiloxane-hydrogermethylsiloxane block polymer may be (HMe 2 SiO 1/2 ) (Me 2 SiO) 8 (HM 3 SiO) 2 (HMe 2 SiO 1/2 ).

The dimethyl hydrogen siloxy-terminated trimethyl siloxy silicate resin (HMe 2 SiO 1/2) 0.6 ( Me 3 SiO 1/2) 0.1 (SiO 2) 0.2 or (HMe 2 SiO 1/2) 0.5 (Me 3 SiO 1/2) 0 .2 (SiO 2 ) may be 0.3 days.

The aryl group-containing oligomers are (HMe 2 SiO 1/2) 3 (PhSiO 1.5) 1 Or (HMe 2 SiO 1/2 ) 2 (Ph 2 SiO) 1 .

The third organopolysiloxane may have a viscosity at 25 ° C of from 0.005 to 0.15 Pa · s. When the viscosity of the third organopolysiloxane at 25 캜 is out of the above range, there is a problem that mold workability is significantly poor.

Wherein the organopolysiloxane mixture comprises from 40 to 60% by weight of the first organopolysiloxane, from 20 to 50% by weight of the second organopolysiloxane, and the remainder of the third organopolysiloxane, based on the total weight of the organopolysiloxane mixture can do.

The third organopolysiloxane is preferably added in such an amount that the number of moles of hydrogen with respect to the number of moles of the alkenyl groups of the first organopolysiloxane and the second organopolysiloxane is 0.5-5.

If the amount of the first organopolysiloxane is less than 40% by weight, the hardness is lowered and the processability is poor. If the first organopolysiloxane is more than 60% by weight, flowability is lost at room temperature,

If the amount of the second organopolysiloxane is less than 20% by weight, the cross-linking density may be high, and cracks may be easily generated in the heat shock. If the second organopolysiloxane is more than 50% by weight, the hardness may be lowered.

If the number of moles of hydrogen of the third organopolysiloxane is less than 0.5 as compared with the number of moles of the alkenyl groups of the first organopolysiloxane and the second organopolysiloxane, a sufficient cured product can not be formed, If it is more than 5, cross-linking density becomes high so that the cured product easily cracks, and hydrogen gas is generated during curing to form voids, and mold workability may be deteriorated.

The pigment may be selected from the group consisting of titanium oxide, alumina, zinc oxide, zirconium oxide, magnesium oxide, and barium sulfate as a component that realizes a white color by lowering the transmittance of a cured product and realizes a reflectance in a visible light region, May be titanium oxide.

The pigment preferably has a particle size of from 0.05 to 10 탆. When the pigment is less than 0.05 탆, the dispersibility is poor and the viscosity is easily increased. When the pigment is more than 10 탆, Can be lowered.

The pigment may be added in an amount of 80 to 200 parts by weight based on 100 parts by weight of the organopolysiloxane mixture. When the amount of the pigment is less than 80 parts by weight, the light transmittance of the thin film may be lowered, If it is added in an amount exceeding the weight part, the flowability is deteriorated and a fixed amount of the ink may not be discharged.

The hydrosilylation catalyst is a reaction catalyst component that accelerates the hydrosilylation reaction of the hydrogen groups bonded to the silicon of the first organopolysiloxane, the second organopolysiloxane, and the silicon of the third organopolysiloxane. The platinum catalyst, Catalyst and a palladium catalyst.

The platinum-based catalyst may be a platinum-alkenylsiloxane complex consisting of a finely divided platinum powder, chloroplatinic acid, an alcoholic solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex .

The platinum-based catalyst is preferably added in an amount of 0.01 to 100 ppm based on the total weight of the organopolysiloxane mixture. If it is less than 0.01, the reaction rate becomes slow or does not sufficiently react. When the amount exceeds 100, have.

The curable organopolysiloxane composition is selected from additives consisting of conventional adhesion promoters, inorganic fillers, silicone rubber powders, resin powders, heat resisting agents, antioxidants, radical scavengers, light stabilizers, flame retardant additives, silicone based diluents and retarders And may further include at least one.

