CN1784471A

CN1784471A - Curable organopolysiloxane resin composition for optical transmission components, optical transmission components, and fabrication process thereof

Info

Publication number: CN1784471A
Application number: CN 200480012634
Authority: CN
Inventors: 栉引信男; 小川琢哉; 竹内贵久子
Original assignee: Dow Corning Corp
Current assignee: DuPont Toray Specialty Materials KK; Dow Silicones Corp
Priority date: 2003-04-07
Filing date: 2004-04-07
Publication date: 2006-06-07
Anticipated expiration: 2024-04-07
Also published as: CN100451070C

Abstract

The present invention relates to a hydrosilation-curable organopolysiloxane resin composition comprising (A) an organopolysiloxane resin having three or more monovalent unsaturated aliphatic hydrocarbon groups and aromatic hydrocarbon groups, (B) an organosilicon compound having two or more silicon-bonded hydrogen atoms and aromatic hydrocarbon groups, (C) a hydrosilation catalyst, and optionally (D) (d1) a solvent or (d2) a hydrosilation -reactive organosiloxane-based diluent, for optical transmission components, especially for optical transmission components serving as optical communication elements, relates to optical transmission components, represented by optical waveguides, comprisiong a hydrosilation-cured product of the aforementioned organopolysiloxane resin and organosilicon compound, and relates to a process for fabricatiing optical transmission components.

Description

The curable organopolysiloxane resin composition that is used for light-transmitting component, light-transmitting component and manufacture method thereof

Technical field

The present invention relates to be used for light-transmitting component, be particularly useful for curable organopolysiloxane resin composition as the light-transmitting component of optical communication device, relating to the optical waveguides is the light-transmitting component of representative, comprises the hydrosilation cured product of organopolysiloxane resins, also relates to the method for making light-transmitting component.

Background technology

Quartzy and glass not only is used as the optical fiber material, and owing to be the high reliability material, also is used as the material of optical communication device.Yet this type of inorganic materials needs pyroprocessing, has relatively poor productivity characteristic, and this has caused the demand to the organic materials that is used for optical communication device that has sufficient workability and weather resistance.The most reliable material is a polyimide, and it is widely used as the material of electronic package.

On the other hand, because their optical transparence, electrical insulation capability, light stability, thermostability etc., organopolysiloxane section bar material has also attracted considerable attention in optoelectronic areas.In the middle of the required physicals of optical communication device material, be stressed that optical characteristics especially, such as because polymer chain orientation does not absorb and free of birefringence and the high moisture resistance in the device assembling process, low water-absorbent and thermotolerance in 1300-1660nm telecom wavelengths scope.The improvement of above-mentioned characteristic makes progress, and mainly concentrates on polyimide and organopolysiloxane section bar material.

In Japanese Patent Application Publication No.Sho 63-217306, silicone rubber provides as the cured product that is used for the organopolysiloxane of optical waveguides, and in Japanese Patent Application Publication No.Hei1-131505, yielding organopolysiloxane elastomerics provides as the cured product that is used for the organopolysiloxane of optical waveguides.In Japanese Patent Application Publication No.Hei 11-43605, provide the liquid addition curing silicone rubber that contains silica filler, as light transmissive material.Yet, in view of their molecular structure, silicone rubber and organopolysiloxane elastomerics have showed sizable change on its refractive index and other optical characteristics after envrionment temperature changes, in other words, they have the problem with regard to temperature change stability and thermotolerance.

Japanese Patent Application Publication No.Hei 3-43423 provides by two organic radical silicane dichlorides and has had the organopolysiloxane resins (comprising the unitary organopolysiloxane resins of single organopolysiloxane unit and diorganosiloxane) that the hydrolysis cocondensation of the organic radical trichlorosilane of deuterate alkyl or halogenated alkyl is obtained, and organic polysilsesquioxane of obtaining of the hydrolytic condensation of the organic radical trichlorosilane by having deuterate alkyl or halogenated alkyl.Consider the high transmission rate of organopolysiloxane, Japanese Patent Application Publication No.Hei4-157402 provides the organopolysiloxane resins of the alkyl with no deuterium replacement or halogen replacement.The phenyl polysiloxane resin that contains epoxy group(ing) that Japanese Patent Application Publication No.Hei9-124793 provides the hydrolysis cocondensation by phenyl-trichloro-silicane and diphenyl dichlorosilane in the presence of the alcohol that contains epoxy group(ing) to be obtained.

Yet, though this type of organopolysiloxane resins has excellent optical at normal temperatures, but the dehydrating condensation that belongs to by silanol comes the solidified type, the result, if at high temperature do not heat the long period, will can fully not solidify, and when when light-transmitting component is being made the process of optical communication device etc. such as optical waveguides in, being exposed to high temperature (for example about 260 ℃), further dehydrating condensation has taken place, and has caused the change of optical characteristics.

In Japanese Patent Application Publication No.Hei 9-124793, UV solidifies and is undertaken by light-cured catalyst being joined in the phenyl polysiloxane resin that contains epoxy group(ing), yet this interpolation has caused comprising the absorption increase of Communication ray and the problem of scattering proneness.

By the way, optical waveguides is made up of the two class materials with differing refraction indices that are called core and covering.Their index difference depends on the design of optical waveguides, but it is said that the refractive index of core must be than the about 0.1-1.5% of refractive index height of covering, so that light is propagated by this core.Under the situation of dehydrating condensation curable organopolysiloxane resin, index difference is regulated by the introducing amount of fluoridizing alkyl, and this is fluoridized alkyl and helps to reduce refractive index.For example, Japanese Patent Application Publication No.2000-230052 provides has organic polysilsesquioxane of fluoridizing alkyl, but the problem that this method had is to fluoridize the cost that alkyl has increased material owing to having introduced.

The purpose of this invention is to provide the curable organopolysiloxane resin composition that is used for light-transmitting component, its do not introduce the deuterate alkyl and fluoridize have low refractive index temperature dependency under the situation of alkyl, high heat resistance, at the high transparent of communication wavelength, have feasible elasticity and the hardness that is difficult to be out of shape, and in the preparation process of core material and clad material, regulate index difference easily.

In addition, purpose of the present invention also provides the light-transmitting component of the cured product that comprises organopolysiloxane resins, described assembly do not introduce the deuterate alkyl and fluoridize have low refractive index temperature dependency under the situation of alkyl, high heat resistance, at the high transparent of communication wavelength region, have feasible elasticity and the hardness that is difficult to be out of shape, and in the preparation process of core material and clad material, regulate index difference easily.

In addition, simple and the economic method that the purpose of this invention is to provide the light-transmitting component of making the cured product that comprises organopolysiloxane resins, described assembly do not introduce the deuterate alkyl and fluoridize have low refractive index temperature dependency under the situation of alkyl, high heat resistance, at the high transparent of communication wavelength region, have feasible elasticity and the hardness that is difficult to be out of shape, and in the preparation process of core material and clad material, regulate index difference easily.

Summary of the invention

Be the result of the further investigation that addresses the above problem as purpose, the contriver has realized the present invention.That is to say, the present invention relates to following technical scheme:

[1] be used for the curable organopolysiloxane resin composition of light-transmitting component, said composition comprises (A) organopolysiloxane resins, and it is with averaged unit formula (average unit formula) (1) expression:

(R ¹ ₃SiO _1/2) _a(R ² ₂SiO _2/2) _b(R ³SiO _3/2) _c(SiO _4/2) _d (1)

(R wherein ¹, R ²And R ³Represent a kind of, two or more univalence hydrocarbyls, be selected from unit price aliphatic hydrocarbyl with 1～6 carbon atom and unit price aromatic hydrocarbyl with 6～10 carbon atoms, 0＜a≤0.5,0≤b＜0.2,0.3＜c＜1,0≤d≤0.4,0≤(b+d)/(a+C)≤0.25, and a+b+c+d=1), and have three or more unit price unsaturated aliphatic alkyl/molecules, wherein the 10mol% that is not less than of univalence hydrocarbyl is the unit price aromatic hydrocarbyl, (B) has the silicoorganic compound of the hydrogen atom/molecule of two or more silicon keyed jointings, wherein the substituent 5mol% of being not less than of the unit price of all silicon keyed jointings is unit price aromatic hydrocarbyl and (C) hydrosilylation catalysts.

[2] according to the curable organopolysiloxane resin composition that is used for light-transmitting component of [1], wherein the viscosity of said composition is no more than 1 * 10 under 25 ℃ ⁷MPas.

[3] be used for the curable organopolysiloxane resin composition of light-transmitting component, said composition comprises (A) organopolysiloxane resins, and it is with averaged unit formula (1) expression:

(R ¹ ₃SiO _1/2) _a(R ² ₂SiO _2/2) _b(R ³SiO _3/2) _c(SiO _4/2) _d (1)

(R wherein ¹, R ², R ³A, b, c, d, (b+d)/(a+c), and a+b+c+d is with above identical), and have three or more unit price unsaturated aliphatic alkyl/molecules, wherein the 10mol% that is not less than of univalence hydrocarbyl is the unit price aromatic hydrocarbyl, (B) has the silicoorganic compound of the hydrogen atom/molecule of two or more silicon keyed jointings, and wherein the substituent 5mol% of being not less than of the unit price of all silicon keyed jointings is the unit price aromatic hydrocarbyl, (C) hydrosilylation catalysts, and (D) (d1) solvent or (d2) hydrosilation reaction organic silicon oxygen alkane type thinner.

