JP2005163009A - (meth)acryloxy group-containing organopolysiloxane resin, high-energy beam curable organopolysiloxane resin composition, optical transmission member, and method for producing the optical transmission member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a high-energy beam curable organopolysiloxane resin composition capable of being rapidly cured by irradiation of a high-energy beam and capable of giving a cured product having high light transmittance in a communication wavelength range, to obtain an organopolysiloxane resin used for the composition, to provide an optical transmission member formed of the cured product having the high light transmittance in the communication wavelength range, and to provide a method for simply, rapidly and efficiently producing the optical transmission member. <P>SOLUTION: The organopolysiloxane resin contains (meth)acryloxy groups and aromatic groups. The high-energy beam curable organopolysiloxane resin composition (which is, for example, cured by ultraviolet light) comprises the organopolysiloxane resin containing the (meth)acryloxy groups and the aromatic groups, a photopolymerization catalyst, and if necessary, an organic solvent. The optical transmission member is formed of the cured product which is given by irradiating the organopolysiloxane resin with the high-energy beam in the coexistence of the photopolymerization catalyst. The method for producing the optical transmission member comprises coating a base material with the composition and irradiating the coated material with the high-energy beam. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a (meth) acryloxy group-containing organopolysiloxane resin having a high monovalent aromatic hydrocarbon group content, a high energy ray-curable organopolysiloxane resin composition comprising the organopolysiloxane resin as a main component, and the organopolysiloxane. The present invention relates to an optical transmission member made of a cured siloxane resin and a method for producing an optical transmission member from the organopolysiloxane resin composition.

Quartz or glass is used as a highly reliable material not only as an optical fiber material but also as an optical material for optical communication. However, since these inorganic materials require high-temperature processing and are inferior in productivity, organic materials for communication elements that are workable and durable have been demanded. The most reliable organic material is polyimide, which is widely used as a material for electronic parts. On the other hand, organopolysiloxanes are attracting attention in the field of optoelectronics because of their excellent light transmission, insulation, light stability, thermal stability, and the like. Among the physical properties required for optical transmission materials, optical properties such as no absorption in the communication wavelength band of 1300 to 1660 nm, no birefringence due to polymer chain orientation, heat resistance and moisture absorption resistance in device assembly Water resistance is regarded as important, and the above-mentioned property improvement is being promoted mainly on polyimide and organopolysiloxane materials.

As an organopolysiloxane optical transmission material, in JP-A-3-43423, (R ₁ R ₂ SiO _2/2 ) unit (wherein R ₁ and R ₂ are deuterium atoms of alkyl group or phenyl group hydrogen atom). Or (R ₁ SiO _3/2 ) (R ₂ SiO _3/2 ) units (wherein R ₁ and R ₂ are alkyl groups or phenyl groups). An optical element and an optical material made of an organopolysiloxane composed of a deuterium atom or a halogen atom, or a copolymer of these units have been proposed. Has proposed an optical waveguide made of a similar organopolysiloxane, in which a hydrogen atom of an alkyl group or a phenyl group is substituted with a deuterium atom or a halogen atom. Problem that the material cost is high, and heat resistance because it is cured, there is a problem that solvent resistance is poor. In Japanese Patent Laid-Open No. 2000-230052, (R ₁ SiO _3/2 ) unit and (R ₁ (HO) SiO _2/2 ) unit (wherein R ₁ is a fluorinated alkyl group or a fluorinated arylalkyl group). An optical material made of a polymer consisting of: fluorinated alkyl group and fluorinated arylalkyl group has a problem that the material cost is high, and it takes high temperature and a long time to cure. There's a problem.

Compositions for optical waveguides that are cured by irradiation with high energy rays typified by ultraviolet rays have also been proposed. In JP-A No. 2000-180643, (PhSiO _3/2 ) units and (R ₁ SiO _3/2 ) units (wherein R ₁ is an alkyl group having 1 to 3 carbon atoms, Ph is a phenyl group or a derivative thereof. A photosensitive composition for an optical waveguide comprising an organic oligomer comprising a polymerization initiator, a (PhSiO _3/2 ) unit and a (R ₁ R ₂ SiO _2/2 ) unit (wherein R ₁ and R ₂ are (Ph (ZCH ₂ O) SiO _3/2 ), a photosensitive composition for an optical waveguide comprising an organic oligomer composed of an alkyl group having 1 to 3 carbon atoms, Ph is a phenyl group or a derivative thereof, and a polymerization initiator. A photosensitive composition for an optical waveguide comprising an organic oligomer comprising a polymerization initiator and a (PhSiO _3/2 ) unit (wherein Ph is a phenyl group or a derivative thereof, and Z is an epoxy group) and a polymerization initiator. Proposed However, the former two are inferior in photopolymerizability, and the latter are inferior in water resistance and heat resistance because the epoxy-containing organic group is bonded to a silicon atom through an oxygen atom, and heat resistance is poor. There is a problem that the refractive index is likely to change later.

On the other hand, an ultraviolet curable composition based on a (meth) acryloxy functional organopolysiloxane resin has also been proposed.
JP-A-61-111330 (US Pat. No. 4,568,566) describes 75-100 mol% of units selected from the group consisting of R ₃ Si _0.5 units, RSiO _1.5 units and SiO ₂ units and R ₂ SiO units 0-25. A silicone resin comprising mol% (wherein R is a monovalent organic group (eg, methyl group, phenyl group), and part of R is an acryloxyalkyl group or a methacryloxyalkyl group), and An ultraviolet curable silicone resin composition comprising a silicone resin and a photopolymerization initiator is disclosed.
Japanese Patent Application Laid-Open No. 61-181835 (Japanese Patent Publication No. 6-78433) comprises R ₂ SiO units, R ¹ SiO _1.5 units, and R ² SiO _1.5 units, each having a predetermined number, and containing 0.1 to 20 mol% of R ³ RSiO units. Silicone copolymer (wherein R is an alkyl group, aryl group or aralkyl group, R ¹ is an aryl group or aralkyl group, R ² is an alkyl group, R ³ is an acryloxyalkyl group or a methacryloxyalkyl group), For example, a polymethylsiloxane block obtained by cohydrolysis of silanol group-blocked polydimethylsiloxane with phenyltrichlorosilane, methyltrichlorosilane and methacryloxypropylmethyldichlorosilane has both ends of polydimethylsiloxane having phenylmethylmethacryloxypropylpolysiloxane blocks. A bonded block copolymer, and the block copolymer and a photoinitiator. UV curable compositions are disclosed. This composition is mainly composed of diorganosiloxane units in consideration of flexibility. Japanese Patent Laid-Open No. 1-299827 (Japanese Patent No. 2839150) discloses a composite polysiloxane having an MTQ structure and a linear silicon chain and having an acrylic functional group at the terminal, and an ultraviolet ray comprising the composite polysiloxane and an ultraviolet initiator. Curable compositions are disclosed and are useful as coatings and cast encapsulants.
JP-A-6-306173 discloses ladder-like polysilsesquioxane in which the silicon-bonded organic groups are a methyl group, a phenyl group, and a methacryloxypropyl group, but 50 mol% or more of the silicon-bonded organic groups are methyl groups. It is used for copolymerization with acrylic monomers and is not described as being cured by irradiation with high energy rays. JP-A-8-31139 discloses a photocurable composition comprising an organopolysilsesquioxane which is a co-hydrolysis condensate of (meth) acryloxypropyltrialkoxysilane and phenyltrialkoxysilane and a photosensitizer. JP-A-10-319597 discloses a photosensitive silicone ladder resin composition having a (meth) acryloxy group. However, these patent documents do not describe optical properties, find no examples of studies as optical materials, and do not even suggest application to optical materials, particularly optical transmission members.
However, JP 2003-227949 A discloses an optical waveguide forming material comprising a photocurable organopolysiloxane composition containing a (meth) acryloyloxy functional organopolysiloxane and a photosensitizer, and an optical waveguide using the same. A manufacturing method is disclosed. (Meth) acryloyloxy functional organopolysiloxane contains alkoxy groups, specifically, it is manufactured by cohydrolyzing (meth) acryloyloxyalkyltrialkoxysilane and phenyltrialkoxysilane, so that the molecular weight It is not easy to manufacture with good accuracy by controlling. Therefore, a (meth) acryloxy functional organopolysiloxane resin that can be cured by irradiation with high energy rays and can be easily manufactured with high accuracy and stability, and an optical component comprising such a (meth) acryloxy functional organopolysiloxane resin as a main component. A high energy ray-curable organopolysiloxane resin composition useful for a material, particularly an optical transmission member, has not been known so far.