The curable organopolysiloxane composition of the present invention is preferably liquid at room temperature (for example, 25 ° C). When the curable organopolysiloxane composition is in a liquid state at room temperature, it is easy to handle in injection molding, It is possible. The curable organopolysiloxane composition preferably has a viscosity of 20 to 1,000 Pa · s. When the viscosity is less than 20 Pa · s, the composition penetrates into molds during mold molding, s, molding unfavorable to the composition of the entire mold is liable to occur when molding a complex structure of a thin film.

The curable organopolysiloxane composition preferably contains an aryl group (for example, phenyl group) in an amount of less than 30 mol% of the total organic groups. If the proportion is more than 30 mol%, discoloration due to the oxidation reaction of the aryl group The reflectance may be lowered.

2. Reflective material for optical semiconductor

Another aspect of the present invention provides a reflective material for optical semiconductors comprising a cured product of a curable organopolysiloxane composition.

The cured product is formed by curing the curable organopolysiloxane composition. The shape of the cured product is not particularly limited and may be, for example, a sheet type, a film type, a convex lens type, a concave lens type, a Fresnel lens type, a cone shape, and a square cone platform. The cured product may be handled alone, or it may be covered, sealed, or adhered to an optical semiconductor element or the like.

If the hardness of the cured product is lower than the Shore A 90, burrs are likely to be generated when the molded material is cut, and the workability is lowered.

The thickness of the cured product is preferably 30 to 1000 m, and the visible light transmittance at 450 nm may be 10% or less within the numerical range.

The use of the reflective material for optical semiconductors including the cured product is not particularly limited, and can be used for, for example, a backlight module for a liquid crystal display, a flash module for a mobile phone, and a vehicle lighting module.

Hereinafter, the present invention will be described in detail with reference to examples.

However, the following examples illustrate the present invention in detail, and the present invention is not limited by the following examples.

[ Example  And Comparative Example ]

A curable organopolysiloxane composition was prepared using a mechanical mixer, a hand mixer and a rotary mixer for confinement, which are generally known in the art as listed in Table 1 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6
(A) 40 52 56 40 40 40 65 38 56 40 70 45
(B-1) 28 53
(B-2) 50 50 50 20 50 18
(B-3) 22 15
(B-4) 35
(B-5)
(B-6) 50
(C-1) 10 10
(C-2) 20 12
(C-3) 22 10 26 15
(C-4) 10 5 7 20
(C-5)
(C-6)
(C-7) 10
A + B + C
= Total
(weight%)
100 100 100 100 100 100 100 100 100 100 100 100
(D)
(Parts by weight)
100 100 100 100 100 100 100 100 100 100 50 100
(E) (ppm) 0.05 0.05 0.05 0.05 0.5 0.5 0.05 0.05 0.05 0.05 0.05 0.05
(F) (ppm) 0.02 0.02 0.02 0.02 0.5 0.5 0.02 0.02 0.02 0.02 0.02 0.02
H / Vi 1.5 One One 1.8 1.4 3 1.0 One 1.6 1.3 0.6 2.5
Phenyl group content (mol%) 0 0 0 6 0 0 2 0 0 4 0 40

division Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17
(A) 40 40 40 52 56 65 38 56 40 40 40
(B-1) 20
(B-2) 55 20 50 18 55 50 50
(B-3)
(B-4)
(B-5) 50 28 22
(B-6)
(C-1) 40 10 15 12 26 5
(C-2) 20
(C-3) 5 22
(C-4)
(C-5) 10
(C-6) 10
(C-7)
A + B + C
= Total
(weight%)
100 100 100 100 100 100 100 100 100 100 100
(D)
(Parts by weight)
100 100 100 100 100 100 100 100 100 100 100
(E) (ppm) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05
(F) (ppm) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02
H / Vi 0.35 6.0 1.5 One One 0.74 1.44 0.91 1.73 3.4 1.5
Phenyl group content (mol%) 0 0 0 0 0 0 0 0 0 0 0

- (A) Primary organopolysiloxane: VMQ-20, SiO 2 in Si Unit is 50wt%, the vinyl group content is 1.5mmol / g, and the silicone resin on 25 ° C powder

- (B-1) Secondary organopolysiloxane-1: VEP-70K, polydimethylsiloxane having both ends of a dimethylvinylsiloxy group and having a vinyl group content of 0.027 mmol / g and a viscosity at 25 DEG C of 70 Pa.s Siloxane