[4] light-transmitting component, this assembly comprise (A) and hydrosilation cured product (B):

(A) organopolysiloxane resins, it is represented with averaged unit formula (1):

(R ¹ ₃SiO _1/2)a(R ² ₂SiO _2/2) _b(R ³SiO _3/2) _c(SiO _4/2) _d (1)

(R wherein ¹, R ²And R ³Represent a kind of, two or more univalence hydrocarbyls, be selected from unit price aliphatic hydrocarbyl with 1～6 carbon atom and unit price aromatic hydrocarbyl with 6～10 carbon atoms, 0＜a≤0.5,0≤b＜0.2,0.3≤c＜1,0≤d≤0.4,0≤(b+d)/(a+C)≤0.25, and a+b+c+d=1), and have three or more unit price unsaturated aliphatic alkyl/molecules, wherein the 10mol% that is not less than of univalence hydrocarbyl is the unit price aromatic hydrocarbyl

(B) have the silicoorganic compound of the hydrogen atom/molecule of two or more silicon keyed jointings, wherein the substituent 5mol% of being not less than of the unit price of all silicon keyed jointings is the unit price aromatic hydrocarbyl.

[5] light-transmitting component, this assembly comprise (A), (B) and hydrosilation cured product (d2):

(R ¹ ₃SiO _1/2) _a(R ² ₂SiO _2/2) _b(R ³SiO _3/2) _c(SiO _4/2) _d (1)

(R ¹, R ², R ³, a, b, c, d, (b+d)/(a+c), and a+b+c+d is as mentioned above), and have three or more unit price unsaturated aliphatic alkyl/molecules, wherein the 10mol% that is not less than of univalence hydrocarbyl is the unit price aromatic hydrocarbyl,

(B) have the silicoorganic compound of the hydrogen atom/molecule of two or more silicon keyed jointings, wherein the substituent 5mol% of being not less than of the unit price of all silicon keyed jointings be the unit price aromatic hydrocarbyl and

(d2) hydrosilation reaction organic silicon oxygen alkane type thinner.

[6] according to the light-transmitting component of [4], wherein light-transmitting component is an optical waveguides.

[7] according to the light-transmitting component of [5], wherein light-transmitting component is an optical waveguides.

[8] according to the light-transmitting component of [6], wherein the covering of optical waveguides and core are made up of the hydrosilation cured product of component (A) and component (B), and the refractive index of core is than the refractive index height at least 0.1% of covering.

[9] according to the light-transmitting component of [7], wherein the covering of optical waveguides and core are formed by the hydrosilation cured product of component (A), component (B) and component (d2), and the refractive index of its SMIS is than the refractive index height at least 0.1% of covering.

[10] according to the light-transmitting component of [8], wherein component (A) and the total content of unit price aromatic hydrocarbyl in component (B) total content that be higher than the unit price aromatic hydrocarbyl of the component (A) that be used for covering and component (B) of index difference by being used in core regulated.

[11] according to the light-transmitting component of [9], wherein the total content of index difference by the unit price aromatic hydrocarbyl in the component (A), component (B) and the component (d2) that the are used in core total content that is higher than the unit price aromatic hydrocarbyl of the component (A), component (B) and the component (d2) that are used for covering is regulated.

[12] light-transmitting component of each of basis [4]-[11], it has film sample shape.

[13] be used to make the method for light-transmitting component, wherein by heating each the curable organopolysiloxane resin composition that is used for light-transmitting component that solidifies according to [1]-[3].

[14] be used to make the method for light-transmitting component, wherein will be applied over base material, solidify by heating again according to each the curable organopolysiloxane resin composition that is used for light-transmitting component of [1]-[3].

[15] be used to make the method for strip optical waveguides, wherein will be applied over base material and solidify by heating according to each the curable organopolysiloxane resin composition that is used for light-transmitting component (1) of [1]-[3], the refractive index of cured product is applied over the cured product of described composition (1) than the curable organopolysiloxane resin composition that is used for light-transmitting component (2) of the refractive index height at least 0.1% of above-mentioned composition (1) and solidifies, then above-mentioned composition (1) is applied over the cured product of above-mentioned composition (2) and solidifies by heating by heating.

[16] be used to make the method for light-transmitting component, wherein according to each the curable organopolysiloxane resin composition that is used for light-transmitting component of claim 1～3 casting and solidify in having the mould of required inner surface configuration by heating.

[17] be used to make the method for light-transmitting component, wherein 1. will have on the surface within it corresponding to casting in the outstanding mould of core according to each the curable organopolysiloxane resin composition that is used for light-transmitting component (3) of [1]-[3], and solidify by heating, 2. in mould, take out moulded product, 3. will be according to each the curable organopolysiloxane resin composition that is used for light-transmitting component (4) (refractive index of its cured product is than the refractive index height at least 0.1% of above-mentioned composition (3)) of [1]-[3] at the hollow space casting of the cured product that in mould, takes out, and solidify by heating, after this 4. above-mentioned composition (3) is applied over the top of the cured product of the cured product of above-mentioned composition (4) and above-mentioned composition (3), and solidifies by heating.

The accompanying drawing summary

Fig. 1 is the sectional view of the strip optical waveguide of embodiment 3.

Fig. 2 is the sectional view of the mould that adopts in the method for the manufacturing slot type optical waveguides of embodiment 4.

Fig. 3 is the sectional view of the mould that adopts in the method for the manufacturing slot type optical waveguides of embodiment 4.

Fig. 4 is the sectional view of the mould that adopts in the method for the manufacturing slot type optical waveguides of embodiment 4.

Fig. 5 is the sectional view of the mould that adopts in the method for the manufacturing slot type optical waveguides of embodiment 4.

Fig. 6 is the sectional view of the mould that adopts in the method for the manufacturing slot type optical waveguides of embodiment 4.

Fig. 7 is the sectional view of the mould that adopts in the method for the manufacturing slot type optical waveguides of embodiment 4.

Fig. 8 is the sectional view of the slot type optical waveguides of embodiment 4.

Reference number in the accompanying drawing is as follows:

A is a strip optical waveguide,

B is the slot type optical waveguides,

The 1st, the cured product of composition 5,

The 2nd, the cured product of composition 3,

3 is first moulds,

The 4th, projection,

The 5th, composition 4 (not containing toluene),

6 is second moulds,

The 7th, the cured product of composition 4 (not containing toluene),

The 8th, hollow space,

The 9th, the cured product of composition 3 (not containing toluene) and

10 is the 3rd moulds.

Implement best mode of the present invention

At the curable organopolysiloxane resin composition that is used for light-transmitting component of the present invention, the hydrogen atom of the silicon keyed jointing of the unit price unsaturated aliphatic alkyl of component (A) and component (B), perhaps the hydrogen atom of the silicon keyed jointing of the unit price unsaturated aliphatic alkyl of component (A) and component (d2) and component (B) comes crosslinked by hydrosilation reaction under the effect of component (C) and solidifies.

Component (A) is represented with averaged unit formula (1):

(R ¹ ₃SiO _1/2) _a(R ² ₂SiO _2/2) _b(R ³SiO _3/2) _c(SiO _4/2) _d (1)

(R wherein ¹, R ²And R ³Represent a kind of, two or more univalence hydrocarbyls, be selected from unit price aliphatic hydrocarbyl with 1～6 carbon atom and unit price aromatic hydrocarbyl with 6～10 carbon atoms, 0＜a≤0.5,0≤b＜0.2,0.3≤c＜1,0≤d≤0.4,0≤(b+d)/(a+c)≤0.25, and a+b+c+d=1), a and c anything but 0, but b and d can equal 0, unit R that Here it is ¹ ₃SiO _1/2And unit R ³SiO _3/2Be necessary unit, and unit R ² ₂SiO _2/2With cell S iO _4/2It is the reason of option unit.

Therefore, the organopolysiloxane resins that comprises the following units can be arranged:

(R ¹ ₃SiO _1/2) _a(R ³SiO _3/2) _c, (R ¹ ₃SiO _1/2) a (R ² ₂SiO _2/2) _b(R ³SiO _3/2) _c, (R ¹ ₃SiO _1/2) _a(R ³SiO _3/2) _c(SiO _4/2) _dAnd (R ¹ ₃SiO _1/2) _a(R ² ₂SiO _2/2) _b(R ³SiO _3/2) _c(SiO _4/2) _d

Yet, unit R ¹ ₃SiO _1/2Cause the reduction of molecular weight too much, Here it is 0＜a≤0.5 why, the reason of preferred 0＜a≤0.3.Unit R ³SiO _3/2Cause the decline of the degree of branching very little, Here it is 0.3≤c＜1 why, the reason of preferred 0.5≤c＜1.

Though with unit R ² ₂SiO _2/2Be incorporated into and caused generally in the organopolysiloxane resins that resin is elastic to be increased, but this can cause the reduction of its heat-drawn wire, and be the important factor that influences alteration of form.For this reason, 0≤b＜0.2, preferred 0≤b＜0.1.On the other hand, SiO _4/2Unitary introducing has caused significantly increasing of resin hardness, and resin often becomes fragile.Therefore, 0≤d≤0.4 and 0≤(b+d)/(a+c)≤0.25.