Japanese Patent Laid-Open No. 3-43423 Japanese Patent Laid-Open No. 4-157402 Japanese Unexamined Patent Publication No. 2000-230052 JP 2000-180643 A JP 61-111330 A Japanese Patent Laid-Open No. 61-181835 Japanese Patent Laid-Open No. 1-299827 JP-A-6-306173 JP-A-8-311139 Japanese Patent Laid-Open No. 10-319597 JP 2003-227949 A

An object of the present invention is to quickly cure by irradiation with high energy rays typified by ultraviolet rays, and the cured product has excellent shape retention and high light transmittance in a communication wavelength band and has high light transmittance. PROBLEM TO BE SOLVED: To provide a composition and an organopolysiloxane resin therefor, and to provide an optical transmission member, particularly an optical waveguide, comprising a cured organopolysiloxane resin having excellent shape retention and high light transmittance in a communication wavelength band. Furthermore, another object of the present invention is to provide a simple, rapid and efficient manufacturing method for such an optical transmission member, particularly an optical waveguide.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention
[1] Siloxane unit formula (1):
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (1)
[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, Group and Formula (2): CH ₂ = C (R ⁷ ) COOR ⁸ − (2)
(Wherein R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkylene group having 2 or more carbon atoms), or one or more monovalent organic groups selected from the group represented by The siloxane unit having a group represented by the formula (2) in the molecule is 5 mol% to 50 mol%, and the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the molecule is 10 wt% to 50% by weight, a is average 0 ≦ a <0.4, b is average 0 <b <0.5, c is average 0 <c <1, d is average 0 ≦ d < 0.4, b and c average 0.01 ≦ b / c ≦ 0.3, and a + b + c + d = 1. ] (Meth) acryloxy group containing organopolysiloxane resin represented by these.
[2] The monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms is a methyl group, the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is a phenyl group, and R ⁷ is a hydrogen atom. [1] The acryloxy group-containing organopolysiloxane resin according to [1].
[3] (A) Siloxane unit formula (1)
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (1)
[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, Group and Formula (2): CH ₂ = C (R ⁷ ) COOR ⁸ − (2)
(Wherein R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkylene group having 2 or more carbon atoms) one or two selected from (meth) acryloxy group-containing hydrocarbon groups The above monovalent organic group, the siloxane unit having a (meth) acryloxy group-containing hydrocarbon group in the molecule is 5 to 50 mol%, and the monovalent aromatic having 6 to 10 carbon atoms in the molecule. The hydrocarbon group is 10% to 50% by weight, a is average 0 ≦ a <0.4, b is average 0 <b <0.5, and c is average 0 <c <1 , D has an average of 0 ≦ d <0.4, b and c have an average of 0.01 ≦ b / c ≦ 0.3, and a + b + c + d = 1. A high-energy beam comprising 100 parts by weight of a (meth) acryloxy group-containing organopolysiloxane resin represented by: (B) 0.01 to 10 parts by weight of a photopolymerization initiator, and (C) 0 to 5000 parts by weight of an organic solvent. Curable organopolysiloxane resin composition.
[4] The monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms is a methyl group, the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is a phenyl group, and R ⁷ is a hydrogen atom. [3] The high energy ray-curable organopolysiloxane resin composition according to [3]
[5] The high energy ray-curable organopolysiloxane resin composition according to [3] or [4], which is for an optical transmission member.
[6] The high energy ray-curable organopolysiloxane resin composition according to [5], wherein the light transmission member is an optical waveguide.
[7] The high energy ray-curable organopolysiloxane resin composition according to any one of [3] to [6], wherein the high energy rays are ultraviolet rays.
[8] (A) Siloxane unit formula (1)
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (1)
[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, Group and Formula (2): CH ₂ = C (R ⁷ ) COOR ⁸ − (2)
(Wherein R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkylene group having 2 or more carbon atoms), or one or more monovalent organic groups selected from the group represented by The siloxane unit having a group represented by the formula (2) in the molecule is 5 mol% to 50 mol%, and the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the molecule is 10 wt% to 50% by weight, a is average 0 ≦ a <0.4, b is average 0 <b <0.5, c is average 0 <c <1, d is average 0 ≦ d < 0.4, b and c average 0.01 ≦ b / c ≦ 0.3, and a + b + c + d = 1. An optical transmission member comprising a cured product by irradiation with high energy rays in the presence of a photopolymerization initiator (B) of a (meth) acryloxy group-containing organopolysiloxane (A) represented by:
[9] The optical transmission member according to [8], wherein the optical transmission member is an optical waveguide.
[10] The optical transmission member according to [8], wherein the high energy ray is ultraviolet light.
[11] (a) characterized in that it comprises a step of applying the high energy ray-curable organopolysiloxane resin composition according to [3] to a substrate, and then (b) a step of curing the applied material by high energy ray irradiation. A method for manufacturing an optical transmission member.
[12] The high energy ray-curable organopolysiloxane resin composition according to [3] is applied to a substrate, and the applied material is irradiated with high energy rays and cured to form a lower clad layer. [3] The high energy ray-curable organopolysiloxane resin composition described in [3] is applied (however, the refractive index of the cured product is larger than that of the cured product for the cladding layer), and the applied product is cured by irradiation with high energy rays. To form a core layer, and the core layer is processed into a desired shape as necessary. The high energy ray-curing property according to [3] is formed on the core layer or on the core layer and the lower clad layer of the desired shape. A method for producing an optical waveguide, comprising: applying an organopolysiloxane resin composition; and curing the coating by high energy ray irradiation to form an upper clad layer.
[13] The production method according to [11] or [12], wherein the high energy ray is ultraviolet rays.
About.