- (B-2) Secondary organopolysiloxane-2: VEP-10K, polydimethylsiloxane having both terminal ends of dimethylvinylsiloxy groups and having a vinyl group content of 0.055 mmol / g and a viscosity of 10 Pa · s at 25 ° C Siloxane

- (B-3) Secondary organopolysiloxane-3: VEP-100, a polydimethylsiloxane having both ends of a dimethylvinylsiloxy group and a vinyl group content of 0.4 mmol / g and a viscosity of 10 Pa · s at 25 ° C Siloxane

- (B-4) Second organopolysiloxane-4: PMVP-2K, polymethylphenylsilicone having dimethylvinylsiloxy groups at both terminals and having a vinyl group content of 0.45 mmol / g and a viscosity at 25 ° C of 2 Pa · s Siloxane

- (B-5) Secondary organopolysiloxane-5: VEP-2K, polydimethylsiloxane having both terminals of a dimethylvinylsiloxy group and a vinyl group content of 0.088 mmol / g and a viscosity of 2 Pa · s at 25 ° C Siloxane

- (B-6) Secondary organopolysiloxane-6: VEP-5K, a polydimethylsiloxane having vinylphenylsiloxy groups at both ends and a vinyl content of 0.038 mmol / g and a viscosity at 25 ° C of 50 Pa · s

- (C-1) tertiary organopolysiloxane-1: MHBP-073T, polydimethylsiloxane having both ends of a trimethylsiloxy group and a hydrogen content of 7.3 mmol / g and a viscosity at 25 DEG C of 0.04 Pa.s Methylhydrogen siloxane

- (C-2) tertiary organopolysiloxane-2: MHBP-043T, polydimethylmethylmethylsiloxane having both terminal ends of a trimethylsiloxy group and a hydrogen content of 4.3 mmol / g and a viscosity at 25 ° C of 0.04 Pa.s Hydrogen siloxane

- (C-3) tertiary organopolysiloxane-3: MHBP-0357, polydimethylmethyl having both terminal ends of a trimethylsiloxy group and a hydrogen content of 3.5 mmol / g and a viscosity at 25 DEG C of 0.06 Pa.s Hydrogen siloxane

- (C-4) tertiary organopolysiloxane-4: TDPS, 3 - [(Dimethylsilyl) oxy] -1,1,5,5-tetramethyl-3-phenyltrisiloxane

- (C-5) tertiary organopolysiloxane-5: HD4 1,2,5,7-Hexamethylcyclootetrasiloxane, polysiloxane having a hydrogen content of 16.63 mmol / g and a viscosity of 4 mPa · s

- (C-6) tertiary organopolysiloxane-6: a polydimethylmethylmethylpolysiloxane having both terminal ends of a trimethylsiloxy group and a hydrogen content of 4.3 mmol / g and a viscosity at 25 DEG C of 0.2 Pa.s Hydrogen siloxane

- (C-7) tertiary organopolysiloxane-7: polydimethylmethylhydrogensiloxane having both terminals at the trimethylsiloxy group and having a hydrogen content of 14.4 mmol / g and a viscosity at 25 ° C of 0.02 Pa · s

- (D) Pigment: Titanium oxide having an average particle size of 0.25 占 퐉 (TIPAQUE CR-57 manufactured by Ishihara Sangyo Co., Ltd.)

- (E) hydrosilylation catalyst: Pt 1.0 VTSC, platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl- Tetramethyldisiloxane solution (platinum content: 1% by weight)

- (F) Reaction retardant: ECH, 1-ethynyl-1-cyclohexanol

[Experimental Example]

- Viscosity (Pa · s): The viscosity was measured at 25 ° C using a Rheometer (model name: MCR301, MCR302) manufactured by Anton Paar.

- Hardness (Shore A): The hardness was measured at 25 ° C with a Shore A type hardness meter after curing the composition at 150 ° C for 2 hours in a mold capable of forming a specimen of 6 mm thickness.

- Transmittance (%): Measured using a UV-Vis Spectrometer (Model Lambda 950). Base is air.

- Reflectance (%): Reflectance was measured by UV-Vis Spectrometer (model name Lambda 950) manufactured by Perkin Elmer, after removing the composition and forming a coating of 50 탆 on a quadrangular applicator and curing the coating at 150 캜 for 2 hours. . Base is a standard specimen of barium sulphate provided by the measuring equipment manufacturer.