Unit price aliphatic hydrocarbyl with carbon atom of 1～6 silicon keyed jointing comprises methyl, ethyl, propyl group, butyl, hexyl and other unit price radical of saturated aliphatic alkyl, and vinyl, allyl group, hexenyl and other unit price unsaturated aliphatic alkyl.The example of the unit price aromatic hydrocarbyl of silicon keyed jointing is a phenyl, tolyl, xylyl, and naphthyl.Described unit price aliphatic hydrocarbyl is methyl preferably, and described unit price unsaturated aliphatic alkyl is vinyl preferably, and described unit price aromatic hydrocarbyl phenyl preferably.In organopolysiloxane resins, the univalence hydrocarbyl of its silicon keyed jointing 〉=10mol% must be the unit price aromatic hydrocarbyl.Be lower than loss of transmission in communication wavelength region of cured product that 10mol% causes organopolysiloxane resins.

When organic polyorganosiloxane resin was used for the light-transmitting component be made up of core and covering such as the core section of optical waveguides, the unit price aromatic hydrocarbyl preferably accounted for 〉=20mol%.The refractive index that belongs to important optical properties is regulated by the type that changes univalence hydrocarbyl.Use the substituting group of mainly forming often to make refractive index be lower than 1.5, and use the substituting group of mainly forming often to make refractive index be higher than 1.5 by phenyl and other unit price aromatic hydrocarbyl by methyl and other unit price aliphatic hydrocarbyl.

By (PhSiO _3/2) and (Me ₂ViSiO _1/2) organopolysiloxane resins formed of unit, by (PhSiO _3/2), (Me ₂SiO _2/2) and (Me ₂ViSiO _1/2) organopolysiloxane resins formed of unit, by (PhSiO _3/2), (MeSiO _3/2) and (Me ₂ViSiO _1/2) organopolysiloxane resins formed of unit, by (PhSiO _3/2), (MeSiO _3/2), (Me ₂ViSiO _1/2) and (SiO _4/2) organopolysiloxane resins formed of unit, by (PhSiO _3/2), (Me ₂ViSiO _1/2) and (SiO _4/2) organopolysiloxane resins formed of unit, by (PhSiO _3/2), (Ph ₂SiO _2/2) and (Me ₂ViSiO _1/2) organopolysiloxane resins formed of unit, by (MeSiO _3/2), (Ph ₂SiO _2/2) and (Me ₂ViSiO _1/2) organopolysiloxane resins formed of unit, by (PhSiO _3/2) and (MePhViSiO _1/2) organopolysiloxane resins formed of unit, by (PhSiO _3/2), (MeSiO _3/2) and (MePhViSiO _1/2) organopolysiloxane resins formed of unit, and by (PhSiO _3/2), (MePhViSiO _1/2) and (SiO _4/2) organopolysiloxane resins formed of unit [wherein Me represent methylidene, Ph represent phenyl, represents vinyl with Vi] is as the object lesson proposition [following identical] of organopolysiloxane resins.Two or more these type of organopolysiloxane resins can be used in combination.These organopolysiloxane resins have netted and three-dimensional structure usually.

The method that in the preparation of this type of organopolysiloxane resins, adopts be well-known (for example, " Silicone Handbook " referring to Kunio Itoh, (publish by Nikkan KogyoShinbunsha, 1990), the 468-470 page or leaf, perhaps M.Wada, " NewestSilicone Technology:Research and Applications " (published by CMC, 1986), 80-81 page or leaf).For example, they can the incompatible preparation of hydrolysis cocondensation in organic solvent by corresponding organic radical chlorosilane or organic radical organoalkoxysilane easily, the perhaps incompatible preparation of hydrolysis cocondensation in organic solvent, in the presence of strong acid catalyst by corresponding organo-siloxane oligopolymer and organic radical organoalkoxysilane.

Zhi Bei organopolysiloxane resins generally has the alkoxyl group of high-load silanol and silicon keyed jointing like this.Because the existence of the alkoxyl group of silanol and silicon keyed jointing has caused the stability in storage and the stable on heating reduction of organopolysiloxane resins, so should be preferably come dehydrating condensation or dealcoholysis condensation, the content of the alkoxyl group of silanol and silicon keyed jointing is reduced to trace by heating resin in the presence of a small amount of potassium hydroxide.Preferably, this type of group should be no more than the substituent 2mol% of all silicon keyed jointings, also more preferably no more than 1mol%.

Molecular weight for the organopolysiloxane resins of component (A) does not have specific limited, but preferably, its molecular weight should make resin become liquid at least under≤200 ℃.This is owing to the following fact: solidify and molded operation is promoted under heating, cause the resin decomposition but resin is heated to above 200 ℃ high temperature.On the other hand, in order to keep intensity after curing, organopolysiloxane resins should preferably have high molecular and wide molecular weight distribution.In addition, (the R in the suggestion averaged unit formula (1) ³SiO _3/2) unit and (R ¹ ₃SiO _1/2) unitary ratio, i.e. c/a should be not less than 0.6 and be no more than 9.0, and the viscosity under 25 ℃ is not less than 1000mPaS.Nature, when adding component (d2), viscosity will be higher than this value.

Organopolysiloxane resins must have the unit price unsaturated aliphatic alkyl/molecule of at least 3 silicon keyed jointings.From hydrosilation reaction with the thermotolerance after solidifying, vinyl is preferably as unit price unsaturated aliphatic alkyl.Even have two this unit price unsaturated aliphatic alkyl/molecules, (if having the hydrogen atom of three or more silicon keyed jointing in the silicoorganic compound as component (B)) also will take place in crosslinking reaction, but will be difficult to produce the cured product with sufficient consistency and elasticity for light-transmitting component is used.

Silicoorganic compound with component (B) of the hydrogen atom/molecule of two or more silicon keyed jointings can be organosilanes, organo-siloxane oligopolymer or organopolysiloxane.Though do not have specific limited for its molecular structure, in order to produce the cured product with high transparent, preferably it is similar with component (A) on molecular structure.That is to say that the substituent 5mol% of being not less than of unit price of its all silicon keyed jointings must be the unit price aromatic hydrocarbyl, and preferably the 10mol% that is not less than of this type of group should be the unit price aromatic hydrocarbyl.If this content is lower than 5mol%, the transparency of cured product reduces, in the transparency reduction of communication wavelength region.

The example of unit price aromatic hydrocarbyl is a phenyl, tolyl, and xylyl, and naphthyl, wherein phenyl is preferred.The preferably above-mentioned unit price radical of saturated aliphatic of organic group except unit price aromatic hydrocarbyl alkyl, wherein methyl is preferred.In addition, when light-transmitting component was made by come curing component (A) and this assembly by hydrosilation reaction such as optical waveguides, high volatile volatile had caused solidifying insufficient, the preferred reason of low voc compounds why that Here it is.Specifically, under normal pressure boiling point to be lower than 200 ℃ compound be unfavorable.

Diphenyl silane, 1, two (dimetylsilyl) benzene, 1 of 2-, two (dimetylsilyl) benzene of 4-and other have the organosilane of the hydrogen atom of two silicon keyed jointings; Phenyl three (dimethylsilane oxygen base) silane, three (aminomethyl phenyl siloxy-) silane, four (aminomethyl phenyl siloxy-) silane and other have the organo-siloxane oligopolymer of the hydrogen atom of three or four silicon keyed jointings;

By (PhSiO _3/2) and (Me ₂HSiO _1/2) organopolysiloxane resins formed of unit, by (PhSiO _3/2), (Me ₂SiO _2/2) and (Me ₂HSiO _1/2) unit organopolysiloxane resins or the branching organo-siloxane oligopolymer formed, by (PhSiO _3/2), (MeSiO _3/2) and (MeHSiO _1/2) unit organopolysiloxane resins or the branching organo-siloxane oligopolymer formed, by (PhSiO _3/2) and (MeHSiO _2/2) unit organopolysiloxane resins or the branching organo-siloxane oligopolymer formed, by (Me ₂HSiO _1/2), (MePh ₂SiO _1/2) and (SiO _4/2) unit organopolysiloxane resins or the branching organo-siloxane oligopolymer formed, by (MePhSiO _2/2) and (Me ₂HSiO _1/2) unit linear organopolysiloxane or the organo-siloxane oligopolymer formed, by (Me ₂SiO _2/2), (MePhSiO _2/2) and (Me ₂HSiO _1/2) unit linear organopolysiloxane or the organo-siloxane oligopolymer formed, by (MePhSiO _2/2), (MeHSiO _2/2) and (Me ₃SiO _1/2) unit linear organopolysiloxane or the organo-siloxane oligopolymer formed, by (MePhSiO _2/2), (MeHSiO _2/2) and (Me ₂HSiO _1/2) unit linear organopolysiloxane or the organo-siloxane oligopolymer formed, by (PhHSiO _2/2) and (Me ₃SiO _1/2) unit linear organopolysiloxane or the organo-siloxane oligopolymer formed, by (MeHSiO _2/2) and (MePh ₂SiO _1/2) the linear organopolysiloxane formed of unit or organo-siloxane oligopolymer and only by (PhHSiO _2/2) unit ring-type organopolysiloxane or the organo-siloxane oligopolymer formed propose as object lesson.

