KR101190530B1 - Active energy ray-curable organopolysiloxane resin composition, optical transmission component, and manufacturing method thereof - Google Patents

Abstract

The present invention provides (A) 100 parts by weight of an organopolysiloxane resin containing an epoxy group and an aromatic hydrocarbon group, (B) 0.05 to 20 parts by weight of a photoacid generator, (C) a photosensitizer or a photo-radical generator to 0.01 to 20 An active energy ray (for example, UV-ray) curable organopolysiloxane resin composition containing a weight part and 0-5,000 weight part of (D) organic solvents. The present invention also relates to a light transmitting member made of the composition cured by irradiation of active energy rays (eg UV-rays). Also provided is a method of producing a light transmitting member by irradiating the composition with an active energy ray (eg UV-rays).

Organopolysiloxane resin, active energy ray, light transmission member, organic solvent.

Description

Active energy ray-curable organopolysiloxane resin composition, optical transmission member and manufacturing method thereof {active energy ray-curable organopolysiloxane resin composition, optical transmission component, and manufacturing method}

The present invention relates to an active energy ray-curable organopolysiloxane resin composition useful for the production of a light transmission member, a light transmission member consisting of a cured product obtained by irradiating the organopolysiloxane resin composition with an active energy ray, and a light transmission member It relates to a manufacturing method.

Quartz and glass are used not only as optical fiber materials, but also as reliable optical materials for optical communication. However, since such materials require high temperature treatment and provide poor productivity, there is a need to have better durability and processability for organic materials for communication devices. Polyimide, the most reliable organic material, is widely used as a raw material for electronic parts. Organopolysiloxanes, on the other hand, have received attention in the optoelectronics field due to their excellent optical transmittance, electrical insulation, optical stability, and thermal stability. Physical properties required for optically transmissive materials, for example, birefringent members due to nonabsorption and polymer chain orientation in the communication wavelength band 1300 nm to 1660 nm, as well as heat resistance, hygroscopicity and water resistance which are considered very important properties for the assembly of the device. Is constantly being improved mainly using the polyimide and organopolysiloxane-based materials described above.

Catalytic amounts of onium salts to organopolysiloxanes prepared from organochlorosilanes (eg phenyltrichlorosilane, methyltrichlorosilane) and hydroxyl-containing epoxy compounds (eg glycidyl alcohol) as raw materials Although well-known polymeric optical materials, especially those for optical waveguides, obtained by adding a photoinitiator and irradiating the mixture with light, are described in Japanese Patent Application Publication (hereinafter referred to as "Japanese Patent Publication"). (Pri. 9) 124793], a problem arises with the fact that the materials can be readily hydrolyzed by Si-OC bonds due to insufficient adhesion to the substrate and bonding of epoxy-containing organic groups. . Hydrolyzable silanes of the formula R _m Si (X) ₄ , wherein R is an unhydrolysable organic group, X is a hydrolyzable group, m is 0-3, or a condensation product thereof (eg, phenyl Co-hydrolysis and condensation products of trimethoxysilane, methyltrimethoxysilane and dimethyldimethoxysilane) (A), organic onium salt-containing radiation (e.g. UV curable compositions containing curable compositions (B) and condensed aromatic compounds (e.g., anthracene, anthraquinone) (C) are known (Japanese Patent Laid-Open No. 2003). -185860), a composition of this type has a problem that if it is not blended with an antifoaming agent it contains bubbles in the cured film due to curing by condensation.

While alkoxy- and epoxy-containing organopolysiloxanes (a), cationic photoinitiators (e.g. onium salts) (b) and free radical photoinitiators (e.g. benzoin, acetophenones) or photosensitizers (e.g. There is a known radiation (eg UV) curable silicone composition comprising thioxanthone (c). Furthermore, liquid cationic polymerizable organopolysiloxanes (epoxy-containing organopolysiloxanes) (A), cationic polymerization photoinitiators (B) having onium salt structures and sensitizers (naphthalene derivatives, anthracene derivatives and phenanthrene derivatives) (C There are known release coating radiation curable silicone-containing compositions, which are all used to provide peelability and release property to the tacky material, in particular by coating and curing the paper with such a composition. Alkoxy- and epoxy-containing methylpolysiloxanes (a) are believed to be suitable for use in the compositions mentioned earlier, and in later mentioned compositions the cationic polymerizable organopolysiloxanes are silicon bonded monovalent hydrocarbon groups represented by methyl groups. Although it is considered suitable to be linear or comminuted, having at least 85 mol%, the cured products of these compositions have a refractive index and optical transmittance when morphological retention properties, solvent resistance and optical transmission in the communication wavelength band are insufficient and are exposed to high temperatures. There is a problem that indicates a significant change in.

Therefore, as a result of close investigation for the purpose of developing an active energy ray-curable organopolysiloxane resin composition without such a problem, the inventors of the present application cure rapidly upon irradiation with an active energy ray (for example, UV ray), and cure It contains no air bubbles, the cured product has good resistance to hydrolysis, morphology and solvent resistance, provides high optical transmission in the communication wavelength band, and refractive index and optical transmittance when exposed to high temperatures. An active energy ray-curable organopolysiloxane resin composition showing only a slight change in was invented and patented thereon (Japanese Patent Application No. 2003-412452). Incidentally, when such a composition is applied to a substrate (e.g., a silicon substrate) and cured by irradiation with UV radiation, the cured product exhibits insufficient adhesion to the substrate (e.g., a silicon substrate) and is weak. After storage for three months or after aging at about 100 ° C., it can easily peel off from the substrate, which is a cause for concern about the stability of the product quality. While attempts have been made to reduce the stress remaining in the cured film, a special primimg treatment is used and the substrate is treated with alkali to improve the adhesion to the substrate where the composition comes into contact with the curing process, A sufficient effect was not obtained.

The present invention has been made by finding that the adhesion is improved when the composition is combined with a photosensitizer or a photo-radical generating agent.

It is an object of the present invention to provide good adhesion to a substrate, to cure rapidly upon irradiation with active energy rays such as UV rays, to contain no bubbles in the cured product, and the cured product is hydrolyzed. An energy ray-curable organopolysiloxane resin composition having excellent resistance to morphology, shape retention properties and solvent resistance, providing high optical transmittance in a communication wavelength band, and exhibiting only slight changes in refractive index and optical transmittance when exposed to high temperature. To provide.

The present invention relates to the following [1] to [9].

[1] (A) 100 parts by weight of an epoxy-containing organopolysiloxane resin of the following average siloxane unit:

(B) 0.05 to 20 parts by weight of the photoacid generator,

(C) 0.01 to 20 parts by weight of a photosensitizer or photo-radical generating agent and

(D) Active-energy-ray-curable organopolysiloxane resin composition containing 0-5,000 weight part of organic solvents.

(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

In the above formula (1)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are selected from the C ₁ to C ₆ monovalent aliphatic hydrocarbon groups, C ₆ to C ₁₀ monovalent aromatic hydrocarbon groups and epoxy-containing monovalent hydrocarbon groups Selected organic groups, wherein the siloxane units contain 2 to 50 mol% of epoxy containing monovalent hydrocarbon groups per molecule and at least 15 mol% of all organic groups of monovalent aromatic hydrocarbon groups of C ₆ to C ₁₀ ,

a + b + c + d is 1, and 0 ≦ a <0.4, 0 <b <0.5, 0 <c <1, 0 ≦ d <0.4 and 0.1 ≦ b / c ≦ 0.3.

[2] An active energy ray curable organopolysiloxane resin composition as mentioned in the above [1], for use in a light transmitting member.

[3] The active energy ray curable organopolysiloxane resin composition as mentioned in the above [2], wherein the light transmitting member is adhered to the substrate.

[4] The active energy ray-curable organopolysiloxane resin composition as mentioned in the above [2] or [3], wherein the light transmitting member is an optical waveguide.

[5] The active energy ray-curable organopolysiloxane resin composition as mentioned in any one of [1] to [4], wherein the active energy ray is UV ray.

[6] A light transmission member made of a cured product obtained by irradiating an active energy ray curable organopolysiloxane resin composition as mentioned in [1] using an active energy ray.

[7] The light transmitting member as mentioned in the above [6], wherein the cured product is adhered to the substrate.

[8] The light transmission member as mentioned in the above [6] or [7], wherein the active energy ray is UV ray.

[9] (1) applying an active energy ray curable organopolysiloxane resin composition as mentioned in the above [1] to a substrate, and (2) applying the applied active energy ray curable organopolysiloxane resin composition as an active energy ray. Irradiating and curing, and if necessary, subsequently heating.

The active energy ray-curable organopolysiloxane resin composition of the present invention is cured rapidly upon irradiation with active energy rays such as UV rays, exhibits excellent morphological properties even in the form of thin films, does not contain bubbles in the cured product, and is cured. The product retains resistance to hydrolysis and solvent resistance. Specifically, the composition has sufficient elasticity and hardness so that it is not easily bent and does not actually cause warping or cracking. In addition, the composition has good adhesion to the substrates that come into contact during the curing process. The cured product has high optical transmission and very small transmission loss in the communication wavelength band. The refractive index is easier to control than the conventional composition, and the change in optical transmittance and refractive index is very small even when exposed to high temperature. The light transmitting member of the present invention does not contain bubbles, has excellent resistance to hydrolysis, morphology and solvent resistance, provides high optical transmittance in a communication wavelength band, and optical transmittance and refractive index when exposed to high temperature. Insignificant change in. The light transmission member formed on the substrate exhibits excellent adhesion to the substrate.

The epoxy-containing organopolysiloxane resin of the following average siloxane units of formula (1) is the main component of the active energy ray curable organopolysiloxane resin composition of the present invention.

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

In the above formula (1)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are selected from the C ₁ to C ₆ monovalent aliphatic hydrocarbon groups, C ₆ to C ₁₀ monovalent aromatic hydrocarbon groups and epoxy-containing monovalent hydrocarbon groups Selected organic groups, wherein the siloxane units contain 2 to 50 mol% of epoxy containing monovalent hydrocarbon groups per molecule and at least 15 mol% of all organic groups of monovalent aromatic hydrocarbon groups of C ₆ to C ₁₀ ,

a + b + c + d is 1, and 0 ≦ a <0.4, 0 <b <0.5, 0 <c <1, 0 ≦ d <0.4 and 0.1 ≦ b / c ≦ 0.3. Since the resin composition contains an epoxy group, the resin is rapidly released upon irradiation with active energy rays such as UV rays, electron beams or ionizing radiation in the presence of a photo acid generator (B) and a photosensitizer or photo-radical generator (C). Hardened. When the composition is in contact with a substrate (eg, a silicon substrate), the composition is cured and firmly adhered to the substrate by irradiating it with active energy rays such as UV rays, electron beams or ionizing radiation.

Average siloxane units In the epoxy-containing organopolysiloxane resin of formula (A) (R ⁴ R ⁵ SiO _2/2 ) units and (R ⁶ SiO _3/2 ) units are essential, while (R ¹ R ² R ³ SiO _1/2 ) units and (SiO _4/2 ) units are any structural unit. Thus, there may be epoxy-containing organopolysiloxane resins comprising the following units:

(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

(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

If too many (R ¹ R ² R ³ SiO _1/2 ) units are present, the index a is 0 ≦ a <0.4, since the molecular weight of the epoxy-containing organopolysiloxane resin (A) is low, and (SiO _{4 / 2} ) When units are introduced, the hardness of the cured product of the epoxy-containing organopolysiloxane resin (A) is increased significantly, so that the product can be easily broken. For this reason, the index d is 0 ≦ d <0.4, preferably 0 ≦ d <0.2, more preferably d = 0. The molar ratio b / c of the (R ⁴ R ⁵ SiO _2/2 ) unit and the (R ⁶ SiO _3/2 ) unit, which is an essential structural unit, is 0.01 or more and 0.3 or less. Outside this range in the preparation of the epoxy-containing organopolysiloxane resin (A) can lead to the formation of insoluble by-products, tend to crack the product due to reduced toughness, or reduce the strength and elasticity of the product The tendency for scratching is increased. The preferable range of molar ratio b / c is 0.01 or more and 0.25 or less, More preferably, it is 0.02 or more and 0.25 or less. Epoxy-containing organopolysiloxane resins (A) contain (R ⁴ R ⁵ SiO _2/2 ) units and (R ⁶ SiO _3/2 ) units as essential structural units, the molecular structure of which in most cases is a molar ratio Since b / c is 0.01 or more and 0.3 or less, it is a network structure or three-dimensional structure.

Examples of silicon-bonded C ₁ to C ₆ monovalent aliphatic hydrocarbon groups in component (A) are methyl, ethyl, propyl, butyl, hexyl and other monovalent aliphatic saturated hydrocarbon groups, and vinyl, allyl, hexenyl and other Monovalent aliphatic unsaturated hydrocarbon groups. In addition, examples of silicon-bonded C ₆ to C ₁₀ monovalent aromatic hydrocarbon groups in component (A) are phenyl, tolyl, xylyl and naphthyl. Refractive index, an important optical property, is controlled by alteration of monovalent hydrocarbon groups. When methyl and other monovalent aliphatic unsaturated hydrocarbon groups are used as the main substitution group, the refractive index tends to be less than 1.5, whereas when phenyl and other monovalent aromatic hydrocarbon groups are used as the main substituent group, the refractive index is 1.5 or more. Tends to be set to The monovalent aliphatic saturated hydrocarbon group is preferably a methyl group and the monovalent aromatic hydrocarbon group is preferably a phenyl group. Vinyl groups are preferred when the composition contains monovalent aliphatic unsaturated hydrocarbon groups.

The monovalent aromatic hydrocarbon group constitutes preferably at least 15 mol%, more preferably at least 20 mol% and most preferably at least 25 mol% of all organic groups in component (A). The reason is that when the monovalent aromatic hydrocarbon group is lower than the lower limit of the above range, the optical transmittance of the cured product of the active energy ray-curable organopolysiloxane resin composition of the present invention is decreased in the communication wavelength band, and the cured product is reduced. This is because it shows a tendency to crack due to toughness.

In component (A), the siloxane units having an epoxy-containing monovalent hydrocarbon group comprise from 2 mol% to 50 mol%, preferably from 10 mol% to 40 mol%, more preferably from 15 mol% to 40 mol% of all siloxane units. If these siloxane units are less than 2 mol%, the crosslink density during the curing is low, making it impossible to obtain sufficient hardness for the light transmitting member. On the other hand, if it exceeds 50 mol%, it is not suitable because it reduces the optical transmittance and heat resistance of the cured product. The epoxy groups in the epoxy-containing monovalent hydrocarbon groups are preferably bonded to silicon atoms via alkylene groups such that such epoxy groups are not directly bonded to silicon atoms.

Examples of such groups include the 3- (glycidoxy) propyl group of the formula

2- (glysidoxycarbonyl) propyl group of the formula

2- (3,4-epoxycyclohexyl) ethyl group of the formula

2- (4-methyl-3,4-epoxycyclohexyl) propyl group of the formula

Specific examples of the epoxy-containing organopolysiloxane resin (A) include organopolysiloxane resins including (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), and (E ¹ SiO _3/2 ) units; Organopolysiloxane resin comprising (Me ₃ SiO _1/2 ), (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), and (E ¹ SiO _3/2 ) units; Organopolysiloxane resin comprising (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), (E ¹ SiO _3/2 ), and (SiO _4/2 ) units; Organopolysiloxane resin comprising (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), (MeSiO _3/2 ) and (E ¹ SiO _3/2 ) units; Organopolysiloxane resin comprising (Ph ₂ SiO _2/2 ), (PhSiO _3/2 ) and (E ¹ SiO _3/2 ) units; Organopolysiloxane resin comprising (MePhSiO _2/2 ), (PhSiO _3/2 ) and (E ¹ SiO _3/2 ) units; Organopolysiloxane resin comprising (Me ₂ SiO _2/2 ), (PhSiO _3/2 ) and (E ² SiO _3/2 ) units; Organopolysiloxane resin comprising (Me ₂ SiO _2/2 ), (PhSiO _3/2 ) and (E ³ SiO _3/2 ) units; _{(Me 2 SiO 2/2), (} PhSiO 3/2) and (E ⁴ SiO _3/2) organopolysiloxane resin comprising units; Organopolysiloxane resin comprising (MeViSiO _2/2 ), (PhSiO _3/2 ) and (E ³ SiO _3/2 ) units; Organopolysiloxane resin comprising (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), (MeSiO _3/2 ), and (E ³ SiO _3/2 ) units; Organopolysiloxane resin comprising (Ph ₂ SiO _2/2 ), (PhSiO _3/2 ) and (E ³ SiO _3/2 ) units; Organopolysiloxane resins comprising (Me ₂ SiO _2/2 ), (Ph ₂ SiO _2/2 ) and (E ¹ SiO _3/2 ) units; Organopolysiloxane resin comprising (Me ₂ SiO _2/2 ), (Ph ₂ SiO _2/2 ), and (E ³ SiO _3/2 ) units; Organopolysiloxane resin comprising (Me ₂ ViSiO _1/2 ), (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), and (E ¹ SiO _3/2 ) units; Organopolysiloxane resin comprising (Me ₃ SiO _1/2 ), (Ph ₂ SiO _2/2 ), (PhSiO _3/2 ), and (E ¹ SiO _3/2 ) units; Organopolysiloxane resin comprising (Me ₃ SiO _1/2 ), (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), and (E ³ SiO _3/2 ) units; Organopolysiloxane resin comprising (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), (E ³ SiO _3/2 ) and (SiO _4/2 ) units; Organopolysiloxane resin comprising (Me ₂ SiO _2/2 ), (Ph ₂ SiO _2/2 ), (E ¹ SiO _3/2 ), and (SiO _4/2 ) units; Organopolysiloxane resins including (Me ₃ SiO _1/2 ), (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), (E ¹ SiO _3/2 ), and (SiO _4/2 ) units; Organopolysiloxane resins comprising (Me ₃ SiO _1/2 ), (Me ₂ SiO _2/2 ), (PhSiO _3/2 ), (E ³ SiO _3/2 ) and (SiO _4/2 ) units [Where Me is a methyl group, Vi is a vinyl group, Ph is a phenyl group, E ¹ is a 3- (glycidoxyoxy) propyl group and E ² is a 2- (glycidoxyoxyyl) propyl group , E ³ is a 2- (3,4-epoxycyclohexyl) ethyl group, and E ⁴ is a 2- (4-methyl-3,4-epoxycyclohexyl) propyl group. Homology below].

Epoxy-containing organopolysiloxane resin (A) can be manufactured by a well-known conventional manufacturing method like the method of Unexamined-Japanese-Patent No. 6-298940, for example.

For example, a method of co-hydrolysis and condensation of a silane of the formula R ⁴ R ⁵ SiCl _{2 with} a silane of the formula R ⁶ SiCl ₃ , optionally comprising these silanes of the formula R ¹ R ² R ³ SiCl Co-hydrolyzing and condensing only with silane, or with only a silane of formula SiCl ₄ , or with a silane of formula R ¹ R ² R ³ SiCl and a silane of formula SiCl ₄ ; And methods of co-hydrolysis and condensation using a silane obtained by substituting a chlorine atom in the aforementioned silane with a methoxy or ethoxy group (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are organic groups selected from C ₁ to C ₆ monovalent aliphatic hydrocarbon groups, C ₆ to C ₁₀ monovalent aromatic hydrocarbon groups and epoxy-containing monovalent hydrocarbon groups). In addition, methylphenylpolysiloxane resins containing silicon-bonded epoxy groups, such as 3- (glycidoxyoxy) propyl, may be co-used of dimethyldichlorosilane and phenyltrichlorosilane, or methyldichlorosilane, methyltrichlorosilane and phenyltrichlorosilane. Prepared by preparing a silanol-containing methylphenylpolysiloxane resin by hydrolysis and condensation, basifying the reaction system and then adding an epoxy-containing organopolysiloxane such as 3- (glycidoxy) propyltrimethoxysilane to condense There is a way. Indices a, b, c and d in the average unit formula 1 can be adjusted by controlling the amount of raw silanes used and their molar ratios.

Incidentally, depending on the preparation method and conditions, the organopolysiloxane resin may contain residual hydroxyl and alkoxy groups bonded to silicon atoms. The amount of these substituent groups should be reduced as much as possible, since they have a negative effect on the storage stability of the organopolysiloxane resin and act as a factor in lowering the heat resistance of the cured organopolysiloxane resin. The content of these substituent groups can be reduced, for example, by carrying out a dehydration condensation reaction or a dealcohol condensation reaction by heating the organopolysiloxane resin in the presence of trace amounts of potassium hydroxide. The preferred range for the content of these substituent groups is 2 mol% or less, more preferably 1 mol% or less.

The number average molecular weight of the epoxy-containing organopolysiloxane resin (A) is not particularly limited, but considering the toughness of the cured product and its solubility in an organic solvent, the molecular weight is preferably 10 ³ or more and 10 ⁶ or less. Combinations of two or more of these epoxy-containing organopolysiloxane resins having different contents and different kinds of epoxy-containing organic groups and monovalent hydrocarbon groups or different molecular weights can be used.

As long as the photoacid generator (B) is used as the photoacid generator for the epoxy-containing organopolysiloxane, the photoacid generator is not particularly limited, for example, sulfonium salt, iodonium salt, selenium salt, Phosphonium salts, diazonium salts, paratoluene sulfonates, trichloromethyl-substituted triazines and trichloromethyl-substituted benzenes.

Salts of formula R ⁷ ₃ S ⁺ X ^- are preferred as sulfonium salts. In the above formula, R ⁷ is methyl, ethyl, propyl, butyl and other C ₁ to C ₆ alkyl groups; Phenyl, naphthyl, biphenyl, tolyl, propylphenyl, decyl phenyl, dodecyl phenyl, and other C aryl group or a substituted aryl group of _{1 to 24,} in formula X ^- is _{^{SbF 6 -, AsF 6 -,}} PF _{^{6 -, BF 4 -, B}} (C 6 F 5) 4 -, HSO 4 -, ClO 4 -, CF 3 SO 3 - , and other non-nucleophilic represents a non-basic anion. Salts of formula R ⁷ ₂ I ⁺ X ^- are preferred as iodonium salts, in which R ⁷ and X ^- are as defined above. Salts of formula R ⁷ ₃ Se ⁺ X ^- are preferred as selenium salts, in which R ⁷ and X ^- are as defined above. Salts of formula R ⁷ ₄ P ⁺ X ^- are preferred as phosphonium salts, in which R ⁷ and X ^- are as defined above. Salts of formula R ⁷ N ₂ ⁺ X ^- are preferred as diazonium salts, in which R ⁷ and X ^- are as defined above. Compounds of the formula CH ₃ C ₆ H ₄ SO ₃ R ⁸ are preferred as paratoluene sulfonate, in which R ⁸ represents an organic group comprising an electron-attracting group such as a benzoylphenylmethyl group, a phthalimide group, or the like. . Compounds of the formula [CCl ₃ ] ₂ C ₃ N ₃ R ⁹ are preferred as trichloromethyl-substituted triazines wherein R ⁹ is phenyl, substituted or unsubstituted phenylethyl, substituted or unsubstituted furanyl Ethynyl and other electron-attracting groups. Compounds of the formula CCl ₃ C ₆ H ₃ R ⁷ R ¹⁰ are preferred as trichloromethyl-substituted benzene, in which R ⁷ is as defined above, R ¹⁰ is a halogen group, a halogen-substituted alkyl group and Other halogen-containing groups.

When compatibility and miscibility with epoxy-containing organopolysiloxane resin (A) are considered, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium triflate, tri ( p-tolyl) sulfonium hexafluorophosphate, p-tert-butylphenyldiphenylsulfonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate , p-tert-butylphenylbiphenyl iodonium hexafluoroantimonate, di (p-tert-butylphenyl) iodonium hexafluoro antimonate, bis (dodecylphenyl) iodonium hexafluoro Roantimonate, triphenyl selenium tetrafluoroborate, tetraphenylphosphonium tetrafluoroborate, tetraphenylphosphonium hexafluoroantimonate, p-chlorophenyldiazonium tetrafluoroborate , Benzoylphenylmethylparatoluene sulfonate, bistrichloromethylphenyltriazine, bistrichloromethylfuranyltriazine and p-bistrichloromethylbenzene are proposed as preferred photoacid generators. Among the compounds, triphenylsulfonium tetrafluoroborate, di (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium hexafluoroantimonate and p More preferred is -chlorophenyldiazonium tetrafluoroborate.

Commonly known carbonyl-containing aromatic compounds can be used as photosensitizers or photo-radical generating agents (C), but these compounds form a photosensitive effect and are miscible or compatible with epoxy-containing organopolysiloxane resins (A). As long as it can be dissolved in D), these compounds are not particularly limited. Specific examples thereof are isopropyl-9H-thioxanthene-9-one, xanthone, anthracene, anthrone, anthraquinone, benzophenone, 4,4'-bis (dimethylamino) benzophenone, diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1 -Propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1 and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. Among these compounds, isopropyl-9H-thioxanthene-9-one, anthrone, 1-hydroxy-cyclohexyl-phenylketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one are more desirable.

The organic solvent (D) is not an essential component, but the epoxy-containing organopolysiloxane resin (A) is solid or present in the form of a viscous liquid at the temperature at which the molding is carried out, or the epoxy-containing organopolysiloxane resin (A) This is necessary when is molded into a film. In addition, when the photoacid generator (B) is not dissolved in the epoxy-containing organopolysiloxane resin (A), a solvent is necessary to dissolve it. As long as the organic solvent (D) can dissolve the epoxy-containing organopolysiloxane resin (A), the photoacid generator (B) and the photosensitizer or photo-radical generator (C), the form of the organic solvent (D) is There is no particular limitation, and the boiling point of the solvent is preferably 80 ° C to 200 ° C. Specific examples of such solvents are isopropyl alcohol, tertiary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, anisole, toluene, xylene, mesitylene, chlorobenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether , Diethylene glycol dimethyl ether, ethoxy-2-propanol acetate, methoxy-2-propanol acetate, octamethylcyclotetrasiloxane and hexamethyldisiloxane. Such organic solvents may be used alone or as a mixture of two or more solvents.

The active energy ray-curable organopolysiloxane resin composition of the present invention comprises (A) 100 parts by weight of an epoxy-containing organopolysiloxane resin, (B) 0.05 to 20 parts by weight of a photoacid generator, (C) a photosensitizer or a photo-radical generator And (D) 0 to 5,000 parts by weight of an organic solvent. If component (A) is a liquid, or if component (A) can be very well mixed with components (B) and (C), component (D) does not need to be added. If the amount of component (B) is less than 0.05 part by weight, curing becomes insufficient, and if it exceeds 20 parts by weight, it is not suitable because it degrades the optical properties due to the presence of the residual catalyst. When the amount of the added component (C) is less than 0.01 part by weight, curing is insufficient and the adhesiveness is lowered. On the other hand, if it exceeds 20 parts by weight, it is not suitable because it degrades the optical properties due to the presence of the residual catalyst. In addition, when the addition amount of the component (D) exceeds 5000 parts by weight, as described below, it is not suitable because it is difficult to obtain a high quality thin film during the production of the optical transmittance component. The amount of component (D) added depends on its type and the nature or solubility of components (C), (B) and (A), but usually in the range of 1 to 1000 parts by weight, preferably 1 to 500 parts by weight. It is the range of weight part.

When the active energy ray-curable organopolysiloxane resin composition of the present invention is used to form a cured film or light transmitting member, the composition is preferably liquid at room temperature, particularly preferably 20 to 10,000 mPa? has a viscosity of s. Outside this range, it becomes more difficult to obtain a thin film having a high optical quality, causing a decrease in processing performance.

The refractive index of the cured active energy ray-curable organopolysiloxane resin composition of the present invention is determined by changing the molar ratio of the silicon-bonded groups, ie monovalent aliphatic hydrocarbon groups (typically methyl in the epoxy-containing organopolysiloxane resin (A)). Groups) and monovalent aromatic hydrocarbon groups (typically phenyl groups) can be precisely controlled. Increasing the proportion of monovalent aromatic hydrocarbon groups results in a higher refractive index and increasing the number of monovalent aliphatic hydrocarbon groups results in a lower refractive index. When the optical waveguide is made from the active energy ray curable organopolysiloxane resin composition of the present invention, the refractive index of the cured organopolysiloxane resin used for the core is more than the refractive index of the cured organopolysiloxane resin used for cladding. It should be high because the amount of monovalent aromatic hydrocarbon groups in the organopolysiloxane resin composition used for the core is formed higher than the amount of the organopolysiloxane resin composition used for the cladding. To do this, two kinds of organopolysiloxane resins containing different molar ratios of [monoaliphatic hydrocarbon group] / [monovalent aromatic hydrocarbon group] are separately and / or two kinds of organopolysiloxane for the core and the cladding. Resin can be mixed and used in a different ratio.

The light transmitting member made of the cured epoxy-containing organopolysiloxane resin (A) of the general formula (1) of the present invention has excellent shape retention properties even in a thin film form. Specifically, the member has sufficient elasticity and hardness so that it is not easily bent and in fact no distortion or cracking occurs. The birefringence of such cured film is negligibly small according to the birefringence measurement by the prism coupling technique. The light transmitting member formed on the substrate (e.g., silicon substrate) from the cured epoxy-containing organopolysiloxane resin (A) of Formula 1 of the present invention exhibits excellent adhesion to the substrate (e.g., silicon substrate). .

The light transmitting member of the present invention can be used for both the passive member and the active member. Specific examples of passive transmission members are unbranched optical waveguides, branched optical waveguides, multiplexers / demultiplexers, photosynthetic adhesives, etc. Examples of active transmission members are waveguide optical switches, waveguide optical modulators, optical attenuators, optical amplifiers, and the like. .

The method used to prepare the light transmitting member from the cured active energy ray curable epoxy-containing organopolysiloxane resin composition of the present invention is illustrated below.

The light transmitting member can be manufactured by the following steps 1) and 2) described below.

First, the epoxy-containing organopolysiloxane is obtained by uniformly applying the active energy ray-curable organopolysiloxane resin composition according to claim 1 to a substrate, and then removing the organic solvent (D) by air drying or heating, if necessary. A thin film having a uniform thickness made of a resin (A), a photo acid generator (B) and a photosensitive agent or a photo-radical generator (C) is prepared. Examples of materials that are preferably used to produce substrates that are smooth in surface, in solvents, in active energy rays used for curing, and heat stable are silicon wafers, glass, ceramics, and heat resistant plastics. Spin-coating techniques are commonly used for coating, and the continuous heating temperature is preferably in the range of 30 ° C. or higher and 120 ° C. or lower. Subsequently, 2) the produced thin film is cured by irradiating with an active energy ray. The active energy rays used in this case are UV rays, electron beams and ionizing radiation, and UV rays are preferable in terms of safety and equipment cost. Suitable UV ray sources include high pressure mercury lamps, medium pressure mercury lamps, Xe-Hg lamps and deep-UV lamps. The irradiation amount of UV rays is preferably in the range of 100 to 8000 mJ / cm ² . Depending on the type of active energy ray curable organopolysiloxane used, it may sometimes be impossible to carry out curing using only active energy rays alone. In such a case, curing can be completed by heating the thin film (so-called "post-heating") after irradiation with an active energy ray. The preferred temperature range for this subsequent heating is 50 to 200 ° C.

Therefore, the light transmitting member having a high transmittance in the designated wavelength region is applied to 1) the active energy ray-curable organopolysiloxane resin composition on the substrate, and 2) the applied active energy ray-curable organopolysiloxane resin composition to the active energy ray such as UV ray. It is irradiated using and, if necessary, prepared by subsequent heating. Also, a typical light transmission member such as an optical waveguide can be manufactured by repeating steps 1) and 2). An example of such a typical manufacturing method used for an optical waveguide is described next.

First, the lower coating layer is formed by spin coating an active energy ray-curable organopolysiloxane resin composition used for cladding onto a substrate and irradiating and curing the coating with an active energy ray. Subsequently, the core layer is formed by spin coating the active energy ray-curable organopolysiloxane resin composition used for the core to the lower cladding layer and irradiating and curing the resulting coating with active energy ray, if necessary at the time of molding, The core layer is used as a core layer having a higher refractive index than the cladding layer. In order to impart the desired shape to the core layer, i.e. to pattern it, the core layer is irradiated with active energy rays through a photomask having the contour of the shape and, if necessary, by subsequent heat treatment as described above, thereby exposing Unconjugated portions can be dissolved and removed using an organic solvent. The organic solvent (C) can be used as the organic solvent used for this purpose. An optical waveguide comprising a cladding layer, a core layer and another cladding layer is applied with the active energy ray curable organopolysiloxane resin composition used for the cladding on top of the core layer, ie on top of the patterned core layer and the bottom cladding layer. If obtained. The upper cladding layer is formed through curing by irradiation using active energy rays. In the above-mentioned manufacturing method, the cured active energy ray curable organopolysiloxane resin composition used for the core has a refractive index higher than that of the active energy ray curable organopolysiloxane resin composition used for the cladding. Solvent casting techniques may be used instead of spin coating while applying the active energy ray curable organopolysiloxane resin composition.

Hereinafter, examples and comparative examples are provided to specifically illustrate the present invention. However, the present invention is not limited to this embodiment.

The structure of the epoxy-containing organopolysiloxane resin used in these examples is determined by performing ¹³ C NMR and ²⁹ Si NMR measurements. The number average molecular weight of the epoxy-containing organopolysiloxane resin is calculated using GPC based on comparison with polystyrene standards. The content of silanol and methoxy groups is determined with the help of ²⁹ Si NMR method. The deep UV irradiation apparatus of Yamashita Denso Corporation is utilized as an active energy ray source for curing an active energy ray curable organopolysiloxane resin composition.

To measure the index of refraction of the cured product, the cured product is cut into cubes with 5 mm corners, the faces of the cube are polished and then KPR-200 from Kalnew Optical Industrial Co., Ltd. The refractive index is measured in the wavelength range of 435 nm to 1550 nm using a digital precision refractive index meter.

The optical transmittance of the cured product is determined by cutting and polishing the cured product to produce a plate having a thickness of 3 mm, which is measured by using a UV-visible spectrophotometer in the wavelength range 300 to 2500 nm.

Film thickness is measured using Tencor Alphastep 200.

In the following average siloxane unit formulas, Me, Ph, Vi and E ³ respectively represent methyl, phenyl, vinyl and 2- (3,4-epoxycyclohexyl) ethyl groups.

Reference Example 1

Preparation of Epoxy-Containing Organopolysiloxane Resin (A1)

A solution of silanol-containing methylphenylpolysiloxane resin is prepared by co-hydrolysis and condensation of a mixture of 505 g of phenyltrichlorosilane and 47 g of dimethyldichlorosilane in a mixture of 500 g of toluene, 142 g of 2-propanol and 142 g of water. The solution is neutralized with aqueous sodium hydrogen carbonate solution and washed with water, then the water is removed completely under heating. 226 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2 g of a 50% by weight aqueous solution of potassium hydroxide are added to the residual solution, and water, methanol and toluene are removed by azeotropic dehydration while heating and stirring. During the process, a suitable amount of toluene is added to maintain the concentration of the solid material at about 50% by weight. When the dehydration condensation reaction of the silanol groups is complete, the solution is refluxed for a few more hours to complete the equilibrium reaction. After cooling, toluene solution of epoxy-containing organopolysiloxane resin having an average siloxane unit formula of [Me ₂ SiO _2/2 ] _0.10 [PhSiO _3/2 ] _0.65 [E ³ SiO _3/2 ] _0.25 (solids content: 499 g) is obtained by neutralizing the reaction system using a solid acidic absorbent and filtering off the absorbent. The number average molecular weight of the epoxy-containing organopolysiloxane resin is 2500, the phenyl group content is 59 mol%, and the total content of silanol and methoxy groups is 0.8 mol%. Toluene is removed for use in the examples below.

Reference Example 2

Preparation of Epoxy-Containing Organopolysiloxane Resin (A2)

The average unit formula is [3] except that 315 g of phenyltrichlorosilane, 191 g of methyltrichlorosilane, 55 g of dimethyldichlorosilane and 262 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are used as starting materials. Toluene solution (solid matter content: 490 g) of epoxy-containing organopolysiloxane resin with Me ₂ SiO _2/2 ] _0.10 [MeSiO _3/2 ] _0.30 [PhSiO _3/2 ] _0.35 [E ³ SiO _3/2 ] _0.25 Obtained by carrying out the reaction in the same manner as in Reference Example 1. The number average molecular weight of the epoxy-containing organopolysiloxane resin is 3700, the phenyl group content is 32 mol%, and the total content of silanol and methoxy groups is 0.9 mol%. Toluene is removed for use in the examples below.

Example 1

The UV-curable epoxy-containing organopolysiloxane resin compositions 1 to 10 used in the cladding are epoxy-containing organopolysiloxane resins (A2) obtained in Reference Example 2 as component (A), p-tolyldode as component (B). Silphenyliodonium hexafluoroantimonate, isopropyl-9H-thioxanthene-9-one (ITX) as component (C), xanthone, anthrone, benzophenone, 4,4'-bis (dimethyl Amino) Benzophenone (Keton of Michler), diethoxyacetophenone and the product of Ciba Specialty Chemicals, for example, Darocure 1173 (2-hydroxy-2- Methyl-1-phenylpropan-1-one), Irgacure 184 (1-hydroxy-cyclohexyl-phenylketone), Irgacure 369 [2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1] or irgacure 651 (2,2-dimethoxy-1,2-diphenylethan-1-one) and anisole as component (D) in a weight ratio of 100: 3 Mixed with: 0.6: 40 It is manufactured by. In the chamber closing system, the above-mentioned UV-curable epoxy-containing organopolysiloxane resin compositions 1 to 10 are spin-coated stepwise by adjusting the rotation speed to a range of 100 to 1000 rpm on the silicon substrate, and the sample is removed to remove surface adhesion. For 5 minutes at 80 ° C. The cured product of each epoxy-containing organopolysiloxane resin having a uniform thickness of 50 μm is obtained by irradiating a thin film on a silicon substrate using UV rays of 1 J / cm ² . Subsequent heating is performed by placing the cured product formed on the silicon substrate on a hot plate heated to 100 ° C., 120 ° C. and 140 ° C. for 1 minute. Table 1 shows the results obtained by observing the peeling of the cured product from the silicon substrate.

Comparative Example 1

The UV-curable epoxy-containing organopolysiloxane resin composition (comparative composition 1) used in the cladding is epoxy-containing organopolysiloxane resin (A2) obtained in Reference Example 2 as component (A), p- as component (B). Tolyldodecylphenyl iodonium hexafluoroantimonate and anisole as component (D) are prepared by mixing in a weight ratio of 100: 3: 40. A film of cured epoxy-containing organopolysiloxane resin having a thickness of 50 μm adhered to the silicon substrate is obtained by spin coating the composition onto the silicon substrate in the same manner as in Example 1, irradiating it with UV rays, and then heating. In the same manner as in Example 1, the result obtained by subsequently heating the cured product adhered to the silicon substrate and observing the peeling of the cured product from the silicon substrate is shown in Table 1.

Peeling of the Cured Cladding Composition Component (C) Peeling Composition 1 ITX radish Composition 2 Xanthone radish Composition 3 Antron radish Composition 4 Benzophenone radish Composition 5 4,4'-bis (dimethylamino) benzophenone radish Composition 6 Diethoxyacetophenone radish Composition 7 Tarocure 1173 radish Composition 8 Irgacure 184 radish Composition 9 Irgacure 369 radish Composition 10 Irgacure 651 radish Comparative Composition 1 - U

As shown in Table 1, the cured product of Comparative Composition 1 (which contains neither the photosensitizer nor the photo-radical generator) shows delamination during subsequent heating, while the photo-radical generator or the photosensitizer of Example 1 contains The cured product of compositions 1 to 10 shows no peeling during subsequent heating, which indicates that the adhesion to the silicon substrate is improved by adding a photo-radical generator or a photosensitizer.

Example 2

The UV-curable epoxy-containing organopolysiloxane resin compositions 11 to 15 used in the core are epoxy-containing organopolysiloxane resins (A1) obtained in Reference Example 1 as components (A) and epoxy-referred to in Reference Example 2- A mixture having a weight ratio of 7/3 of the containing organopolysiloxane resin (A2), p-tolyldodecylphenyl iodonium hexafluoroantimonate as component (B), ITX, xanthone, anthrone, It is prepared by mixing arocsole 1173 or Irgacure 184 and anisole as component (D) in a weight ratio of 100: 3: 0.6: 40. Anisole is removed under vacuum from these organopolysiloxane resin compositions 11-15 in a polytetrafluoroethylene resin cup, the composition is molded into 1 cm thick discs, and the cured product of epoxy-containing organopolysiloxane resin is 10 J. Obtained by irradiating the disk from above and from below with UV rays of / cm ² . The cured product is cut into pieces and polished to prepare a test sample and its optical transmittance and refractive index are measured and listed in Table 2. The numerical values listed in the table are those obtained at 1550 nm. In addition, the test sample does not contain bubbles. The cured product has high optical transmission and very low transmission loss in the communication wavelength band. This change in optical transmittance and refractive index is very small even when exposed to high temperatures.

Comparative Example 2

The UV-curable epoxy-containing organopolysiloxane resin composition (comparative composition 2) was prepared by using the epoxy-containing organopolysiloxane resin (A1) obtained in Reference Example 1 as component (A) and the epoxy-containing organo obtained in Reference Example 2. A mixture produced by mixing the polysiloxane resin (A2) with a weight ratio of 7/3, p-tolyldodecylphenyl iodonium hexafluoroantimonate as component (B) and anisole as component (D) by weight ratio 100: Prepared by mixing at 3:40. Comparative Composition 2 is cured in the same manner as in Example 2 to prepare a cured product of epoxy-containing organopolysiloxane resin. The optical transmittance and refractive index of the cured product were measured, and the results are shown in Table 2.

Example 3

In the chamber closed system, the UV-curable epoxy-containing organopolysiloxane resin composition 1 (containing ITX as component (C)) used in the cladding, prepared in Example 1, was increased on the silicon substrate in the range of 100 to 1000 rpm. Spin step by step, and the sample is left at 80 ° C. for 5 minutes to remove surface adhesion. A thin film of a cured epoxy-containing organopolysiloxane resin having a uniform thickness of 50 μm is obtained by irradiating the thin film on a silicon substrate using UV rays of 1 J / cm ² and then heating at 80 ° C. for 5 minutes. The cured thin film was then used as the bottom cladding layer, in which the UV-curable epoxy-containing organopolysiloxane resin composition 11 (containing ITX as component (C)) used in the core prepared in Example 2 was described above. Spin coat under the same conditions as above, and the sample is left at 80 ° C. for 5 minutes to remove surface adhesion. The uncured film of organopolysiloxane resin composition 11 was irradiated with UV rays of 1.0 J / cm ² through a glass mask having a rectangular optical path having a line width of 50 μm and a length of 5 cm, and heated at 80 ° C. for 5 minutes. Curing the exposed part. A core pattern of a cured epoxy-containing organopolysiloxane resin having a uniform thickness of 50 μm, a line width of 50 μm and a length of 5 cm is prepared by dissolving and removing unexposed portions using methylisobutylketone. The UV-curable epoxy-containing organopolysiloxane resin composition 1 (containing ITX as component (C)) used for cladding is spin coated onto the prepared core pattern and lower cladding layer and irradiated with UV rays. UV-curable epoxy-containing organopolysiloxane resin composition 1 was spin-coated once again on the resulting coating, cured by UV irradiation of 3J / cm ² , and then heated at 80 ° C. for 5 minutes, onto a silicon substrate. A channel optical waveguide having an overall thickness of 150 μm is obtained. It is confirmed that the lower cladding layer of the channel optical waveguide is firmly adhered to the silicon substrate and no peeling occurs even after subsequent heating under the same conditions as in Example 1, which shows excellent adhesion to the silicon substrate. Subsequently, instead of the UV-curable epoxy-containing organopolysiloxane resin composition 1 (containing ITX as component (C)) used for the cladding, UV-curable epoxy-containing organopolysiloxane resin compositions 2, 3, 7 and A channel optical waveguide is prepared under the same conditions as above from 8 (containing xanthone, antron, Darocure 1173 or Irgacure 184 as component (C)). It was confirmed that the lower cladding layer of the channel optical waveguide does not peel off even after subsequent heating under the same conditions as in Example 1, which shows excellent adhesion to the silicon substrate. In addition, the fact that the cured exposed parts cannot be dissolved with methyl isobutyl ketone, while the unexposed parts are dissolved with methyl isobutyl ketone and removed, indicates that the cured product retains solvent resistance. Cured layers do not contain bubbles.

Comparative Example 3

It is carried out using the UV-curable epoxy-containing organopolysiloxane resin composition used for the cladding prepared in Comparative Example 1, and the UV-curable epoxy-containing organopolysiloxane resin composition 11 used for the core prepared in Example 2 Attempts to fabricate channel optical waveguides in the same manner as in Example 3 were unsuccessful because the lower cladding layer was peeled off from the silicon substrate during manufacture, thereby making it impossible to manufacture the channel optical waveguides.

Example 4

In the chamber closed system, the UV-curable epoxy-containing organopolysiloxane resin composition 1 (containing ITX as component (C)) used in the cladding, prepared in Example 1, was increased on the silicon substrate in the range of 100 to 1000 rpm. Spin step by step, and the sample is left at 80 ° C. for 5 minutes to remove surface adhesion. A cured thin film of epoxy-containing organopolysiloxane resin having a uniform thickness of 50 μm is obtained by irradiating the thin film on a silicon substrate using UV rays of 1 J / cm ² and then heating at 80 ° C. for 5 minutes. Subsequently, the cured thin film attached to the silicon substrate was used as the lower cladding layer, and the UV-curable epoxy-containing organopolysiloxane resin compositions 11 to 15 used in the core prepared in Example 2 were used as described above. Spin coat under the same conditions and the sample is left at 80 ° C. for 5 minutes to remove surface adhesion. The thin film is irradiated with UV rays of 1.0 to 1.25 J / cm ² through a glass mask having a rectangular optical path having a line width of 50 μm and a length of 5 cm and heated at 80 ° C. for 5 minutes to cure the exposed portion. The core pattern of the cured epoxy-containing organopolysiloxane resin having a uniform thickness of 50 μm, a line width of 50 μm and a length of 5 cm is prepared by dissolving and removing the unexposed portions using methylisobutylketone. Table 2 shows the pattern properties such as the lowest amount of UV rays in which the cross section of the patterned core becomes rectangular. In addition, the fact that the cured exposed parts cannot be dissolved with methyl isobutyl ketone, while the unexposed parts are dissolved and removed with methyl isobutyl ketone, indicates that the cured product retains solvent resistance. Cured layers do not contain bubbles. The core pattern did not lose its rectangular shape after subsequent heating to 140 ° C., which shows excellent shape retention properties.

Comparative Example 4

Use of the UV-curable epoxy-containing organopolysiloxane resin composition (comparative composition 2) used for the core prepared in Comparative Example 2 instead of the UV-curable epoxy-containing organopolysiloxane resin compositions 11 to 15 used for the core. Except for forming the core pattern on the lower cladding layer under the same conditions as in Example 4. The pattern characteristics produced are shown in Table 2.

Properties of Cured Cladding Compositions Component (C) Pattern properties Refractive index Optical transmittance (%) Composition 11 ITX 0.5 1.520 95.1 Composition 12 Xanthone 1.0 1.520 94.7 Composition 13 Antron 0.5 1.519 95.4 Composition 14 Tarocure 1173 1.25 1.519 95.4 Composition 15 Irgacure 184 1.0 1.520 95.5 Comparative Composition 2 - 1.25 1.520 95.8

The "Pattern Properties" column shows the lowest amount of UV radiation (J / cm ² ) in which the cross section of the patterned core becomes rectangular.

As shown in Table 2, the UV-curable epoxy-containing organopolysiloxane resin compositions 11 to 15 used in the core containing the photosensitizer or the photo-radical generator have UV-free photoresist and no photo-radical generator. The core pattern can be prepared using irradiation at a dose equal to or lower than the UV radiation dose required for the curable epoxy-containing organopolysiloxane resin composition (comparative composition 2).

The refractive index and optical transmittance of the cured UV-curable epoxy-containing organopolysiloxane resin compositions 11 to 15 used in the core, containing a photosensitizer or photo-radical generating agent, are UV-curable containing no photosensitizer and no photo-radical generator. It is substantially the same as the refractive index and the optical transmittance of the epoxy-containing organopolysiloxane resin composition (comparative composition 2). These results indicate that the photosensitizer and the photo-radical generating agent have virtually no influence on the optical properties.

The active energy ray-curable organopolysiloxane resin composition of the present invention is very useful for the production of light transmitting members such as optical waveguides. The light transmission member of the present invention is suitable for use as a material for an optical integrated circuit or a material for optical communication. The manufacturing method of the light transmission member of the present invention is useful for the production of a light transmission member, especially a light transmission member adhered to a substrate.

Claims (10)

(A) 100 parts by weight of an epoxy-containing organopolysiloxane resin having an average siloxane unit of the following formula (1), (B) 0.05 to 20 parts by weight of the photoacid generator, (C) 0.01 to 20 parts by weight of a photosensitizer or photo-radical generating agent and (D) Active-energy-ray-curable organopolysiloxane resin composition containing 0-5,000 weight part of organic solvents. 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 In the above formula (1) R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are C ₁ to C ₆ monovalent aliphatic hydrocarbon groups, C ₆ to C ₁₀ monovalent aromatic hydrocarbon groups and a total carbon number of 5 to 10 epoxy- An organic group selected from the group consisting of monovalent aliphatic hydrocarbons, wherein the siloxane units contain 2 to 50 mol% per molecule of epoxy-containing monovalent aliphatic hydrocarbon groups having 5 to 10 carbon atoms in total and a C ₆ to C ₁₀ monovalent aromatic hydrocarbon group Possesses at least 15 mol% of all organic groups in, a + b + c + d is 1, and 0 ≦ a <0.4, 0 <b <0.5, 0 <c <1, 0 ≦ d <0.4 and 0.1 ≦ b / c ≦ 0.3. The active energy ray curable organopolysiloxane resin composition according to claim 1, for use in a light transmission member. The active energy ray curable organopolysiloxane resin composition according to claim 2, wherein the light transmitting member is bonded to the substrate. The active energy ray curable organopolysiloxane resin composition according to claim 2 or 3, wherein the light transmitting member is an optical waveguide. The active energy ray curable organopolysiloxane resin composition according to any one of claims 1 to 3, wherein the active energy ray is a UV ray. A light transmission member made of a cured product obtained by irradiating an active energy ray curable organopolysiloxane resin composition according to claim 1 using an active energy ray. The light transmitting member of claim 6, wherein the cured product is adhered to the substrate. (1) applying the active energy ray-curable organopolysiloxane resin composition according to claim 1 to a substrate; and (2) curing the applied active energy ray-curable organopolysiloxane resin composition with an active energy ray, if necessary. And subsequently heating. The method of claim 1, wherein the epoxy-containing monovalent aliphatic hydrocarbon group having 5 to 10 carbon atoms as the epoxy-containing group is glycidoxy, glycidoxycarbonyl, 3,4-epoxycyclohexyl or 4-methyl-3, An active energy ray curable organopolysiloxane resin composition containing 4-epoxycyclohexyl. 10. The method of claim 9, wherein the epoxy-containing monovalent aliphatic hydrocarbon group having 5 to 10 carbon atoms in total is a 3- (glycidoxyoxy) propyl group, a 2- (glycidoxyoxycarbonyl) propyl group, 2- (3,4- An active energy ray curable organopolysiloxane resin composition, which is an epoxycyclohexyl) ethyl group or a 2- (4-methyl-3,4-epoxycyclohexyl) propyl group.