- Heat Resistance Reflectance (%): Initial reflectance The specimens were measured for reflectance after heat storage at 200 ° C for 1500 hours.

- Mold workability: MQFP-244 is classified into five stages based on the measured mold release force and the degree of warpage of the molding during continuous molding with Book mold.

?: Very good,?: Good,?: Normal, X: poor, XX: not workable

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6
Viscosity (Pa · s) 125 203 507 80 370 80 Room temperature solid phase 90 320 120 Room temperature solid phase 68
Hardness (ShoreA) 90 95 95 92 90 97 98 70 98 80 95 98
Transmittance (%) 2.5 2 1.5 2 1.7 1.3 One 2.5 1.5 2.5 11.5 2
reflectivity(%) 97 97.5 98 97 98 98 98.5 97 98 97 88 98
Heat resistance
reflectivity
(%)
95 96 95 95 96 95 96 95 96 93 86 89
Mold
Workability
XX X X O

division Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17
Viscosity (Pa · s) 480 10 67 43 50 713 93 280 510 15 1470
Hardness (ShoreA) 25 98 91 97 98 98 63 98 98 98 90
Transmittance (%) 2.3 2 2.3 2.2 1.8 1.5 2.7 2.3 1.8 2 2.7
reflectivity(%) 97 98 98.3 97.1 97.7 98.8 98.2 98.8 98.5 98 97
Heat resistance
reflectivity
(%)
95 94 96.5 96.8 96.3 95.3 96.6 97.1 96.8 93 94
Mold
Workability
XX XX X X X XX X X XX XX

Referring to Tables 3 and 4, Examples 1 to 6 corresponding to the curable organopolysiloxane composition of the present invention had a hardness of 90 or more, a transmittance of 10% or less, a reflectance and a heat resistance reflectance of 90% , And a viscosity of 20 to 1,000 Pa · s was satisfied, confirming that the mold workability was excellent. On the other hand, in Comparative Example 1 in which the mixing ratio of the first to third organopolysiloxanes constituting the organopolysiloxane mixture, the viscosity of the second organopolysiloxane or the third organopolysiloxane, the content of the phenyl group and the like were outside the range of the present invention To 17, it can be confirmed that the physical properties are very poor.

Claims (9)

  1. At least one alkenyl group in one molecule and at least one SiO 2 A second organopolysiloxane having a straight chain containing at least two alkenyl groups in one molecule and a third organopolysiloxane having a hydrogen group directly bonded to at least two silicon atoms in one molecule An organopolysiloxane mixture,
    Pigment, and
    A hydrosilylation catalyst,
    A curing organopolysiloxane comprising 40 to 60 wt% of the first organopolysiloxane, 20 to 50 wt% of the second organopolysiloxane, and the remainder of the third organopolysiloxane, based on 100 wt% of the organopolysiloxane mixture, Composition.
  2. The method according to claim 1,
    Wherein the first organopolysiloxane is represented by the following formula (1).
    [Chemical Formula 1]
    (R 1 3 SiO 1/2 ) a (R 2 3 SiO 1/2 ) b (SiO 2 ) c
    Wherein R 1 is independently an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, at least one of R 1 is an alkenyl group having 2 to 6 carbon atoms, R 2 are each independently 1 to 6 alkyl groups, a is a number of 0.05 to 0.25, b is a number of 0.1 to 0.5, and c is a number of 0.4 to 0.6.
  3. The method according to claim 1,
    Wherein the second organopolysiloxane is represented by the following formula (2).
    (2)
    (R 3 3 SiO 1/2 ) 2 (R 3 R 4 SiO) d (R 4 2 SiO) e
    Wherein R 3 is independently an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms and R 4 is each independently an alkyl group having 1 to 6 carbon atoms, An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and at least two of R 3 and R 4 are alkenyl groups having 2 to 6 carbon atoms. d and e are each independently 0 or an integer of 1 or more, d + e is an integer of 10 to 10,000, and d / (d + e) is 0 to 0.1.
  4. The method according to claim 1,
    Wherein the third organopolysiloxane is represented by the following formula (3).
    (3)
    H f R 5 g SiO (4-fg) / 2
    Wherein R 5 is independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, f is a number of 0.001 to 2, g is a number of 0.7 to 2, f + g is a number of 0.8 to 3.
  5. The method according to claim 1,
    Wherein the third organopolysiloxane is added in an amount such that the number of moles of hydrogen is 0.5 to 5 relative to the number of moles of alkenyl groups of the first organopolysiloxane and the second organopolysiloxane.
  6. The method according to claim 1,
    Wherein the pigment is added in an amount of 80 to 200 parts by weight based on 100 parts by weight of the organopolysiloxane mixture.
  7. The method according to claim 1,
    Wherein the hydrosilylation catalyst is added in an amount of 0.01 to 100 ppm based on the total weight of the organopolysiloxane mixture.
  8. The method according to claim 1,
    At least one selected from the group consisting of an adhesion promoter, an adhesion promoter, an inorganic filler, a silicone rubber powder, a resin powder, a heat resistant agent, an antioxidant, a radical scavenger, a light stabilizer, a flame retardant additive, Curable organopolysiloxane composition.
  9. A reflective material for an optical semiconductor comprising a cured product of the curable organopolysiloxane composition according to claim 1.
KR1020180030964A 2017-05-19 2018-03-16 Curable organopolysiloxane composition and reflective materials for optical semiconductor compring the same KR102007490B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020170062367 2017-05-19
KR20170062367 2017-05-19