Two classes or the multiclass of these silicoorganic compound can be used in combination.The method that is used to prepare these silicoorganic compound is known, this compounds for example can be by only using the hydrogen atom contain the silicon keyed jointing the hydrolysis-condensation reaction of organochlorosilane prepare the perhaps organochlorosilane of the hydrogen atom by having the silicon keyed jointing and do not have hydrolysis cocondensation between the organochlorosilane of hydrogen atom of silicon keyed jointing and react and prepare.

The hydrosilylation catalysts of component (C) is the metal of VIII family of periodictable or their compound, and wherein platinum and platinic compound are preferred.Their example is a particulate platinum, Platinic chloride, platinum-diolefine title complex, platinum-diketone complex, platinum-divinyl tetramethyl disiloxane title complex, and platinum-phosphine composition.Its addition is 0.05-300ppm, is more preferably 0.1-50ppm, is benchmark in the weight with respect to the metal of the gross weight of component (A) and component (B).Below the scope, crosslinking reaction may be carried out insufficiently at this, is unnecessary and surpass this scope, can reduce owing to kish causes optical property.

The organopolysiloxane resin composition that is used for light-transmitting component of the present invention is by preparing component (A), component (B) and component (C) uniform mixing.When mixing these three kinds of components, even also crosslinking reaction can take place at normal temperatures, cause viscosity increased, final curing, why Here it is prepares the mixture of component (A) and component (B), when molding, component (C) and this mixture are merged again, perhaps prepare the mixture of component (A) and component (C), the more better reason of way that when molding, component (B) and this mixture is merged.

Component (A) and component (B) blended ratio should make the mol ratio 0.2-5.0 preferably of the hydrogen atom of the silicon keyed jointing in the component (B) and the unsaturated aliphatic group in the component (A), also more preferably 0.7-1.5.Component (A) preferably changes according to the desired use of gained cured product with the blending ratio of component (B).

If cured product plans to use in the near ultraviolet wavelength zone, it is desirable to amount by the hydrogen atom of regulating the silicon keyed jointing, make it surpass the amount of all unsaturated aliphatic alkyl slightly, guarantee after curing, not have the unsaturated aliphatic alkyl to keep.The hydrogen atom of residual silicon keyed jointing does not have absorption band in this zone, can not damage optical characteristics.

On the other hand,, it is desirable to, make it surpass the amount of the hydrogen atom of all silicon keyed jointings slightly, thereby guarantee after curing, not have the hydrogen atom of silicon keyed jointing residual by regulating the amount of unsaturated aliphatic alkyl if cured product plans to use near infrared wavelength zone.This is owing to the following fact: when using cured product, the hydrogen atom of silicon keyed jointing experiences oxidation under the effect of environment, may become the hydroxyl that shows the silicon keyed jointing that absorbs at this wavelength zone, and wherein hydroxyl plays the site of absorption ambient moisture.

Though the viscosity of curable organopolysiloxane resin composition of the present invention changes according to employed molding methods, preferably, it is no more than 1 * 10 under 25 ℃ ⁷MPas also more preferably, is no more than 1 * 10 ⁶MPas.Under the situation of spin coating on the base material, it preferably is no more than 1 * 10 under 25 ℃ at normal temperatures ⁴MPas.Under higher viscosity, when spin coating composition on base material, be difficult to obtain the film of uniform thickness.Though the lower value for viscosity does not have specific limited, it is higher than 500mPas (25 ℃) usually, because it is subjected to the influence of the viscosity of component (A), is higher than the viscosity of component (d2) naturally.When the viscosity of component (A) and component (B), especially the viscosity of component (A) is too high and when being not suitable for spin coating, said composition is preferably used (d1) solvent cut.When the viscosity of component (A) and component (B), especially the viscosity of component (A) is too high, makes when said composition is unsuitable in mould casting, and said composition is preferably used the dilution of (d2) hydrosilation reaction organic silicon oxygen alkane type thinner.

Solvent with boiling point of 80～200 ℃ is recommended as solvent (d1).Their object lesson is a Virahol, the trimethyl carbinol, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene, 1, chlorobenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diglyme, oxyethyl group-2-propyl alcohol acetic ester, methoxyl group-2-propyl alcohol acetic ester, octamethylcyclotetrasiloxane and hexamethyldisiloxane.This kind solvent (d1) can use separately or use as the mixture of two or more solvents.

Though depend on the thickness of filming that will form in concentration with the solid matter in the composition of solvent cut, and the viscosity and the molecular weight of component (A) and component (B), especially the viscosity and the molecular weight of component (A), but it is desirable to, this concentration should be not less than 20wt%.In addition, be suitable for general spinner form excellent quality film with the viscosity of solvent (d1) dilute compositions preferably 10～1 * 10 ⁴MPas (25 ℃).

Hydrosilation reaction organic silicon oxygen alkane type thinner (d2) can effectively reduce the viscosity of composition, and does not significantly damage the physical and mechanical properties of the cured product of organopolysiloxane resins.Recommend to use organo-siloxane oligopolymer with at least two unit price unsaturated aliphatic alkyl/molecules, wherein the univalence hydrocarbyl of all in molecule 〉=5mol% is that the number of unit price aromatic hydrocarbyl and Siliciumatom is no more than 15.

Their 25 ℃ of viscosity should preferably be no more than 500mPas, also more preferably, are no more than 300mPas.This type of organo-siloxane oligopolymer with have the component (B) of unit price aromatic hydrocarbyl and component (A) and have excellent consistency, participation crosslinking reaction, and have high transparent in the communication wavelength of the cured product of organopolysiloxane resins.

The example of this component is 1,3-divinyl dimethyl diphenyl sily oxide, and 1,5-divinyl tetramethyl-phenylbenzene trisiloxanes, phenyl three (dimethylvinylsiloxy) silane, and by (PhSiO _3/2) and (Me ₂ViSiO _1/2) the methyl ethylene phenyl siloxane oligopolymer formed of unit.

Because when its molecule contains the alkoxyl group of silanol and silicon keyed jointing, component (d2) has negative effect and causes that the thermotolerance and the temperature change stability of the cured product of organopolysiloxane resins reduce the stability in storage of composition, so preferably it should only contain trace, perhaps do not contain the alkoxyl group of silanol and silicon keyed jointing fully.When the amount of the component in being added to composition (d2) increased, the physical strength of the cured product of organopolysiloxane resins depended on its molecular structure and reduces to a certain extent.

For this reason, should determine its addition, the feasible balance that reaches between these physicalies.The addition of recommending should make that the weight ratio of [reactive diluent]/[component (A)+component (B)] is the scope at 5/95-80/20, and more preferably, recommended amounts should make that this ratio is the scope at 5/95-40/60.With the viscosity of component (d2) dilute compositions preferably 20～1 * 10 ⁴MPas (25 ℃).

Because to comprise the curable organopolysiloxane resin composition of component (A), component (B), component (C) and solvent (d1) be liquid at normal temperatures and have excellent flowability, said composition is particularly suitable for spin coating.Because to comprise the curable organopolysiloxane resin composition of component (A), component (B), component (C) and hydrosilation reaction organic silicon oxygen alkane type thinner (d2) be liquid at normal temperatures and have excellent flowability, so said composition is particularly suitable for casting.

When component (A), component (B) and component (C) are mixed, even crosslinking reaction also takes place at normal temperatures, cause viscosity increased and final curing, why if necessary Here it is, in order to prevent viscosity increased and to solidify and promote the curing under heat effect at normal temperatures and cure retarder is joined reason in the composition.Cure retarder is included in compound commonly used in the hydrosilation solidification compound, for example, and 3-methyl isophthalic acid-butine-3-alcohol, 3,5-dimethyl-1-hexin-3-alcohol, phenyl butynol and other alkynes (alkyene) alcohol; 3-methyl-pirylene, 3,5-dimethyl-1-oneself-3-alkynes and other alkene-alkine compounds; The ketone that contains alkynyl; Methyl three (1,1-dimethyl propylene alkynyloxy group) silane, dimethyl two (1,1-dimethyl propylene alkynyloxy group) silane and other contain the organosilane of alkynyl; Benzotriazole; Maleic acid ester, and fumarate.

The addition of advising them should make that the weight ratio of [cure retarder]/[metal in the hydrosilylation catalysts] is 10～10,000.When adding a large amount of above-mentioned cure retarder, said composition can be the one-part organopolysiloxane resin combination that comprises all components.In addition, only otherwise damage purpose of the present invention, it can merge with tackifier and other additive of silane coupling agent representative.

Light-transmitting component of the present invention comprises (A) and hydrosilation cured product (B): (A) organopolysiloxane resins, it is represented with averaged unit formula (1): (R ¹ ₃SiO _1/2) _a(R ² ₂SiO _2/2) _b(R ³SiO _3/2) _c(SiO _4/2) _d(1) (R wherein ¹, R ²And R ³Represent a kind of, two or more univalence hydrocarbyls, be selected from unit price aliphatic hydrocarbyl with 1～6 carbon atom and unit price aromatic hydrocarbyl with 6～10 carbon atoms, 0＜a≤0.5,0≤b＜0.2,0.3≤c＜1,0≤d≤0.4,0≤(b+d)/(a+c)≤0.25, and a+b+c+d=1), and have three or more unit price unsaturated aliphatic alkyl/molecules, wherein the 10mol% that is not less than of univalence hydrocarbyl is the unit price aromatic hydrocarbyl, (B) has the silicoorganic compound of the hydrogen atom/molecule of two or more silicon keyed jointings, and wherein the substituent 5mol% of being not less than of the unit price of all silicon keyed jointings is the unit price aromatic hydrocarbyl.

Light-transmitting component generally is made up of core with high index and the covering with low refractive index such as optical waveguides.In the organopolysiloxane resins of component (A), when being used for core and covering at the same time, the univalence hydrocarbyl of its silicon keyed jointing 〉=10mol% must be the unit price aromatic hydrocarbyl.In the silicoorganic compound of component (B), the substituent 5mol% of being not less than of unit price of its whole silicon keyed jointings is unit price aromatic hydrocarbyls.If the above-mentioned requirements of content about them is not satisfied, and will be deleterious, because the transparency of the cured product of organopolysiloxane resins in communication wavelength reduces.

The refractive index of the cured product of organopolysiloxane resins can use the unit price aliphatic hydrocarbyl (methyl usually) of silicon keyed jointing and the ratio of unit price aromatic hydrocarbyl (phenyl usually) to regulate.The increase of the ratio of unit price aromatic hydrocarbyl causes the increase of refractive index, and the ratio of increase unit price aliphatic hydrocarbyl causes the reduction of refractive index.Because the refractive index of cured product of organopolysiloxane resins that preferably is used in core is than the refractive index height at least 0.1% of the cured product of the organopolysiloxane resins that is used for covering, so the content of the preferred unit price aromatic hydrocarbyl that makes the organopolysiloxane resins that is used for core is higher than the unit price aromatic hydrocarbyl content of the organopolysiloxane resins that is used for covering.

Therefore, can be by the independent method that adopts two class organopolysiloxane resins to be used for core and covering with different [unit price aliphatic hydrocarbyl]/[unit price aromatic hydrocarbyl] mol ratio, and/or be used for the method for core and covering by the independent two class components (B) that adopt mol ratio with difference [unit price aliphatic hydrocarbyl]/[unit price aromatic hydrocarbyl], make the refractive index of the cured product that is used for core be higher than the refractive index of the cured product that is used for covering.Here, about the details of component (A) and component (B) as described in the part of the component of curable organopolysiloxane resin composition.

The light-transmitting component that comprises the cured product of organopolysiloxane resins of the present invention has the optical transparence near 100%, if be eliminated in the reflection of visible region.In addition, if use polarizer to measure polarization, can not observe polarization, double refraction is very little, can ignore.Also have, even because cured product also keeps its original shape and do not show that significant weight changes when being heated to 260 ℃, be higher than thermoplastic resin as optical material such as the thermotolerance of fluoridizing plexiglass so we can say thermotolerance that it has.In addition, cured product has elasticity and the hardness that is not easy the bending and has sufficient self-sustaining intensity.

Light-transmitting component of the present invention can be used as passive light-transmitting component or active light-transmitting component.The example of its possible purposes is no branch-waveguide, branch-waveguide, optical splitter, opticcoupler, optical adhesive and other passive light-transmitting component; Waveguide class optical switch, waveguide class optical modulator, optical attenuator, image intensifer and other active light-transmitting component.In the light-transmitting component of the present invention of the cured product that comprises organopolysiloxane resins, light-transmitting component can be made up of the cured product of independent organopolysiloxane resins, perhaps it can cover with other material or assembly, or be clipped between other assembly or the element, perhaps be inserted in other assembly or the device.

The light-transmitting component of the present invention that comprises the cured product of organopolysiloxane resins is made by the above-mentioned curable organopolysiloxane resin composition that heating and curing are used for light-transmitting component.This manufacture method can be divided into following two types roughly.In other words, there is a kind of method of making light-transmitting component, in the method, the curable organopolysiloxane resin composition that will be used for light-transmitting component is coated on the base material and by heating and is solidified, and a kind of method of making light-transmitting component, in the method, by coming casting at mould internal heating and solidifying the curable organopolysiloxane resin composition that is used for light-transmitting component with required inner surface configuration.Can also use injection moulding, extrusion molding and other manufacture method.

The base material that adopts in first manufacture method preferably has flat surface, and for solvent that in solidification process, uses and temperature-stable.Its example is a silicon chip, glass, pottery, and heat resistant plastice.

The light-transmitting component that has high-transmission rate at specified wavelength zone is coated base material by the above-mentioned curable organopolysiloxane resin composition that will be used for light-transmitting component and is made by being heating and curing, but if necessary, film sample light-transmitting component obtains by peeling off cured product from base material.In addition, strip optical waveguide can prepare by following steps: the above-mentioned curable organopolysiloxane resin composition (1) that 1. will be used for light-transmitting component is applied over base material and solidifies by heating, the curable organopolysiloxane resin composition (2) (refractive index of its cured product is than the refractive index height at least 0.1% of above-mentioned composition (1)) that 2. will be used for light-transmitting component is applied over the cured product of above-mentioned composition (1) and solidifies by heating, 3. above-mentioned composition (1) is applied over this cured product and solidifies, 4. peel off cured product then from base material by heating.

In this case, the cured product of above-mentioned composition (1) is used for bottom covering and top covering, and the cured product of above-mentioned composition (2) is as sandwich layer.Film like slot type optical waveguides obtains through the following steps: the cured product of giving above-mentioned composition (2) is with desired shape, then above-mentioned composition (1) is coated the cured product of above-mentioned composition (1) and the cured product of above-mentioned composition (2), solidify again, if necessary peel off subsequently from base material.

When the cured product of giving above-mentioned composition (2) during, preferably use required pattern to carry out etching with desired shape.At this moment, form resist pattern, remove the sandwich layer of not protected, remove described resist then and form the core pattern by resist pattern by etching by going up at the cured product (sandwich layer) of above-mentioned composition (2) with photoetch method.In addition, film like slot type optical waveguides also can obtain through the following steps: the above-mentioned curable organopolysiloxane resin composition that will be used for light-transmitting component (1) is coated base material and is heating and curing, peel off cured product (bottom covering) from base material, and form core pattern and upper clad layer on the top of above-mentioned cured product according to main points described above.

The curable organopolysiloxane resin composition that is used for light-transmitting component that uses in aforesaid method preferably is liquid at normal temperatures, especially has 20～1 * 10 under 25 ℃ ⁴The viscosity of mPas.

Preferred compositions contains component (D), especially component (d1).Though at this moment the solidification value of Shi Yonging depends on the component that constitutes described composition, the especially type and the amount of component (C), and the type of cure retarder and amount, it is the scope at 80-200 ℃ usually.It is used for being coated on the preferably spin coating of method of the curable organopolysiloxane resin composition that is used for light-transmitting component that uses in the above-mentioned manufacture method, because can form uniform film fast.In the manufacturing processed of film shape light-transmitting component, can use solvent cast to replace spin coating.

The mould that the mould that adopts in second manufacture method is preferably made by base material, the thermal expansivity of this base material is less than the thermal expansivity of the cured product of organopolysiloxane resins.Nature, the cured product of organopolysiloxane resins must be easy to take out from mould.If it has inadequate demolding performace, preferably only after with the internal surface of releasing agent coating die, carry out molding.

The light-transmitting component that has high-transmission rate in communication wavelength can be made through the following steps: the curable organopolysiloxane resin composition (3) that 1. will be used for light-transmitting component has on internal surface corresponding to casting in the outstanding mould of core, and solidify by heating, 2. in mould, take out solidifying product, 3. will be used for the hollow space casting of the curable organopolysiloxane resin composition (4) (refractive index of its cured product is than the refractive index height at least 0.1% of above-mentioned composition (3)) of light-transmitting component at the cured product that in mould, takes out, and solidify by heating, after this 4. above-mentioned composition (3) is coated on the cured product of the cured product of above-mentioned composition (4) and above-mentioned composition (3), and solidified by heating.

At this moment, the solidifying product that will take out from mould is assembled in another mould, after this, the above-mentioned curable organopolysiloxane resin composition (4) that will be used for light-transmitting component is injected into wherein and solidifies by heating, and solidifies at the top coating above-mentioned composition (3) of the cured product of the cured product of above-mentioned composition (4) and above-mentioned composition (3) and by heating.

The curable organopolysiloxane resin composition that uses in second manufacture method preferably contains component (D), especially component (d2).Its 25 ℃ of viscosity preferably 20～1 * 10 ⁴MPas.

The width of the hollow space of casting curable organopolysiloxane resin composition is no more than tens μ m usually, Here it is be used for the viscosity of the curable organopolysiloxane resin composition of core why must be fully low, to be convenient to casting.Because the viscosity of described composition reduces when temperature raises, so if above-mentioned 25 ℃ of viscosity be≤1 * 10 ⁷MPas just can casting, but requires even littler viscosity at the casting near the temperature range of room temperature.

Though solidification value at this moment depends on the component of forming described composition, the especially type and the amount of component (C), the type and the amount that also have cure retarder in addition, but under the situation of the curable organopolysiloxane resin composition of forming by component (A), component (B) and component (C), preferably 80-180 ℃ of temperature, by component (A), component (B), component (C) and component (D) (d2) under the situation of the curable organopolysiloxane resin composition formed of hydrosilation reaction organic silicon oxygen alkane type reactive diluent, preferably 20-180 ℃ of this temperature.

Under heating, by the in fact not variation of size of metal with little thermal expansivity or the ceramic mould of making, on the other hand, the cured product with organopolysiloxane resins of big thermal expansivity has experienced thermal expansion, and the result has stood pressure.Therefore, the cured product of organopolysiloxane resins closely contacts with the surface of mould, and the pattern on the die surface is accurately transferred on the cured product of organopolysiloxane resins.When solidifying end, cooling die, the cured product of organopolysiloxane resins shrinks.Slowly cooling is preferred, thereby the generation of the string stress that will cause owing to the part cooling reduces to minimum.

The curable organopolysiloxane resin composition that is used for light-transmitting component of the present invention has low refractive index temperature dependency not introducing the deuterate alkyl and fluoridize under the situation of alkyl, high heat resistance, high transparent in communication wavelength, have and make its elasticity that is difficult to be out of shape and hardness, and can regulate index difference between core material and the clad material in such as the manufacturing processed of optical waveguides easily at light-transmitting component.

Also has low refractive index temperature dependency even comprise the light-transmitting component of the cured product of organopolysiloxane resins of the present invention not introducing the deuterate alkyl and fluoridize under the situation of alkyl, high heat resistance, high transparent in communication wavelength, have and make its elasticity that is difficult to be out of shape and hardness, and can regulate index difference between core material and the clad material in such as the manufacturing processed of optical waveguides easily at light-transmitting component.Therefore in addition, the light-transmitting component that comprises the cured product of organopolysiloxane resins of the present invention has seldom shown transmission loss at the telecom wavelengths band, is suitable as the material of the integrated optical circuit of the optical communication of near-infrared region and light interconnection and near-infrared region.

Being used to make the method for light-transmitting component of the present invention can be easily and produce the light-transmitting component of the cured product that comprises organopolysiloxane resins economically, even described assembly do not introduce the deuterate alkyl and fluoridize also have low refractive index temperature dependency under the situation of alkyl, high heat resistance, at the high transparent of communication wavelength region, have and make its elasticity that is difficult to be out of shape and hardness, and in the preparation process of light-transmitting component, eliminated mixing between core and the covering such as optical waveguides.

Embodiment

Though followingly the invention provides embodiment and comparative example, the invention is not restricted to these embodiment in order to specify.Gel permeation chromatography (GPC) is used to measure the molecular weight of employed reactive diluent, silicoorganic compound and organopolysiloxane resins, and their number-average molecular weight is by relatively calculating with polystyrene standard.Viscosity uses rotational viscosimeter to measure down at 25 ℃.

The content of silanol and methoxy or ethoxy passes through ²⁹Si NMR analyzes and measures.The refractive index of cured product uses the prism coupler method to measure under the wavelength of 1550nm, and the thickness of film uses Tencor Alpha-Step 200 to measure.The Young's modulus of cured product uses the dynamic viscoelastic metering facility on the 2mm thick plates, measures in 0～50 ℃ temperature range under the strain of the frequency of 1Hz and 0.5%.In addition, the transparency of cured product uses the spectrophotometer with 3mm thick plates to measure under the wavelength of 1550nm.The optical loss value of cured product under 1550nm measured by dilution method (cutback method).The polarization dependence of cured product uses polarizer to observe under opticmicroscope.The thermotolerance of cured product is estimated by thermogravimetric analysis.

The general introduction of the silicoorganic compound of the organopolysiloxane resins of the component of Shi Yonging (A) and component (B) (in formula, Me represent methylidene and Ph represent phenyl) in an embodiment;

Methyl ethylene phenyl polysiloxane resin (A-1):

Averaged unit formula: [Me ₂(CH ₂=CH) SiO _1/2] _0.25[PhSiO _3/2] _0.75, phenyl content: 50mol%, number-average molecular weight: 1900, viscosity:＞1,000,000mPas, silanol and methoxy content: 0.8mol%, preparation method: with 1,3-divinyl-1,1,3, the 3-tetramethyl disiloxane, phenyltrimethoxysila,e stirs under reflux with the water that contains the trifluoromethanesulfonic acid of catalytic amount, impels hydrolytic condensation, in using alkali and after the described acid catalyst, carry out water and methanol-eluted fractions, a spot of potassium hydroxide is joined in the residue that is dissolved in toluene, dewater, in using acid and after the potassium hydroxide in heating with under stirring, filter out salt, carry out the toluene wash-out.

Methyl ethylene phenyl polysiloxane resin (A-2):

Averaged unit formula: [Me ₂(CH ₂=CH) SiO _1/2] _0.25[PhSiO _3/2] _0.65Phenyl content: 46mol%, number-average molecular weight: 2300, viscosity:＞1,000,000mPas, silanol and oxyethyl group content: 1mol%, the preparation method: with vinyl-dimethyl base chlorosilane, phenyl-trichloro-silicane, tetraethyl orthosilicate and water stir under reflux, impel hydrolytic condensation, in with alkali and after the hydrochloric acid that is produced, carry out water and ethanol elution, a spot of potassium hydroxide is joined in the residue that is dissolved in toluene, dewater in heating with under stirring, with in the acid and after the potassium hydroxide, filter out the salt that is produced, carry out the toluene wash-out.

Methyl ethylene phenyl polysiloxane resin (A-3):

Averaged unit formula: [Me ₂(CH ₂=CH) SiO _1/2] _0.25[MeSiO _3/2] _0.40[PhSiO _3/2] _0.35, phenyl content: 23mol%, number-average molecular weight: 4600, viscosity:＞1,000,000mPas, silanol and methoxy content: 1mol%, the preparation method: with 1,3-divinyl-1,1,3, the 3-tetramethyl disiloxane, methyltrimethoxy silane, phenyltrimethoxysila,e stirs under reflux with the water that contains the trifluoromethanesulfonic acid of catalytic amount, impel hydrolytic condensation, with in the alkali and after the described acid catalyst, carry out water and methanol-eluted fractions, a spot of potassium hydroxide is joined in the residue that is dissolved in toluene, dewater in heating with under stirring, with in the acid and after the potassium hydroxide, filter out the salt that is produced, carry out the toluene wash-out.

Aminomethyl phenyl hydrogenation polysiloxane (B-1):

Averaged unit formula: [Me ₂HSiO _1/2] _0.6[PhSiO _3/2] _0.4, phenyl content: 18mol%, number-average molecular weight: 900, viscosity: 30mPas, silanol and methoxy content: 0.2mol%, preparation method: with 1,1,3, the 3-tetramethyl disiloxane, the trifluoromethanesulfonic acid of phenyltrimethoxysila,e and catalytic amount stirs under cooling, impel hydrolytic condensation, with in the alkali and after the described acid catalyst, filter out salt, carry out water elution.

Aminomethyl phenyl hydrogenation polysiloxane (B-2):

Averaged unit formula: [Me ₂HSiO _1/2] _0.2[MeHSiO] _0.4[MePhSiO] _0.4, phenyl content: 18mol%, number-average molecular weight: 900, viscosity: 25mPas, silanol and methoxy content: 0.1mol%, preparation method: with 1,1,3, the 3-tetramethyl disiloxane, dimethyl dichlorosilane (DMCS) and dichloromethyl phenylsilane stir under cooling, impel hydrolytic condensation, in with alkali and after the hydrochloric acid that is produced, filter out the salt that is produced, carry out water elution.

Methyl ethylene phenyl siloxane oligopolymer (d2):

Averaged unit formula: [Me ₂(CH ₂=CH) SiO _1/2] _0.67[PhSiO _3/2] _0.33Phenyl content: 14mol%, number-average molecular weight: 650, viscosity: 50mPas, silanol and methoxy content: 0.2mol%, preparation method: with 1,3-divinyl-1,1,3, the 3-tetramethyl disiloxane, phenyltrimethoxysila,e stirs under reflux with the water that contains the trifluoromethanesulfonic acid of catalytic amount, impels hydrolytic condensation, in using alkali and after the described acid catalyst, carry out water and methanol-eluted fractions, a spot of potassium hydroxide is joined in the residue that is dissolved in toluene, dewater, in using acid and after the potassium hydroxide in heating with under stirring, filter out the salt that is produced, carry out the toluene wash-out.

Embodiment 1

Present embodiment has illustrated the formation of the cured product of the methyl ethylene phenyl polysiloxane resin that is used for light-transmitting component.By using the ratio (unit of in following table 1, enumerating: g) with above-mentioned methyl ethylene phenyl polysiloxane resin (A-1), (A-2) and (A-3) (they are as component (A)), above-mentioned aminomethyl phenyl hydrogenation polysiloxane (B-1) and (B-2) (they as component (B)), platinum/1,3-divinyl tetramethyl disiloxane title complex [platinum content: 2wt%] is (it is as component (C)) (C), methyl (three (1,1-dimethyl-2-third alkynyloxy group)) silane (E) (it is as cure retarder) and toluene (it is as component (d1)) mix and prepare the coating solution that comprises the curable organopolysiloxane resin composition that is used for light-transmitting component.

Adopt uncovered cell-type system, under 2000rpm, this coating solution is spun on the silicon substrate, at room temperature left standstill 10 minutes.After this, by 180 ℃ down heating obtained to have the aminomethyl phenyl hydrogenation polysiloxane of uniform thickness of 7～8 μ m and the hydrosilation cured product of methyl ethylene phenyl polysiloxane resin in 90 minutes.

In table 1, enumerated the viscosity of coating solution, and the transparency of the cured product of coating solution and refractive index.

[table 1]

	Composition 1	Composition 2	Composition 3	Composition 4	Composition 5
	Composition 1	Composition 2	Composition 3	Composition 4	Composition 5	(A-1)	20.0	20.0
(A-2)			20.0		17.0	(A-1)	20.0	20.0
(A-2)			20.0		17.0	(A-3)				20.0	3.0
(B-1)	6.4		6.9	8.1	7.1	(A-3)				20.0	3.0
(B-1)	6.4		6.9	8.1	7.1	(B-2)		6.4
(C)	0.004	0.004	0.004	0.004	0.004	(B-2)		6.4
(C)	0.004	0.004	0.004	0.004	0.004	(E)	0.008	0.008	0.008	0.008	0.008
(d-1)	11.3	11.3	11.5	12.0	11.6	(E)	0.008	0.008	0.008	0.008	0.008
(d-1)	11.3	11.3	11.5	12.0	11.6	Viscosity-1	100,000	94,000	170,000	250,000	195,000
Viscosity-2	30	28	35	45	38	Viscosity-1	100,000	94,000	170,000	250,000	195,000
Viscosity-2	30	28	35	45	38	Refractive index	1.530	1.526	1.525	1.500	1.519
Transmissivity	96.0	95.8	95.2	94.0	94.0	Refractive index	1.530	1.526	1.525	1.500	1.519

(annotate: " viscosity-1 " representative does not have the viscosity of the composition of component (d1), and (unit: mPas), " viscosity-2 " representative contains the viscosity (unit: mPas) of the composition of component (d1)." refractive index " and " transparency " is meant the value by the measurement acquisition of cured product.)

All cured products are colourless and transparent, Young's modulus with 0.8～1.0GPa, in other words, they have elasticity and the hardness that prevents its easy bending and have sufficient self-sustaining intensity, even and also do not observe the variation that causes owing to dissolving, swelling etc. after dipping spends the night in toluene.In addition, the transmissivity of the cured product in communication wavelength is 〉=94%, the optical loss value is 0.5dB/cm, it is sufficient promptly using for light-transmitting component.

Embodiment 2

Present embodiment has illustrated forming of the slot type optical waveguides be made up of the cured product of the methyl ethylene phenyl polysiloxane resin of making by coating process.

Adopt uncovered cell-type system, the composition 5 with table 1 under 2000rpm is spun on the silicon substrate, at room temperature leaves standstill 10 minutes.After this, by 180 ℃ down heating obtained to have the film that the hydrosilation cured product by aminomethyl phenyl hydrogenation polysiloxane and methyl ethylene phenyl polysiloxane resin of the uniform thickness of 7 μ m is formed in 90 minutes.Its refractive index is 1.519.Next, the film of being made up of this cured product is used as the bottom covering, and the composition 3 of spin coating table 1 under 2000rpm was at room temperature placed 10 minutes in the above.After this, the film of forming by the hydrosilation cured product that formed uniform thickness in 90 minutes 180 ℃ of following heating by aminomethyl phenyl hydrogenation polysiloxane and methyl ethylene phenyl polysiloxane resin with 7 μ m.

Coating has the photoresist material of the thickness of 2.0 μ m, forms pattern on by the film of forming as the cured product of sandwich layer.Adopt resist as photomask, with containing CF ₄Mixed gas carry out reactive ion etching.Has 50mm length thereby produce, the linear long square pattern of the sandwich layer of 7.0 μ m width and 7.0 μ m height.Remove resist then.At last, the composition 5 with table 1 under 2000rpm is spun on core pattern and the bottom covering, heats 90 minutes down at 180 ℃ subsequently, has obtained the slot type optical waveguides.In this optical waveguides, do not mix between core and the covering, the optical loss value is 0.4dB/cm simultaneously.In addition, when optical waveguides heats, do not observe weight loss until 280 ℃ in airflow, this has confirmed its excellent heat resistance.

Embodiment 3

Present embodiment has illustrated forming of the strip optical waveguide be made up of the cured product of the methyl ethylene phenyl polysiloxane resin of making by coating process.After the composition 5 of table 1 coated on the glass baseplate and at room temperature placed about 30 minutes, by 100 ℃ down heating 1 hour and 180 ℃ down heating solidified said composition in 1 hour, at room temperature peel off the film that the hydrosilation cured product by aminomethyl phenyl hydrogenation polysiloxane and methyl ethylene phenyl polysiloxane resin of making the thickness with 50 μ m is formed then from glass baseplate.Its refractive index is 1.519.The film of being made up of this cured product does not show polarization dependence, and the double refraction that has proved it is very little, can ignore.

The film of being made up of cured product is used for the bottom covering, again the composition 3 of table 1 is coated on it, and be heating and curing in the same manner, thereby formed the sandwich layer with refractive index of 1.525, its film of being made up of the hydrosilation cured product of the aminomethyl phenyl hydrogenation polysiloxane of the thickness with 50 μ m and methyl ethylene phenyl polysiloxane resin is formed.In addition, composition 5 by coating table 1 and being heating and curing in the same manner forms the upper clad layer of the refractive index of thickness with 50 μ m and 1.519 on the film of being made of this cured product, thereby prepared and had three-decker, be the strip optical waveguide of covering-sandwich layer-covering, have the total thickness (referring to Fig. 1) of 150 μ m.This optical waveguides does not show mixing between core and the covering, even do not ftracture after alternating bending yet or peel off, does not find polarization dependence yet.In addition, when optical waveguides heats, also do not observe weight loss until 280 ℃ in airflow, this has confirmed its excellent heat resistance.

Embodiment 4

Present embodiment has illustrated forming of the slot type optical waveguides be made up of the cured product of the methyl ethylene phenyl polysiloxane resin of making by the casting method.

The composition 4 (it does not contain toluene) of table 1 is heated to 80 ℃, have outstanding 4 on 80 ℃ the surface within it (highly: 50 μ m being heated to, width: 50 μ m, length: casting in first mould 3 (referring to Fig. 2) 50mm), solidified (referring to Fig. 3) in other 1 hour by heating 1 hour down and heat down at 180 ℃ then at 100 ℃.Under this temperature, from first mould 3, take out the cured product 7 (not containing toluene) 5 of composition 4, put into again in second mould 6 that is heated to 80 ℃ (referring to Fig. 4), with the composition 3 (not containing toluene) of table 1 (highly: 50 μ m at the hollow space 8 of cured product 7, width: 50 μ m, length: casting 50mm), solidified (referring to Fig. 5) in other 1 hour by at first heating 1 hour down and heat down at 180 ℃ then at 100 ℃.

From second mould 6, take out the cured product 7 (not containing toluene) of composition 4, put in the 3rd mould 10 (referring to Fig. 6), so composition 4 (not containing toluene) is casting therein, solidified (referring to Fig. 7) in other 1 hour by heating 1 hour down and heat down at 180 ℃ then at 100 ℃.Take out cured product from the 3rd mould 10, obtained cord-like slot type optical waveguides (referring to Fig. 8), it has the height of 50 μ m, the width of 50 μ m, the length of 50mm, wherein the refractive index of core segment be 1.525 and the refractive index of clad section be 1.500.This optical waveguides does not show mixing and do not have a cracking between core and the covering, does not ftracture or peels off even have alternating bending after simultaneously yet, and do not observe polarization dependence.In addition, when optical waveguides heats, also do not observe weight loss until 280 ℃ in airflow, this has confirmed its excellent heat resistance.

Embodiment 5

By will be as the methyl ethylene phenyl polysiloxane resin (A-2) of the 10g of component (A) and methyl ethylene phenyl siloxane oligopolymer (d2) uniform mixing as the 10g of component (d2), add aminomethyl phenyl hydrogenation polysiloxane (B-1) then as the 13g of component (B), platinum/1 as the 5mg of component (C), 3-divinyl tetramethyl disiloxane title complex [platinum content: 2wt%] is (C) with as the methyl (three (1 of the 10mg of cure retarder, 1-dimethyl-2-third alkynyloxy group) silane (E), each composition of uniform mixing prepares water white methyl ethylene phenyl polysiloxane resin combination 6 again.The viscosity of said composition is 200mPas.

By will be as the methyl ethylene phenyl polysiloxane resin (A-3) of the 10g of component (A) and methyl ethylene phenyl siloxane oligopolymer (d2) uniform mixing as the 10g of component (d2), add aminomethyl phenyl hydrogenation polysiloxane (B-1) then as the 13.9g of component (B), platinum/1 as the 5mg of component (C), 3-divinyl tetramethyl disiloxane title complex [platinum content: 2wt%] is (C) with as the methyl (three (1 of the 10mg of cure retarder, 1-dimethyl-2-third alkynyloxy group) silane (E), each composition of uniform mixing prepares water white methyl ethylene phenyl polysiloxane resin combination 7 again.The viscosity of said composition is 240mPas.

Except using composition 7 as covering with use composition 6 takes out as core and at 25 ℃ of following castings with from mould, make cord-like slot type optical waveguides according to the mode identical with embodiment 4.The refractive index of clad section is 1.482, and the refractive index of core segment is 1.505.This optical waveguides does not show mixing and do not have a cracking between core and the covering, does not ftracture or peels off even have alternating bending after simultaneously yet, and do not observe polarization dependence.In addition, when optical waveguides heats, also do not observe weight loss until 280 ℃ in airflow, this has confirmed its excellent heat resistance.

The comparative example 1

Present embodiment has illustrated the formation based on the flexible optical waveguide of the Application Example of Japanese Patent Application Publication No.Sho 63-217306.Dimethyl siloxane-methylphenyl siloxane multipolymer (25mol% phenyl in the linear trimethylsiloxy terminal of the viscosity with 5000mPas of 100 weight parts, refractive index: add the chloroformic solution of Platinic chloride 1.50) and in the mixture of the dimethyl siloxane of the trimethylsiloxy terminal of the viscosity with 5mPas of 5 weight parts-hydrogenated methyl silicone copolymers, obtained to have the hydrosilation solidified nature liquid silicones composition of the platinum content of 5ppm (weight).Said composition is extruded in warm air, has formed the wire silicone rubber core of the diameter with 1mm.

Subsequently, coating has the hydrosilation solidified nature liquid silicones rubber combination (principal constituent: the dimethyl polysiloxane of linear dimethylvinylsiloxy terminal of the viscosity of 3000mPas on core, the dimethyl siloxane of trimethylsiloxy terminal-hydrogenated methyl silicone copolymers, and Platinic chloride, refractive index: 1.41) afterwards, by 150 ℃ down 5 minutes curing composition manufacturings of heating have the wire flexible optical waveguide of 1.4mm diameter.This optical waveguides easy deformation does not have self-sustaining intensity.In addition, when it heats in air, found owing to decompose the weight loss that causes, the thermotolerance that this indication is inferior since 200 ℃.

The comparative example 2

Present embodiment has illustrated the formation based on the polysilsesquioxane optical waveguides of the embodiment 2 of Japanese Patent Application Publication No.Hei 4-157402.Adopt poly methyl silsesquioxane (molecular weight Mw=2000, refractive index: 1.423) as covering and polyphenylene silsesquioxane (molecular weight Mw=15000, refractive index: 1.555) as core, by spin coating, photoetch method, the dry etching method, and then use spin coating to make the slot type optical waveguides as final step, its SMIS is made up of the polyphenylene silsesquioxane, width with 8 μ m, the height of 8 μ m, the length of 50mm, and upper clad layer of forming by poly methyl silsesquioxane and the thickness that has 20 μ m by the bottom covering that poly methyl silsesquioxane is formed.The optical loss value of this optical waveguides is no more than 0.5dB/cm.When optical waveguides 260 ℃ of following thermal treatments in the time of 2 minutes, the descend refractive index of 0.3%, two covering of the refractive index of core descends 0.8%, therefore with the difference that before thermal treatment, exists relatively, changed at this index difference between the two.This represents that this optical waveguides has inferior thermotolerance.

Industrial applicability

Curable organopolysiloxane resin composition for light-transmitting component of the present invention can be used for making various light-transmitting components, and be suitable for as the optic communication of near infrared region and the material of integrated optical circuit, light-transmitting component of the present invention can be used as with without branch-waveguide, branch-waveguide, optical splitter, photo-coupler, optical adhesive is the passive light-transmitting component of example, and with waveguide class optical switch, waveguide class optical modulator, optical attenuator, image intensifer are the active light-transmitting component of example. Make processing cost that the method for light-transmitting component of the present invention can be lower for the manufacture of various light-transmitting components.

Claims

1, the curable organopolysiloxane resin composition that is used for light-transmitting component, said composition comprise (A) organopolysiloxane resins, and it is represented with averaged unit formula (1):

(R ¹ ₃SiO _1/2) _a(R ² ₂SiO _2/2) _b(R ³SiO _3/2) _c(SiO _4/2) _d (1)

(R wherein ¹, R ²And R ³Representative is selected from unit price aliphatic hydrocarbyl with 1～6 carbon atom and has a kind of in the unit price aromatic hydrocarbyl of 6～10 carbon atoms, two or more univalence hydrocarbyls, 0＜a≤0.5,0≤b＜0.2,0.3≤c＜1,0≤d≤0.4,0≤(b+d)/(a+c)≤0.25, and a+b+c+d=1), and have three or more unit price unsaturated aliphatic alkyl/molecules, wherein the 10mol% that is not less than of univalence hydrocarbyl is the unit price aromatic hydrocarbyl, (B) have the silicoorganic compound of the hydrogen atom/molecule of two or more silicon keyed jointings, wherein the substituent 5mol% of being not less than of the unit price of all silicon keyed jointings is unit price aromatic hydrocarbyl and (C) hydrosilylation catalysts.

2, according to the curable organopolysiloxane resin composition that is used for light-transmitting component of claim 1, wherein the viscosity of said composition is no more than 1 * 10 under 25 ℃ ⁷MPas.

3, the curable organopolysiloxane resin composition that is used for light-transmitting component, said composition comprise (A) organopolysiloxane resins, and it is represented with averaged unit formula (1):

(R ¹ ₃SiO _1/2) _a(R ² ₂SiO _2/2) _b(R ³SiO _3/2) _c(SiO _4/2) _d (1)

4, light-transmitting component, this assembly comprise (A) and hydrosilation cured product (B):

(R ¹ ₃SiO _1/2) _a(R ² ₂SiO _2/2) _b(R ³SiO _3/2) _c(SiO _4/2) _d (1)

(R wherein ¹, R ²And R ³Representative is selected from a kind of, two or more univalence hydrocarbyls in unit price aliphatic hydrocarbyl with 1～6 carbon atom and the unit price aromatic hydrocarbyl with 6～10 carbon atoms, 0＜a≤0.5,0≤b＜0.2,0.3≤c＜1,0≤d≤0.4,0≤(b+d)/(a+c)≤0.25, and a+b+c+d=1), and have three or more unit price unsaturated aliphatic alkyl/molecules, wherein the 10mol% that is not less than of univalence hydrocarbyl is the unit price aromatic hydrocarbyl

5, light-transmitting component, this assembly comprise (A), (B) and hydrosilation cured product (d2):

(R ¹ ₃SiO _1/2) _a(R ² ₂SiO _2/2) _b(R ³SiO _3/2) _c(SiO _4/2) _d (1)

(d2) hydrosilation reaction organic silicon oxygen alkane type thinner.

6, according to the light-transmitting component of claim 4, wherein light-transmitting component is an optical waveguides.

7, according to the light-transmitting component of claim 5, wherein light-transmitting component is an optical waveguides.

8, according to the light-transmitting component of claim 6, wherein the covering of optical waveguides and core are made up of the hydrosilation cured product of component (A) and component (B), and the refractive index of core is than the refractive index height at least 0.1% of covering.

9, according to the light-transmitting component of claim 7, wherein the covering of optical waveguides and core are formed by the hydrosilation cured product of component (A), component (B) and component (d2), and the refractive index of its SMIS is than the refractive index height at least 0.1% of covering.

10, light-transmitting component according to Claim 8, wherein component (A) and the total content of unit price aromatic hydrocarbyl in component (B) total content that be higher than the unit price aromatic hydrocarbyl of the component (A) that be used for covering and component (B) of index difference by being used in core regulated.

11, according to the light-transmitting component of claim 9, wherein the total content of index difference by the unit price aromatic hydrocarbyl in the component (A), component (B) and the component (d2) that the are used in core total content that is higher than the unit price aromatic hydrocarbyl of the component (A), component (B) and the component (d2) that are used for covering is regulated.

12, according to each light-transmitting component of claim 4～claim 11, it has film sample shape.

13, make the method for light-transmitting component, wherein by heating each the curable organopolysiloxane resin composition that is used for light-transmitting component that solidifies according to claim 1～3.

14, make the method for light-transmitting component, wherein will be applied over base material, solidify by heating again according to each the curable organopolysiloxane resin composition that is used for light-transmitting component of claim 1～3.

15, make the method for strip optical waveguides, wherein will be applied over base material and solidify by heating according to each the curable organopolysiloxane resin composition that is used for light-transmitting component (1) of claim 1～3, the refractive index of cured product is applied over the cured product of above-mentioned composition (1) than the curable organopolysiloxane resin composition that is used for light-transmitting component (2) of the refractive index height at least 0.1% of above-mentioned composition (1) and solidifies, then above-mentioned composition (1) is applied over the cured product of above-mentioned composition (2) and solidifies by heating by heating.

16, make the method for light-transmitting component, wherein according to each the curable organopolysiloxane resin composition that is used for light-transmitting component of claim 1～3 casting and solidify in having the mould of required inner surface configuration by heating.

17, make the method for light-transmitting component, wherein 1. will on internal surface, have corresponding to casting in the outstanding mould of core according to each the curable organopolysiloxane resin composition that is used for light-transmitting component (3) of claim 1～3, and solidify by heating, 2. in mould, take out moulded product, 3. will be according to each the curable organopolysiloxane resin composition that is used for light-transmitting component (4) (refractive index of its cured product is than the refractive index height at least 0.1% of above-mentioned composition (3)) of claim 1～3 at the hollow space casting of the cured product that in mould, takes out, and solidify by heating, after this 4. above-mentioned composition (3) is applied over the top of the cured product of the cured product of above-mentioned composition (4) and above-mentioned composition (3), and solidifies by heating.