The (meth) acryloxy group-containing organopolysiloxane resin of the present invention is rapidly cured by irradiation with high energy rays typified by ultraviolet rays in the presence of a photopolymerization initiator, and the cured product has excellent shape retention and a communication wavelength band. The light transmittance is high and the transmission loss is small.
Since the high energy ray-curable organopolysiloxane resin composition of the present invention comprises at least the above organopolysiloxane resin and a photopolymerization initiator, it is rapidly cured by irradiation with high energy rays typified by ultraviolet rays, and the cured product thereof. Has excellent shape retention, high light transmittance in the communication wavelength band, and low transmission loss.
Since the optical transmission member of the present invention, in particular the optical waveguide, is composed of a cured product of the above-mentioned organopolysiloxane resin by irradiation with high energy rays, the cured product has excellent shape retention and high light transmittance in the communication wavelength band. Low transmission loss.
The method for producing an optical transmission member of the present invention, particularly an optical waveguide, cures the high energy ray-curable organopolysiloxane resin composition by high energy ray irradiation. Can manufacture optical waveguides. Furthermore, the processing of the core shape is easy, the required time is significantly shorter than the production method using reactive ion etching, and the optical transmission member obtained, particularly the optical waveguide, has a well controlled refractive index, Low transmission loss in the communication wavelength band. Therefore, it is suitable as an optical integrated circuit material and an optical communication material in the near infrared light region.

The (meth) acryloxy group-containing organopolysiloxane resin of the present invention is
Siloxane unit formula (1):
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (1)
[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, Group and Formula (2): CH ₂ = C (R ⁷ ) COOR ⁸ − (2)
(Wherein R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkylene group having 2 or more carbon atoms), or one or more monovalent organic groups selected from the group represented by The siloxane unit having a group represented by the formula (2) in the molecule is 5 mol% to 50 mol%, and the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the molecule is 10 wt% to 50% by weight, a is average 0 ≦ a <0.4, b is average 0 <b <0.5, c is average 0 <c <1, d is average 0 ≦ d < 0.4, b and c average 0.01 ≦ b / c ≦ 0.3, and a + b + c + d = 1. ]

In this (meth) acryloxy group-containing organopolysiloxane resin, since a and d may be 0 in the siloxane unit formula (1), (R ⁴ R ⁵ SiO _2/2 ) units and (R ⁶ SiO _3/2 ) units Consisting of units, (R ¹ R ² R ³ SiO _1/2 ) units, (R ⁴ R ⁵ SiO _2/2 ) units and (R ⁶ SiO _3/2 ) units, (R ⁴ R ⁵ SiO _2/2 ) units, (R ⁶ SiO _3/2 ) units and (SiO _4/2 ) units, and (R ¹ R ² R ³ SiO _1/2 ) units and (R ⁴ R Some are composed of ⁵ SiO _2/2 ) units, (R ⁶ SiO _3/2 ) units, and (SiO _4/2 ) units. That is, as a siloxane unit formula, (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c , (R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c , (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d , and (R ¹ R ² R ³ SiO _{1 / 2} ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d . This (meth) acryloxy group-containing organopolysiloxane resin is an organopolysiloxane resin having a methacryloxy group and / or an acryloxy group, such as a branched, network, or three-dimensional structure composed of these siloxane units. The methacryloxy group and / or the acryloxy group Therefore, it is rapidly cured by high energy irradiation represented by ultraviolet rays in the presence of a photopolymerization initiator.

a, b, c, d means the average number of moles of each siloxane unit when the total number of moles of each siloxane unit is 1, and each siloxane unit is contained in an average number of moles per molecule. It shows that. Therefore, a + b + c + d = 1.
When (R ¹ R ² R ³ SiO _1/2 ) units are introduced into (meth) acryloxy group-containing organopolysiloxane resins, the molecular weight generally decreases, so the range is 0 ≦ a <0.4 on average. is there. When the (R ⁴ R ⁵ SiO _2/2 ) unit is introduced, the degree of branching of the organopolysiloxane resin decreases and the modulus of the cured product decreases, but when b = 0, the organopolysiloxane resin Unnecessary organic solvents are easily produced during production, making stable production difficult. Therefore, b has an average of 0 <b <0.5, and preferably has an average of 0 <b <0.3. When the (R ⁶ SiO _3/2 ) unit is introduced, the degree of branching of the resin is generally improved and the modulus of the cured product is increased. Therefore, the average 0 <c <1, and preferably the average 0.3 < c <1.0. In general, when (SiO _4/2 ) units are introduced, the degree of branching of the resin is significantly improved and the modulus of the cured product is significantly increased and becomes brittle. Therefore, d is an average of 0 ≦ d <0.4, Preferably 0 ≦ d <0.2, more preferably d = 0. If the molar ratio between the (R ⁴ R ⁵ SiO _2/2 ) unit and the (R ⁶ SiO _3/2 ) unit is too large, the degree of branching of the resin is reduced and the modulus of the cured product is too low. If it is too small, the degree of branching of the resin is increased and the modulus of the cured product is excessively increased. Therefore, the average of b and c is 0.01 ≦ b / c ≦ 0.3, preferably 0.01 ≦ b / c. ≦ 0.2.

Among the R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ which are substituents bonded to the silicon atom in the organopolysiloxane resin, a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms Examples thereof include monovalent saturated aliphatic hydrocarbon groups such as a methyl group, ethyl group, propyl group, butyl group and hexyl group; and monovalent unsaturated aliphatic hydrocarbon groups such as vinyl, allyl and hexenyl. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. The refractive index, which is an important property of the optical properties, is adjusted by changing the type and content of the monovalent hydrocarbon group. When a monovalent aliphatic hydrocarbon group such as a methyl group is used as a main substituent, the refractive index of the organopolysiloxane resin tends to be less than 1.5, and a monovalent aromatic hydrocarbon group such as a phenyl group is used as a main substituent. Then, the refractive index of the organopolysiloxane tends to be 1.5 or more.
R ⁷ in the group represented by the formula (2) is a hydrogen atom or a methyl group, but a hydrogen atom is preferable in consideration of curability at the time of high energy irradiation represented by ultraviolet rays. R ⁸ is an alkylene group having 2 or more carbon atoms, preferably 3 to 8 carbon atoms. Examples of the group represented by the formula (2) include a 3- (methacryloxy) propyl group, a 3- (acryloxy) propyl group, and a 6- (acryloxy) hexyl group. In consideration of curability at the time of high energy irradiation represented by ultraviolet rays, a 3- (acryloxy) propyl group is preferable. Considering the curability at the time of high energy irradiation represented by ultraviolet rays, the siloxane unit having a group represented by the formula (2) in one molecule of the organopolysiloxane resin is 5 mol% to 50 mol%. If the siloxane unit is less than 5 mol%, the curability is inferior, and the crosslink density of the cured product is low, so that sufficient hardness as an optical transmission member cannot be obtained. On the other hand, if the siloxane unit exceeds 50 mol%, the heat resistance and light transmittance are lowered, which is not suitable.

As (meth) acryloxy group-containing organopolysiloxane resin, organopolysiloxane resin comprising (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), and (A1SiO _3/2 ) units, (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), and (A2SiO _3/2 ) units of organopolysiloxane resin, (Me ₃ SiO _1/2 ), (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), and Organopolysiloxane resin composed of (A2SiO _3/2 ) units, Organopolysiloxane resin composed of (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), (A1SiO _3/2 ) and (SiO _4/2 ) units , (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), (A2SiO _3/2 ) and (SiO _4/2 ) organopolysiloxane resins composed of units, (Me ₂ SiO _2/2 ), (PhSiO _{3 / 2} ), (MeSiO _3/2 ), and (A2SiO _3/2 ) units, an organopolysiloxane resin, (Ph ₂ SiO _2/2 ), (PhSiO _3/2 ), and (A2SiO _3/2 ) units An organopolysiloxane resin comprising (MePhSiO _2/2 ), (PhSiO _3/2 ), and (A2SiO _3/2 ) units Xane resin, (MeViSiO _2/2 ), (PhSiO _3/2 ), and (A1SiO _3/2 ) unit organopolysiloxane resin, (MeViSiO _2/2 ), (PhSiO _3/2 ), and (A2SiO _{3 / 2} ) unit organopolysiloxane resin, (Me ₂ SiO _2/2 ), (Ph ₂ SiO _2/2 ), and (A2SiO _3/2 ) unit organopolysiloxane resin, (Me ₂ ViSiO _{1 / 2} ), (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), and (A2SiO _3/2 ) units of an organopolysiloxane resin, (Me ₃ SiO _1/2 ), (Ph ₂ SiO _2/2 ), (PhSiO _3/2 ), and (A2SiO _3/2 ) unit organopolysiloxane resin, (Me ₃ SiO _1/2 ), (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), ( A2SiO _3/2 ), and an organopolysiloxane resin comprising (SiO ₂ ) units (where Me is a methyl group, Vi is a vinyl group, Ph is a phenyl group, A1 is a 3-methacryloxypropyl group, and A2 is a 3- Represents an acryloxypropyl group]. An acryloxy group containing a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms is a methyl group, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is a phenyl group, and R ⁷ is a hydrogen atom Methylphenyl polysiloxane resin is preferable because it cures rapidly upon irradiation with high energy represented by ultraviolet rays in the presence of a photopolymerization catalyst and is excellent in light transmission at a communication wavelength.

The (meth) acryloxy group-containing organopolysiloxane resin of the present invention can be produced by a conventionally known production method, for example, a production method disclosed in JP-A-8-143675. For example, a mixture of dimethyldichlorosilane, methyltrichlorosilane, and / or phenyltrichlorosilane is cohydrolyzed and condensed to produce an organopolysiloxane intermediate containing no (meth) acryloxy group. In addition, 3-acryloxypropyl group-containing organopolysiloxane resin can be obtained by adding 3-acryloxypropyltrimethoxysilane and carrying out hydrolysis condensation reaction. Such a two-step reaction method is recommended for accurately and stably producing a (meth) acryloxy group-containing organopolysiloxane resin having a desired siloxane structure and molecular weight.
In the organopolysiloxane resin, a hydroxyl group bonded to a silicon atom or an alkoxy group may remain depending on the production method and production conditions. These substituents need to be reduced as much as possible because they adversely affect storage stability and cause a decrease in heat resistance. For example, by heating the organopolysiloxane resin in the presence of a small amount of potassium hydroxide, the concentration of these substituents can be reduced by causing further dehydration condensation or dealcohol condensation reaction. A preferable range of the concentration of these substituents is 3 mol% or less, more preferably 2 mol% or less, of all the silicon atom-bonded substituents.

The number average molecular weight of the (meth) acryloxy group-containing organopolysiloxane resin of the present invention is not particularly limited, but is preferably 10 ³ to 10 ⁶ in consideration of the toughness of the cured organopolysiloxane resin and the solubility in an organic solvent.
In the (meth) acryloxy group-containing organopolysiloxane resin of the present invention, the content of monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms in the molecule needs to be 10 wt% to 50 wt%. Outside this range, the toughness of the cured organopolysiloxane and the light transmittance in the communication wavelength region are low, which is not suitable. Considering light transmittance and mechanical strength, the content of monovalent aromatic hydrocarbon group is preferably 15% by weight to 50% by weight.

The present invention also provides: (A) Siloxane unit formula (1)
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (1)
[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, Group and Formula (2): CH ₂ = C (R ⁷ ) COOR ⁸ − (2)
(Wherein R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkylene group having 2 or more carbon atoms), or one or more monovalent organic groups selected from the group represented by The siloxane unit having a group represented by the formula (2) in the molecule is 5 mol% to 50 mol%, and the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the molecule is 10 wt% to 50% by weight, a is average 0 ≦ a <0.4, b is average 0 <b <0.5, c is average 0 <c <1, d is average 0 ≦ d < 0.4, b and c average 0.01 ≦ b / c ≦ 0.3, and a + b + c + d = 1. ] (Meth) acryloxy functional organopolysiloxane resin represented by 100 parts by weight, (B) 0.01-10 parts by weight of a photopolymerization initiator, and (C) 0-5000 parts by weight of an organic solvent. Regarding the curable organopolysiloxane resin composition, the component (A) is as described above.

(B) The photopolymerization initiator has been used conventionally as a photopolymerization initiator for (meth) acryloxy group-containing organopolysiloxanes, or has the ability to initiate photopolymerization of (meth) acryloxy group-containing organopolysiloxanes. If there is no particular limitation. Examples include diazide compounds, iminoquinone diazide compounds, coumarin dyes, anthraquinones, benzophenone derivatives, aromatic carbonyl compounds, benzoin derivatives, acylphosphine oxides, thioxanthone derivatives, aminocarbonyl compounds, and the like. Specifically, 2,6-bis (p-azidobenzal) -4-methylcyclohexanone, 4,4'-diazidobenzalacetone, 4,4'-diazidodiphenylmethane, 1,4-iminoquinone-diazide (4 ) -2-sulfonamide, 3,3-carbonylbis (7-diethylaminocoumarin), ethyl anthraquinone, 4,4'-dimethylaminobenzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) ) Benzophenone, 2,2'-dimethoxy-1,2-diphenylethane-1-one, [4- (methylphenylthio) phenyl] phenylmethanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) Butanone-1, benzoin methyl ether, benzo Inethyl ether, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-chlorothioxanthone, 2,4-diethylthioxanthone and the like can be preferably used. When the component (B) is less than 0.01 part by weight, curing at the time of high energy irradiation represented by ultraviolet rays is insufficient, and when it exceeds 10 parts by weight, the optical properties of the cured product may be deteriorated by the residual catalyst. Therefore, it is 0.01 weight part-10 weight part per 100 weight part of (A) component, Preferably it is 0.1 weight part-5 weight part.

(C) The organic solvent is blended as necessary when the component (A) is solid or viscous. The component is not particularly limited as long as it can dissolve the component (A) and the component (B) and does not inhibit the photopolymerizability, and those having a boiling point of 80 ° C. or higher and lower than 200 ° C. are recommended. Specifically, i-propyl alcohol, t-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, mesitylene, chlorobenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, ethoxy-2-propanol acetate, methoxy- Examples include 2-propanol acetate, octamethylcyclotetrasiloxane, and hexamethyldisiloxane. Such organic solvents may be used alone or in combination of two or more.
When the component (A) is liquid and the miscibility with the component (B) is very good, it is not necessary to add the component (C). When the blending amount of the component (C) exceeds 5000 parts by weight, it is difficult to obtain a good-quality thin film at the time of manufacturing an optical transmission member to be described later. More preferred is 500 parts by weight.

The high energy ray-curable organopolysiloxane resin composition of the present invention is liquid at room temperature, and preferably has a viscosity of 20 mPa · s to 10,000 mPa · s at 25 ° C. If it is out of this range, the workability during the production of the thin film-like cured product is not so good, and it is difficult to obtain an optically good thin film. The high energy ray-curable organopolysiloxane resin composition of the present invention is easily produced by mixing the component (A) and the component (B), or the component (A), the component (B), and the component (C). can do.
The high energy ray-curable organopolysiloxane resin composition of the present invention is suitable for manufacturing an optical transmission member, particularly an optical waveguide.

The present invention relates to an optical transmission member comprising a cured product obtained by irradiation with high energy rays in the presence of the photopolymerization catalyst (B) of the organopolysiloxane resin (A), particularly an optical waveguide. The component (A), (B) The components are as described above.

The light transmission member made of a cured material by irradiation with high energy rays in the presence of the photopolymerization catalyst (B) of the organopolysiloxane resin (A) of the present invention is almost 100% light except for reflection in the visible light region. It has transmittance. In addition, as long as measurement is performed using a polarizer, polarized light is not observed, so birefringence is negligibly small. Furthermore, it has hardness and elasticity that do not easily deform, and almost no warpage or cracking of the cured product is observed.
Moreover, the optical transmission member of the present invention can be used as both a passive member and an active member. Specifically, non-branching optical waveguides, branching optical waveguides, multiplexers / demultiplexers, active transmissions such as optical adhesives, waveguide optical switches, waveguide optical modulators, optical attenuators, optical amplifiers, etc. A transmission member is mentioned.

Since an optical waveguide, which is a typical example of an optical transmission member, includes a core portion and a cladding portion having a refractive index larger than that of the core portion, it is necessary to precisely adjust the difference in refractive index between the core portion and the cladding portion. The refractive index of the cured product is such that the monovalent aliphatic hydrocarbon group (typically methyl group) and the monovalent aromatic hydrocarbon group (typically methyl group) which are silicon atom bonding groups in the (meth) acryloxy group-containing organopolysiloxane resin. Specifically, it can be precisely adjusted by adjusting the molar ratio of the phenyl group. When the ratio of the monovalent aromatic hydrocarbon group is increased, the refractive index is increased, and when the ratio of the monovalent aliphatic hydrocarbon group is increased, the refractive index is decreased. When an optical waveguide is produced from the high energy ray-curable organopolysiloxane resin composition of the present invention, the core cured product needs to have a higher refractive index than the clad cured product, so the core organopolysiloxane resin composition It is necessary that the amount of the monovalent aromatic hydrocarbon group in the content be higher than that in the organopolysiloxane resin composition for cladding. For this purpose, two types of high energy ray-curable organopolysiloxane resins having different ratios of [monovalent aliphatic hydrocarbon group] / [monovalent aromatic hydrocarbon group] are used separately for the core and the cladding, And / or a method of mixing these two kinds of high energy ray-curable organopolysiloxanes in different ratios may be employed.

The present invention is also characterized by comprising (a) a step of applying the above-mentioned high energy ray-curable organopolysiloxane resin composition to a substrate, and (b) a step of curing the applied product by high energy ray irradiation. The present invention relates to a method for manufacturing an optical transmission member, particularly an optical waveguide. To manufacture the optical transmission member, first, (a) the high energy ray-curable organopolysiloxane resin composition is applied onto a substrate to form a uniform layer. After forming a thin film having a thickness, the organic solvent (C) is removed by heating as necessary, and consists of a (meth) acryloxy group-containing organopolysiloxane resin (A) and a photopolymerization initiator (B). Get a thin film. The substrate used here is preferably one having a smooth surface and being stable to a solvent and light and heat at the time of curing, and examples thereof include a silicon wafer, a glass plate, a ceramic plate, and a heat resistant plastic plate. The method of applying the high energy ray-curable organopolysiloxane resin composition is generally a spin coating method, and the heating temperature after application is preferably in the range of 30 ° C to 120 ° C. (B) Subsequently, the thin film on the substrate is cured by irradiation with high energy rays. Examples of the high energy rays (also referred to as active energy rays) used here include ultraviolet rays, electron beams, and radiation, but ultraviolet rays are preferable from the viewpoint of practicality. As the ultraviolet ray generation source, a high-pressure mercury lamp, a medium-pressure mercury lamp, a Xe-Hg lamp, a deep UV lamp or the like is suitable, and the irradiation amount at that time is preferably 100 to 8000 mJ / cm ² . Depending on the type of the (meth) acryloxy group-containing organopolysiloxane resin used, curing may not be completed by irradiation with the high energy beam alone. In this case, curing can be completed by heating the thin film irradiated with high energy rays (hereinafter referred to as post-heating). A preferable temperature range for the post-heating is 50 to 200 ° C.
Thus, a high energy ray-curable organopolysiloxane resin composition is applied on a substrate, and then the applied composition is irradiated with high energy rays and post-heated as necessary in a specified wavelength range. Although an optical transmission member with high light transmittance can be manufactured, a film-form optical transmission member can be obtained by peeling from a board | substrate as needed. Such an optical transmission member that is not attached to the substrate is useful because it can be arranged at any location in the optical transmission path, so that the degree of freedom in constructing the optical transmission system is widened. Although there is no restriction | limiting in particular in the thickness of this film-form optical transmission member, Generally it is the range of 5-200 microns. Moreover, there is no restriction | limiting also about the peeling method from a board | substrate, Mechanical peeling with a precision jig etc., chemical peeling using chemicals, such as an acid, etc. are applicable.

By repeating the steps (a) and (b), the optical transmission member can be formed into an optical waveguide shape. The typical manufacturing method of an optical waveguide is illustrated.
First, a high energy ray-curable organopolysiloxane resin composition for clad is spin-coated on a substrate, and the coating is cured by high energy ray irradiation to form a lower clad layer. Next, a high energy ray-curable organopolysiloxane resin composition for the core is spin-coated on the lower clad layer, and the coated material is cured by high energy ray irradiation to form a core layer. To form a core layer having a refractive index higher than that of the cladding layer. In this case, a solvent casting method may be used instead of the spin coating method. In order to process the core layer into a desired shape, that is, to pattern it, the core layer is irradiated with high energy rays through a photomask on which the shape is drawn, and the post-heating is performed as necessary. Then, it is preferable to dissolve and remove the unexposed portion using an organic solvent. The organic solvent used here is preferably the organic solvent described as the component (C). When an upper clad layer is formed by applying a high energy ray-curable organopolysiloxane resin composition for clad on this core layer, or a patterned core layer and a lower clad layer, and curing by applying high energy ray, An optical waveguide composed of a cladding layer-core layer-cladding layer is obtained. Similarly to the above, a film-like optical waveguide can be obtained by peeling from the substrate. Also, after forming the lower clad layer from the substrate to form a film, the core optical layer is formed on the lower clad layer, which is the film-like material, and then the upper clad layer is formed, thereby forming the film-like optical waveguide. It can also be manufactured. In the above production method, the cured product of the high energy ray-curable organopolysiloxane resin composition for the core has a higher refractive index than the cured product of the high energy beam curable organopolysiloxane resin composition for the cladding. Yes. The optical waveguide may be either a slab type or a channel type.

In order to describe the present invention specifically, examples will be described below, but the present invention is not limited thereto. The structure of the acryloxy group-containing organopolysiloxane resin was determined by ¹³ C and ²⁹ Si NMR measurements. For the measurement of the number average molecular weight of the acryloxy group-containing organopolysiloxane resin, GPC was used, and the number average molecular weight was calculated from comparison with polystyrene standards. The silanol group and methoxy group contents of the acryloxy group-containing organopolysiloxane resin were measured by ²⁹ Si NMR method. As a high energy ray source for curing the high energy ray curable organopolysiloxane resin composition, a deep UV irradiation device manufactured by Yamashita Denso Co., Ltd. was used. The refractive index of the cured product was measured with a prism coupler method at a wavelength of 1.55 microns, and the film thickness was measured with an alpha step 200 made by Tencor. The light transmittance of the cured product was measured at a wavelength of 1550 nm using a self-recording spectrophotometer by preparing a flat plate having a thickness of 5 mm. As for the optical loss value, the value at 1550 nm for the cured product was measured by the prism coupling method, and the value at 1550 nm for the optical waveguide was measured by the cutback method. Furthermore, the polarization dependence of the cured product was observed by optical microscope observation using a polarizer. In the following siloxane unit formula, Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.

[Reference Example 1]
Preparation of acryloxy group-containing organopolysiloxane resin (A1) 450 g of toluene, 104.6 g of isopropyl alcohol, and 104.7 g of water are placed in a 1 L four-necked glass flask equipped with a stirrer, reflux condenser, and thermometer, and phenyltrichlorosilane is added from a dropping funnel. A mixture of 382.2 g and 25.0 g of dimethyldichlorosilane was added dropwise. After completion of the dropwise addition, the glass flask was attached with a mantle heater and stirred for 1 hour with heating under reflux. After cooling the glass flask, 100 g of water was added and mixed, the mixture was separated with a separatory funnel, and the upper layer was washed twice with 100 g of water and once with 100 g of saturated aqueous NaHCO ₃ solution to remove hydrochloric acid. It was. The washed upper layer was transferred to a 1 L separable flask equipped with a stirrer, a condenser, and a thermometer, and heated to remove water and isopropyl alcohol. 1.9 g of a 50% by weight aqueous solution of CsOH was added to the remaining liquid, and condensed water was removed by azeotropic dehydration with toluene. The flask contents were cooled to 50 ° C., 287.3 g of 3-acryloxypropyltrimethoxysilane and 0.2 g of a polymerization inhibitor were added, and the mixture was stirred for 3 hours under heating and refluxing while bubbling nitrogen gas mixed with 2% oxygen. did. After cooling the flask contents to 50 ° C. or lower, 353.3 g of methanol and 66.7 g of water were added, and the mixture was stirred for 1 hour with heating under reflux, and methanol and water were distilled off while adding a corresponding amount of toluene. The solid content concentration was adjusted to 50% by weight by appropriately removing or adding toluene. After complete dehydration, water and methanol were added again and the same operation was performed. After cooling, add 2 g of filter aid and stir for 1 hour. After filtering this filter aid, concentrate the filtrate with an evaporator to give 498.2 g of toluene solution of acryloxy group-containing organopolysiloxane resin (solid content concentration: 80%) Was prepared. This resin has a siloxane unit formula [Me ₂ SiO _2/2 ] _0.05 [PhSiO _3/2 ] _0.55 [AcSiO _3/2 ] _0.40 [Ac: 3-acryloxypropyl], and its number average molecular weight is 4600. Yes, the phenyl group content was 30% by weight, and the silanol group and methoxy group content was 1.7 mol%.

[Reference Example 2]
Preparation of acryloxy group-containing organopolysiloxane resin (A2) As starting materials 450.9 g of toluene, 126.1 g of isopropyl alcohol, 121.8 g of water, 233.5 g of phenyltrichlorosilane, 149.3 g of methyltrichlorosilane, 28.7 g of dimethyldichlorosilane, 50% by weight of CsOH A synthetic reaction was carried out in the same manner as in Reference Example 1 except that 1.8 g of aqueous solution, 319.7 g of 3-acryloxypropyltrimethoxysilane, and 0.18 g of polymerization inhibitor were used, and the siloxane unit formula [Me ₂ SiO _2/2 ] _0.05 [MeSiO _3/2 ] _0.25 [PhSiO _3/2 ] _0.30 [AcSiO _3/2 ] _0.40 [Ac: 3-Acryloxypropyl] -containing acryloxy group-containing organopolysiloxane resin 544.0 g (solid content concentration: 75 %) Was prepared. Its number average molecular weight was 5,300, phenyl group content was 18% by weight, and silanol group and methoxy group content was 1.9 mol%.

[Example 1]
Preparation of cured product of acryloxy group-containing organopolysiloxane resin Acryloxy group-containing organopolysiloxane resins (A1) and (A2) obtained in the above reference example, and 2-benzyl produced by Nippon Ciba-Geigy Co., Ltd. as photopolymerization initiator (B) -2-dimethylamino-1- (4 morpholinophenyl) -butanone and toluene as the organic solvent (C) are mixed in the blending amounts (unit: g) shown in Table 1 below, and high energy ray curability is obtained. Organopolysiloxane resin compositions 1, 2, 3 and 4 were prepared.

In a chamber closed system, composition 1 and composition 2 were each spin-coated on a silicon substrate at 2000 rpm for 30 seconds, and the resulting thin film composition was allowed to stand at room temperature for 30 minutes and then heated at 110 ° C. for 5 minutes. Thereafter, ultraviolet rays were irradiated at an irradiation amount of 6 J / cm ² and further heated at 110 ° C. for 5 minutes to obtain a cured product of an acryloxy group-containing organopolysiloxane resin having a uniform thickness of 7 to 9 μm. Each cured product was transparent and had hardness and elasticity that did not easily deform. Moreover, peeling from the substrate and cracks were not observed. The refractive index and light transmittance of each cured product are shown in Table 1 above. Each cured product had a light transmittance of 93% or more in the communication wavelength region, an optical loss value of 0.6 dB / cm, and a sufficiently low value suitable for use as an optical transmission member.

[Example 2]
Preparation of channel-type optical waveguide made of cured acryloxy group-containing organopolysiloxane resin In a chamber closed system, composition 2 in Table 1 was spin-coated on a silicon substrate at 2000 rpm for 30 seconds, and the resulting thin film composition was obtained. After standing at room temperature for 30 minutes, it was heated at 110 ° C. for 5 minutes. Thereafter, the film was irradiated with ultraviolet rays at an irradiation dose of 6 J / cm ² and further heated at 110 ° C. for 5 minutes to obtain a cured acryloxy group-containing organopolysiloxane resin thin film having a uniform thickness of 8 μm. Next, the cured thin film was used as a lower clad layer, and the composition 1 shown in Table 1 was spin-coated on the same conditions as above and heat-treated. The exposed portion was cured by irradiating with ultraviolet rays at a dose of 6 J / cm ² through a glass mask having a rectangular optical path shape with a line width of 7 μm and a length of 5 cm, and further heating at 110 ° C. for 5 minutes. By dissolving and removing the unexposed portion with methyl isobutyl ketone, a core pattern made of a cured product of an acryloxy group-containing organopolysiloxane resin having a straight rectangle having a uniform thickness of 8 μm, a line width of 7 μm, and a length of 5 cm was prepared. On the lower clad layer and the core pattern thus produced, composition 2 in Table 1 was spin-coated at 1000 rpm for 30 seconds in a chamber closed system, allowed to stand at room temperature for 30 minutes, then heated at 110 ° C. for 5 minutes, Ultraviolet irradiation was performed at an irradiation amount of 6 J / cm ² and post-heating was performed at 110 ° C. for 5 minutes to form an upper clad layer made of a cured acryloxy group-containing organopolysiloxane resin having a thickness of 10 μm on the core pattern. The channel type optical waveguide fabricated in this way had no intermixing between the core and the clad, and the optical loss value was 0.6 dB / cm.

[Example 3]
Preparation of channel-type optical waveguide made of cured acryloxy group-containing organopolysiloxane resin In a chamber closed system, composition 4 in Table 1 was spin-coated on a silicon substrate at 500 rpm for 20 seconds and 1000 rpm for 10 seconds. The thin film composition thus obtained was allowed to stand at room temperature for 30 minutes and then heated at 110 ° C. for 5 minutes. Thereafter, the film was irradiated with ultraviolet rays at an irradiation dose of 6 J / cm ² and further heated at 110 ° C. for 5 minutes to obtain a cured acryloxy group-containing organopolysiloxane resin thin film having a uniform thickness of 55 μm. Next, this hardened | cured material thin film was used as the lower clad layer, the composition 3 of Table-1 was spin-coated on the same conditions as the above, and it heat-processed. The exposed portion was cured by irradiating with ultraviolet rays at a dose of 6 J / cm ² through a glass mask having a rectangular optical path shape with a line width of 50 μm and a length of 5 cm, and further heating at 150 ° C. for 1 minute. By dissolving and removing the unexposed portion with methyl isobutyl ketone, a core pattern made of a cured product of an acryloxy group-containing organopolysiloxane resin having a straight rectangle having a uniform thickness of 48 μm, a line width of 50 μm, and a length of 5 cm was prepared. On the thus prepared lower clad layer and core pattern, the composition 4 shown in Table-1 was spin-coated under the same conditions as described above and heat-treated. Ultraviolet irradiation was performed at an irradiation amount of 6 J / cm ² and post-heating was performed at 110 ° C. for 5 minutes to form an upper clad layer made of a cured acryloxy group-containing organopolysiloxane resin having a thickness of 55 μm on the core pattern. The channel-type optical waveguide fabricated in this way had no intermixing between the core and the clad, and the optical loss value was 0.6 dB / cm.

[Example 4]
Preparation of slab type optical waveguide made of acryloxy group-containing organopolysiloxane resin cured product In a chamber closed system, composition 4 in Table 1 was spin-coated on a silicon substrate for 20 seconds at 500 rpm and for 10 seconds at 1000 rpm. The resulting uncured coating was left at room temperature for 30 minutes and then heated at 110 ° C. for 5 minutes. Thereafter, the film was irradiated with ultraviolet rays at an irradiation dose of 6 J / cm ² and further heated at 110 ° C. for 5 minutes to obtain a cured acryloxy group-containing organopolysiloxane resin thin film having a uniform thickness of 55 μm. Its refractive index was 1.521. Next, the composition 3 of Table 1 was coated on the film in the same manner, and after the heat treatment, the film was irradiated with ultraviolet rays at an irradiation amount of 6 J / cm ² and further heated at 110 ° C. for 5 minutes, whereby the refractive index was changed. A core layer made of a cured product of an acryloxy group-containing organopolysiloxane resin having a uniform thickness of 50 μm at 1.539 was formed. On this, the composition 4 in Table 1 was coated in the same manner, heat-treated, irradiated with ultraviolet rays at an irradiation amount of 6 J / cm ² , and further heated at 150 ° C. for 1 minute, to have a uniform refractive index of 1.521. An upper clad layer made of a cured product of an acryloxy group-containing organopolysiloxane resin having a thickness of 55 μm was formed. The slab type optical waveguide film thus produced had no intermixing between the core and the clad, did not peel from the crack or the substrate, and no polarization dependency was observed. The optical loss value was 0.6 dB / cm.

[Comparative Example 1]
Photocurable phenylpolysiloxane resin composition according to Example 1 of JP-A-8-311139
3-acryloxypropyl prepared by co-hydrolysis condensation of 3-acryloxypropyltrimethoxysilane and phenyltrimethoxysilane (molar ratio 1: 1) in the presence of hydrochloric acid and co-hydrolysis condensation hexamethyldisilazane treatment Group-containing phenyl polysiloxane resin [siloxane unit formula (Me ₃ SiO _1/2 ) _0.06 (R ¹⁰ SiO _3/2 ) _0.31 (PhSiO _3/2 ) _0.63 ; R ¹⁰ : acryloxypropyl group] 100 g, 2,6- An ultraviolet curable phenyl polysiloxane resin composition comprising 5 g of bis (p-azidobenzal) -4-tamyl cyclohexanone and 30 g of methyl isobutyl ketone was prepared. This composition was spin-coated, air-dried, and then irradiated with ultraviolet rays at an irradiation dose of 0.18 J / cm ² . Cracks were observed in the obtained cured film, which was inappropriate as an optical transmission member.

[Comparative Example 2]
A siloxane unit formula [Me ₂ SiO _2/2 ] _0.05 [MeSiO] was used in the same manner as in Reference Example 1 except that a mixture of 56 g of phenyltrichlorosilane and 200 g of methyltrichlorosilane was used instead of 382.2 g of phenyltrichlorosilane as a starting material. _3/2 ] _0.45 [PhSiO _3/2 ] _0.09 [AcSiO _3/2 ] _0.41 [Ac: 3-acryloxypropyl group] acryloxy group-containing organopolysiloxane resin (number average molecular weight: 5100, phenyl group content: A toluene solution (solid content concentration: 73.5%) of 6% by weight, silanol group and methoxy group content: 0.8 mol%) was prepared. An ultraviolet curable organopolysiloxane resin composition was prepared by mixing 50 g of this acryloxy group-containing organopolysiloxane resin and 1.5 g of 2-benzyl-2-dimethylamino-1- (4 morpholinophenyl) -butanone. This solution was spin-coated, irradiated with ultraviolet rays and heat-treated in the same manner as in Example 1 to obtain a cured acryloxy group-containing organopolysiloxane resin having a uniform thickness of 8.5 μm. This cured product is transparent and has sufficient mechanical strength such as hardness that does not easily deform. No change due to dissolution, swelling, etc. was observed even when immersed in toluene overnight. The occurrence of some cracks was observed. Further, the light transmittance in the communication wavelength region was 85%, which was insufficient for use as an optical transmission member.

The high energy ray-curable organopolysiloxane resin of the present invention is useful as a main component of a high energy ray-curable organopolysiloxane resin composition.
The high energy ray-curable organopolysiloxane resin composition of the present invention is useful for the production of optical materials, particularly optical transmission members represented by optical waveguides.
The optical transmission member of the present invention is useful for materials for optical integrated circuits and materials for optical communication in the near infrared light region.

Claims (13)

Siloxane unit formula (1):
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (1)
[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, Group and Formula (2): CH ₂ = C (R ⁷ ) COOR ⁸ − (2)
(Wherein R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkylene group having 2 or more carbon atoms), or one or more monovalent organic groups selected from the group represented by The siloxane unit having a group represented by the formula (2) in the molecule is 5 mol% to 50 mol%, and the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the molecule is 10 wt% to 50% by weight, a is average 0 ≦ a <0.4, b is average 0 <b <0.5, c is average 0 <c <1, d is average 0 ≦ d < 0.4, b and c average 0.01 ≦ b / c ≦ 0.3, and a + b + c + d = 1. ] (Meth) acryloxy group containing organopolysiloxane resin represented by these. The monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms is a methyl group, the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is a phenyl group, and R ⁷ is a hydrogen atom. The acryloxy group-containing organopolysiloxane resin described. (A) Siloxane unit formula (1)
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (1)
[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, Group and Formula (2): CH ₂ = C (R ⁷ ) COOR ⁸ − (2)
(Wherein R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkylene group having 2 or more carbon atoms), or one or more monovalent organic groups selected from the group represented by The siloxane unit having a group represented by the formula (2) in the molecule is 5 mol% to 50 mol%, and the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the molecule is 10 wt% to 50% by weight, a is average 0 ≦ a <0.4, b is average 0 <b <0.5, c is average 0 <c <1, d is average 0 ≦ d < 0.4, b and c average 0.01 ≦ b / c ≦ 0.3, and a + b + c + d = 1. A high-energy beam comprising 100 parts by weight of (meth) acryloxy group-containing organopolysiloxane resin, (B) 0.01 to 10 parts by weight of a photopolymerization initiator, and (C) 0 to 5000 parts by weight of an organic solvent. Curable organopolysiloxane resin composition. The monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms is a methyl group, the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is a phenyl group, and R ⁷ is a hydrogen atom. High energy ray-curable organopolysiloxane resin composition described The high energy ray-curable organopolysiloxane resin composition according to claim 3 or 4, which is used for an optical transmission member. The high energy ray-curable organopolysiloxane resin composition according to claim 5, wherein the light transmission member is an optical waveguide. The high energy ray-curable organopolysiloxane resin composition according to any one of claims 3 to 6, wherein the high energy ray is an ultraviolet ray. (A) Siloxane unit formula (1)
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (1)
[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, Group and Formula (2): CH ₂ = C (R ⁷ ) COOR ⁸ − (2)
(Wherein R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkylene group having 2 or more carbon atoms), or one or more monovalent organic groups selected from the group represented by The siloxane unit having a group represented by the formula (2) in the molecule is 5 mol% to 50 mol%, and the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the molecule is 10 wt% to 50% by weight, a is average 0 ≦ a <0.4, b is average 0 <b <0.5, c is average 0 <c <1, d is average 0 ≦ d < 0.4, b and c average 0.01 ≦ b / c ≦ 0.3, and a + b + c + d = 1. An optical transmission member comprising a cured product by irradiation with high energy rays in the presence of a photopolymerization initiator (B) of a (meth) acryloxy group-containing organopolysiloxane resin (A) represented by: The optical transmission member according to claim 8, wherein the optical transmission member is an optical waveguide. The optical transmission member according to claim 8, wherein the high energy ray is ultraviolet rays. An optical transmission comprising: (a) a step of applying a high energy ray-curable organopolysiloxane resin composition according to claim 3 to a substrate; and (b) a step of curing the application product by high energy ray irradiation. Manufacturing method of member. A high energy ray-curable organopolysiloxane resin composition according to claim 3 is applied to a substrate, and the coated material is irradiated with high energy rays and cured to form a lower clad layer, and the lower clad layer is formed on the lower clad layer. The high energy ray-curable organopolysiloxane resin composition described above (however, the refractive index of the cured product is larger than that of the cured product for the clad layer), and the coated product is cured by irradiation with high energy rays. 4. The high energy ray-curable organopolysiloxane according to claim 3, wherein a layer is formed, the core layer is processed into a desired shape as necessary, and the core layer or the core layer and the lower clad layer of the desired shape are formed on the core layer. A method for producing an optical waveguide, comprising: applying a resin composition, and curing the applied material by irradiation with high energy rays to form an upper clad layer. The production method according to claim 11 or 12, wherein the high energy ray is ultraviolet rays.