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW107112681A TW201903051A (en) 2017-05-19 2018-04-13 Silicon curable organo siloxane composition, and which comprises a reflective material for an optical semiconductor of

Publications (2)

Publication Number Publication Date
KR20180127174A true KR20180127174A (en) 2018-11-28
KR102007490B1 KR102007490B1 (en) 2019-08-06

Family

ID=

Also Published As

Publication number Publication date
TW201903051A (en) 2019-01-16
WO2018212440A1 (en) 2018-11-22

Similar Documents

Publication Publication Date Title
JP5999132B2 (en) Silicone resin composition for coating an optoelectronic device light transmission surface
EP1505121B1 (en) Hardenable composition, hardening product, process for producing the same and light emitting diode sealed with the hardening product
US20090179180A1 (en) Curable Organopolysiloxane Composition and Semiconductor Device
US20040116640A1 (en) Silicone resin composition for LED devices
EP2196503B1 (en) Thermosetting silicone resin composition, silicone resin, silicone resin sheet and use thereof
KR101607108B1 (en) Resin composition for encapsulating optical semiconductor element and optical semiconductor device
JP5792193B2 (en) The curable composition
KR101395027B1 (en) Curable polyorganosiloxane composition
US20020142174A1 (en) Low temperature, fast curing silicone compositions
JP4678415B2 (en) Light semiconductor case for the silicone resin composition and an optical semiconductor case
CN102532915B (en) Low gas permeability siloxane resin composition and the photovoltaic device
US20110254047A1 (en) Curable Organopolysiloxane Composition, Optical Semiconductor Element Sealant, And Optical Semiconductor Device
US8846828B2 (en) Curable organopolysiloxane composition and semiconductor device
US7649059B2 (en) Addition-curable organopolysiloxane resin composition
US8765264B2 (en) Silicone laminated substrate, method of producing same, silicone resin composition for producing silicone laminated substrate, and LED device
JP5392805B2 (en) The curable organopolysiloxane resin composition and an optical member
EP1988125A2 (en) Addition curable silicone resin composition and silicone lens using same
US8202933B2 (en) Silicone resin composition for encapsulating luminescent element and process for producing optical-semiconductor electronic part with the same through potting
EP0985710B1 (en) Curable silicone composition
US8592030B2 (en) Silicone adhesive for semiconductor element
JP5505991B2 (en) High adhesive silicone resin composition and an optical semiconductor device using the composition
KR101495361B1 (en) Curable silicone rubber composition and optical semiconductor device using the same as sealing material
KR101713087B1 (en) Phosphor-containing cured silicone, process for production of same, phosphor-containing silicone composition, precursor of the composition, sheet-shaped moldings, led package, light-emitting device, and process for production of led-mounted substrate
US8164202B2 (en) Optical semiconductor device encapsulated with silicone resin
KR20080110761A (en) Curable resin composition

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant