JP5897341B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition and a cured product thereof.

  Conventionally, as a high refractive index material, an inorganic material such as a high refractive index glass and an organic material into which an aromatic group, a halogen group other than fluorine, or a sulfur atom is introduced have been used. However, although inorganic materials are excellent in heat resistance, light resistance, dimensional stability, etc., they have problems such as heavy weight, easy cracking and poor moldability. Moreover, although organic materials are excellent in light weight, moldability, etc., they have problems such as poor heat resistance, light resistance, dimensional stability, and the like, and it is difficult to increase the refractive index as much as inorganic materials. Silicone resin is known as a material that is superior in heat resistance and light resistance of inorganic materials and light weight and moldability of organic materials, but it is difficult to increase the refractive index of inorganic materials like organic materials. is there.

  Under such circumstances, in order to improve the above-mentioned problems, many high refractive index resins in which inorganic particles having a high refractive index and organic materials or silicone resins are hybridized have been reported (see Patent Documents 1 to 4).

JP 2007-262252 A JP 2009-132934 A JP 2010-7057 A JP 2011-136857 A

  On the other hand, in order to simplify the curing process, increase productivity, and save energy, there is an increasing demand for conversion from a conventional thermosetting resin to a photocurable resin. In addition, the method of curing the resin with light is roughly divided into a photo radical polymerization type using radical as an active species and a photo cationic polymerization type using proton acid as an active species. However, there are problems such as slow curing, inhibition of curing due to moisture, and the presence of acid in the cured product, which limits the type and use of the resin.

  The zirconia-containing transparent plastic member described in Patent Document 1 has a high refractive index and transparency, but has a problem that the stability to heat is low because the member is thermoplastic.

  In addition, according to the composition described in Patent Document 2, a cured product having excellent curability can be obtained in spite of cationic polymerization, but there is curing inhibition due to moisture, and an acid remains in the cured product. I still have problems.

  Furthermore, the compositions described in Patent Documents 3 and 4 are thermosetting, and are required to be converted to a desired photocurable type.

  Under such circumstances, a photo-radical curable resin composition having a high refractive index and capable of forming a cured product having excellent heat resistance and light resistance is desired.

  In view of the above-described conventional technology, the problems to be solved by the present invention are high refractive index, excellent heat resistance and light resistance, and excellent curability even with a thick film, low linear expansion coefficient, and low shrinkage. It is to provide a photo-radical curable resin composition and a cured product thereof, which can form a cured product capable of maintaining the rate, and are suitable mainly for an optical semiconductor encapsulant and a plastic lens.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and repeated experiments. As a result, the inventors have unexpectedly found that the above-described problems can be solved by the following configuration, and have completed the present invention. That is, the present invention is as follows.

[1] 100 parts by mass of a photosensitive silicon resin (A) containing metal oxide fine particles having a refractive index of 1.6 or more and a photoradical reactive group, and 0.01 to 50 parts by mass of a photoradical polymerization initiator (B) A photosensitive resin composition, wherein the photoradical reactive group equivalent contained in the photosensitive resin composition is 0.2 to 10 mmol / g.
[2] The photosensitivity according to the above [1], further comprising 0.1 to 900 parts by mass of one or more compounds (C) selected from the group consisting of monomers and oligomers having a photoradical reactive group in the molecule. Resin composition.
[3] The photosensitive silicon resin (A) is represented by the following general formula (1):
R ¹ _n1 SiX ¹ _4-n1 (1)
{Wherein R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, n1 is an integer of 0 to 3, and X ¹ is a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms. And a group selected from the group consisting of an acetoxy group, and when there are plural groups, n1, R ¹ and X ¹ may be the same or different. } The photosensitive resin composition as described in said [1] or [2] containing the polysiloxane compound which is a hydrolysis-condensation product of 1 or more types of silane compounds represented by these.
[4] The photosensitive silicon resin (A) is one or both of at least one silane compound represented by the general formula (1) and a polysiloxane compound that is a hydrolysis-condensation product of the silane compound; The photosensitive resin composition according to the above [3], comprising a condensation reaction product with metal oxide fine particles.
[5] The photosensitive resin composition according to the above [4], wherein the condensation reaction product has an aromatic hydrocarbon group.
[6] The photosensitive resin composition according to any one of the above [3] to [5], wherein the photoradical reactive group in the photosensitive silicon resin (A) is derived from the polysiloxane compound.
[7] The photosensitive silicon resin (A) contains the metal oxide fine particles: 20% by mass to 95% by mass, and the total of the polysiloxane compound and the silane compound: 5% by mass to 80% by mass. The photosensitive resin composition in any one of said [3]-[6] which is a mixture containing or a condensation product of this mixture.
[8] The above [3] to [3], wherein the polysiloxane compound is a hydrolysis-condensation product of a condensation raw material containing a silane compound in which n1 is 1 among the silane compounds represented by the general formula (1). 7] The photosensitive resin composition in any one of.
[9] The above [1] to [8], wherein the photoradical polymerization initiator (B) includes at least one selected from the group consisting of an acetophenone derivative, an α-aminoalkylphenone compound, and a phosphine oxide compound. ] The photosensitive resin composition in any one of.
[10] The photosensitive property according to any one of [1] to [9], wherein the metal oxide fine particles include at least one selected from the group consisting of Al, Ti, Zn, Zr, Nb, and Sn. Resin composition.
[11] The photosensitive resin composition according to any one of [1] to [10], wherein the metal oxide fine particles have a band gap of 3.0 eV or more.
[12] From the peak area when the photosensitive silicon resin (A) is measured by ²⁹ Si NMR method, the following calculation formula (2):
Silanol content ratio = (D1 × 1 + T1 × 2 + T2 + Q1 × 3 + Q2 × 2 + Q3) / [M1 + (D1 + D2) × 2 + (T1 + T2 + T3) × 3 + (Q1 + Q2 + Q3 + Q4) × 4] (2)
{Where
M1 is the peak area of one Si-O-Si bond among Si atoms having one bond bonded to an O atom,
D1 is a peak area of one Si atom having two Si—O—Si bonds out of two Si atoms bonded to an O atom;
D2 is a peak area of two Si-O-Si bonds among Si atoms having two bonds bonded to O atoms,
T1 is the peak area of one Si-O-Si bond among Si atoms having three bonds bonded to O atoms,
T2 is the peak area of two Si-O-Si bonds among Si atoms having three bonds bonded to O atoms,
T3 is a peak area of three Si-O-Si bonds among Si atoms having three bonds that are bonded to O atoms,
Q1 is the peak area of one Si atom having four Si—O—Si bonds out of four Si atoms bonded to O atoms,
Q2 is a peak area of two Si-O-Si bonds among Si atoms having four bonds bonded to O atoms,
Q3 is the peak area of 3 Si-O-Si bonds out of 4 Si atoms bonded to O atoms, and Q4 is bonded to O atoms. This is the peak area of four Si-O-Si bonds among Si atoms having four bonds. }
The photosensitive resin composition according to any one of the above [1] to [11], wherein the silanol content ratio calculated in (1) is 0.2 or less.
[13] The photo radical reactive group according to any one of [1] to [12], wherein the photoradical reactive group is at least one group selected from the group consisting of a (meth) acryloyl group, a styryl group, and a mercapto group. Photosensitive resin composition.
[14] The system according to any one of [1] to [13], further including 0.1 to 50 parts by mass of at least one stabilizer (D) selected from the group consisting of an antioxidant and an ultraviolet absorber. Photosensitive resin composition.
[15] The photosensitive resin composition according to any one of [1] to [14], wherein the metal oxide fine particles have an average primary particle size of 1 nm to 100 nm.
[16] A method for producing the photosensitive resin composition according to the above [3], comprising the following steps:
The following general formula (1):
R ¹ _n1 SiX ¹ _4-n1 (1)
{Wherein R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, n1 is an integer of 0 to 3, and X ¹ is a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms. And a group selected from the group consisting of an acetoxy group, and when there are plural groups, n1, R ¹ and X ¹ may be the same or different. } The metal oxide fine particles having a refractive index of 1.6 or more at least at any time before, during, and after the hydrolysis condensation Is added to the reaction system and condensed to obtain a photosensitive silicon resin (A), and
A second step of mixing the obtained photosensitive silicon resin (A) and the radical photopolymerization initiator (B);
The manufacturing method of the photosensitive resin composition containing this.
[17] The method for producing a photosensitive resin composition according to the above [16], wherein the hydrolysis and condensation in the first step is performed in an aqueous alcohol solution under acidic conditions.
[18] In the first step, 5% by mass to 80% by mass of a polysiloxane compound which is a hydrolysis condensation product of the silane compound, and the metal oxide added to the reaction system after the hydrolysis condensation The photosensitive silicon resin (A) is obtained by condensing the fine particles at 20% by mass or more and 95% by mass or less at a pH of 3 to 9, 50 ° C. or more and 100 ° C. or less, and atmospheric pressure in an alcohol aqueous solution having 1 to 4 carbon atoms. The manufacturing method of the photosensitive resin composition as described in said [16].
[19] The boiling point at 1 atm of at least one selected from the group consisting of an alcohol, a ketone, an ester, an ether, and a hydrocarbon solvent is added to the obtained photosensitive silicon resin (A) in the first step. After adding a solvent having a temperature of 100 ° C. or more and 200 ° C. or less, the solvent component is distilled off by distillation, whereby the total content of water and solvent in the photosensitive silicon resin (A) is 0.0001% by mass or more and 5%. The method for producing a photosensitive resin composition according to the above [16], further comprising adjusting the mass% or less.
[20] In the second step, one or more compounds (C) selected from the group consisting of monomers and oligomers having a photoradical reactive group in the molecule, and a group consisting of an antioxidant and an ultraviolet absorber. One or both of the chosen at least 1 sort (s) of stabilizers (D) are further mixed, The manufacturing method of the photosensitive resin composition as described in said [16].
[21] A method for producing a cured product, comprising a step of irradiating the photosensitive resin composition according to any one of [1] to [15] with light having a dominant wavelength of 200 to 500 nm.
[22] The method for producing a cured product according to [21], further including a baking step at 130 ° C. or more and 300 ° C. or less.
[23] A cured product obtained by the method for producing a cured product according to [21] or [22].
[24] An optical semiconductor encapsulant produced by the method for producing a cured product according to [21].
[25] A plastic lens manufactured by the method for manufacturing a cured product according to [21].

  The photosensitive resin composition of the present invention is a cured product having a high refractive index, excellent heat resistance and light resistance, excellent curability even with a thick film, and capable of maintaining a low linear expansion coefficient and a low shrinkage. Can be formed. Moreover, according to the photosensitive resin composition which concerns on the specific aspect of this invention, the hardened | cured material which has favorable crack resistance and is a low thermal weight reduction can be formed.

  Hereinafter, the present invention will be described in detail.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises 100 parts by mass of a photosensitive silicon resin (A) containing metal oxide fine particles having a refractive index of 1.6 or more and a photoradical reactive group, and a photoradical polymerization initiator (B) 0. It is the photosensitive resin composition containing 01-50 mass parts, Comprising: The radical photoactive group equivalent contained in this photosensitive resin composition is 0.2-10 mmol / g, It is characterized by the above-mentioned. When the photosensitive resin composition contains metal oxide fine particles having a refractive index of 1.6 or more, the refractive index of the cured product can be increased, the hardness of the cured product is further increased, and the linear expansion coefficient and photocuring Volumetric shrinkage can be reduced. In addition, the heat resistance and light resistance of the silicon resin can be further increased. Moreover, outstanding sclerosis | hardenability is realizable because the photosensitive resin composition contains a photoradical reactive group in the photosensitive silicon resin (A) and contains a photoradical polymerization initiator (B). The metal oxide fine particles are mixed in the photosensitive silicon resin (A) or condensed in the form of a condensation reaction product described later, or both.

<Photosensitive silicon resin (A)>
The metal oxide fine particles contained in the photosensitive silicon resin (A) are not particularly limited as long as the refractive index is 1.6 or more. If the refractive index is 1.6 or more, a cured product having a high refractive index can be formed. The refractive index is obtained by preparing a transparent dispersion of metal oxide fine particles, and using a multi-wavelength Abbe refractometer (for example, multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd.), the wavelength of sodium D line (wavelength 589.3 nm). ) A value obtained by measuring the refractive index of light and the specific gravity of the metal oxide fine particles and the solvent and extrapolating to 100% by volume of the metal oxide fine particles. Examples of metal elements contained in the metal oxide fine particles include Al, Si, Co, Ni, Zn, Sn, etc. Alkaline earth metals such as Group 2 Mg, Ca, Sr, Ba, Group 3 Y, etc. 4 Group, Ti, Zr, etc., Group V, Nb, etc., Group 6, Cr, Mo, etc., Group 7, Mn, etc., Group 8, Fe, etc., rare earth, etc. are mentioned. These may be contained alone or in combinations of two or more in the metal oxide fine particles. It is preferable to have at least one selected from Al, Ti, Zn, Zr, Nb, and Sn in that the refractive index of the metal oxide fine particles can be increased. In addition, the band gap of the metal oxide fine particles is preferably 3.0 eV or more from the viewpoint that the absorption of light in the visible light region is small and it is suitable for use in optical materials that require colorless transparency. More preferably, it is 3.1 eV or more, More preferably, it is 3.2 eV or more.

  Specifically, as the metal oxide fine particles, zirconium oxide, titanium oxide, zinc oxide, chromium oxide, aluminum oxide, iron oxide, copper oxide, magnesium oxide, yttrium oxide, cerium oxide, hafnium oxide, niobium oxide, tantalum oxide, Examples include tungsten oxide, tin oxide, indium oxide, barium titanate, strontium titanate, ITO, and the like. These metal oxides may be used as they are, or may be mixed with other metal oxides in order to improve stability and refractive index. A composite oxide may be used. Zirconium oxide, titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, yttrium oxide, cerium oxide are suitable for use in optical materials that require little transparency in the visible light region and colorless transparency. , Hafnium oxide, niobium oxide, tin oxide, indium oxide, barium titanate, and strontium titanate are preferable. Zirconium oxide, titanium oxide, barium titanate, and strontium titanate are preferable in that the refractive index can be further increased. Particularly preferred.

  Although the method for producing the metal oxide fine particles is not particularly limited, for example, it can be produced by a dry method or a wet method. Examples of a method for obtaining metal oxide fine particles by a dry method include a method in which a metal chloride or a compound containing a metal element is reacted with oxygen and hydrogen in a gas phase. Examples of a method for obtaining metal oxide fine particles by a wet method include a sol-gel method in which a metal alkoxide compound or a metal halide is hydrolyzed and condensed.

  In the present disclosure, the “fine particles” in the metal oxide fine particles have a general meaning to those skilled in the art, but are typically particles having an average primary particle diameter of 100 nm or less. The average primary particle diameter of the metal oxide fine particles is preferably 1 nm or more and 100 nm or less in that the hardness of the cured product is increased, the transparency is increased, and the curability in the thick film is excellent. From the viewpoint of further increasing the transparency, it is more preferably 1 nm or more and 20 nm or less, and particularly preferably 1 nm or more and 15 nm or less.

  The average secondary particle diameter of the metal oxide fine particles is preferably 2 nm or more and 250 nm or less, more preferably 2 nm or more and 80 nm or less, and further preferably 2 nm or more and 40 nm or less. When the average secondary particle diameter is 2 nm or more, it is preferable because the hardness is improved, and when the average secondary particle diameter is 250 nm or less, it is preferable because the transparency to light having a wavelength region of 300 nm or less of the cured product is improved.

  The average primary particle size can be obtained by image analysis of a scanning electron microscope image and calculating a 50% particle size based on a sphere equivalent volume with respect to the Heywood diameter. The average secondary particle diameter is a value measured with a dynamic light scattering photometer.

  The shape of the metal oxide can be spherical, rod-like, plate-like, or fibrous, or a shape in which two or more of these are combined, but is preferably spherical. Here, the spherical shape means a substantially spherical shape including a true spherical shape, a spheroid, an oval shape and the like.

  The metal oxide fine particles used in the present invention may have a hydroxyl group and / or an alkoxyl group on the surface, or may be modified with another organic group.

  The metal oxide fine particles used in the present invention may be used after being isolated in a powder and then dispersed in a solvent. The metal oxide fine particles originally dispersed in water, an organic solvent or a mixture thereof may be used. You may use. Metal oxide fine particles finely dispersed in water, an organic solvent or a mixture thereof are preferable from the viewpoint of the transparency of the photosensitive silicon resin (A).

  The photosensitive silicon resin (A) in the present invention must contain metal oxide fine particles having a refractive index of 1.6 or more and a photoradical reactive group. The photoradical reactive group is a functional group that undergoes a polymerization reaction upon irradiation with actinic rays such as ultraviolet rays in the presence of the photoradical polymerization initiator (B). It includes a group and a functional group that is photopolymerized only by a combination of two or more. The photoradical reactive group can be photopolymerized by photoradical polymerization or addition reaction by enethiol reaction.

  Examples of the photoradical reactive group include a group having an unsaturated carbon bond, and examples thereof include a (meth) acryloyl group, a vinyl ether, a mercapto group, and a styryl group. A hydrogen atom or a part of the main chain skeleton of these various hydrocarbon groups is a hydrocarbon group, an ether bond, an ester group (or bond), a hydroxyl group, a thioether group, a carbonyl group, a carboxyl group, a carboxylic anhydride bond, Thioether bond, sulfone group, aldehyde group, amino group, substituted amino group, amide group (or bond), imide group (or bond), imino group, urea group (or bond), urethane group (or bond), isocyanate group, It may be substituted with a substituent selected from a polar group (or polar bond) such as a cyano group, or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom. Among the photoradical reactive groups, at least one group selected from the group consisting of (meth) acryloyl group, styryl group, and mercapto group is preferable. In particular, a (meth) acryloyl group is preferable from the viewpoint of curability, a styryl group is preferable from the viewpoint that the refractive index can be further increased, and a mercapto group is preferable from the viewpoint of low curing shrinkage.

  The photosensitive silicon resin (A) is not particularly limited as long as it is a resin having Si atoms in the components excluding the metal oxide fine particles, and examples thereof include a silicone resin.

  It is preferable that the photosensitive silicon resin (A) has an aromatic hydrocarbon group in the resin from the viewpoint of reducing the difference in refractive index between the metal oxide fine particles and the resin and increasing the transparency of the resin. Examples of such aromatic hydrocarbon groups include aralkyl groups such as benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl; araalkenyl groups such as PhCH═CH— group; phenyl groups, tolyl groups, Aryl groups such as styryl group, xylyl, naphthyl group; substituted aryl groups such as 4-aminophenyl group, 4-hydroxyphenyl group, 4-methoxyphenyl group, 4-vinylphenyl group; fluorene group; and the like.

The photosensitive silicon resin (A) has the following general formula (1):
R ¹ _n1 SiX ¹ _4-n1 (1)
{Wherein R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, n1 is an integer of 0 to 3, and X ¹ is a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms. And a group selected from the group consisting of an acetoxy group, and when there are plural groups, n1, R ¹ and X ¹ may be the same or different. }, A polysiloxane compound (hereinafter referred to as “polysiloxane compound” unless otherwise specified) is a hydrolytic condensation product of one or more silane compounds represented by It is preferable at the point which can form hardened | cured material with high property.

  Furthermore, the photosensitive silicon resin (A) comprises at least one silane compound represented by the general formula (1) and / or a polysiloxane compound that is a hydrolysis condensation product of the silane compound, metal oxide fine particles, It is more preferable to contain the condensation reaction product in that the aggregation of the metal oxide fine particles is suppressed, the transparency of the cured product is increased, and the curability in the thick film is excellent.

  Moreover, it is preferable that the polysiloxane compound and / or the condensation reaction product have an aromatic hydrocarbon group from the viewpoint of reducing the difference in refractive index between the metal oxide fine particles and the resin and improving the transparency. In particular, it is more preferable that the condensation reaction product has an aromatic hydrocarbon group in that the effect of suppressing aggregation of metal oxide fine particles is further enhanced.

  The photoradical reactive group in the photosensitive silicon resin (A) is preferably derived from a polysiloxane compound.

R ¹ in the polysiloxane compound is a hydrogen atom or an organic group having 1 to 20 carbon atoms. Examples of the organic group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, butyl (n-butyl, i-butyl, t-butyl, and sec-butyl), pentyl (n-pentyl, i -Pentyl, neopentyl, cyclopentyl, etc.), hexyl (n-hexyl, i-hexyl, cyclohexyl, etc.), heptyl (n-heptyl, i-heptyl, etc.), octyl (n-octyl, i-octyl, t-octyl, etc.) , Nonyl (n-nonyl, i-nonyl etc.), decyl (n-decyl, i-decyl etc.), undecyl (n-undecyl, i-undecyl etc.), dodecyl (n-dodecyl, i-dodecyl etc.), etc. Acyclic or cyclic aliphatic saturated hydrocarbon group; vinyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexenyl, cyclohexenylethyl Acyclic and cyclic alkenyl groups such as norbornenylethyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, styryl; benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, etc. Aralkyl groups; Aralkenyl groups such as PhCH = CH- groups; Aryl groups such as phenyl groups, tolyl groups, styryl groups, xylyl groups; 4-aminophenyl groups, 4-hydroxyphenyl groups, 4-methoxyphenyl groups, 4-vinyls A substituted aryl group such as a phenyl group; a group containing a reactive bonding group such as a methacryloyl group, an acryloyl group, a styryl group, a norbornyl group, a glycidyl group, or a mercapto group; a fluorene group;

In addition, the organic group having 1 to 20 carbon atoms includes a part of the main chain skeleton of the various organic groups described above, an ether bond, an ester group (or bond), a hydroxyl group, a thiol group, a thioether group, a carbonyl group, and a carboxyl group. Carboxylic acid anhydride bond, thiol group, thioether bond, sulfone group, aldehyde group, epoxy group, amino group, substituted amino group, amide group (or bond), imide group (or bond), imino group, urea group (or Bond), urethane group (or bond), isocyanate group, polar group (or polar bond) such as cyano group, or a substituent selected from halogen atoms such as fluorine atom, chlorine atom, bromine atom and the like. May be. When there are a plurality of R ^{1 s} , they may be the same or different.

  N1 in the said General formula (1) is an integer of 0-3.

X ¹ is independently selected from the group consisting of a hydroxyl group, a halogen atom that is a hydrolyzable substituent, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group, specifically, for example, a hydroxyl group; Halogen atoms such as chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, t-butyloxy group, n-hexyloxy group, cyclohexyloxy group And alkoxy groups such as acetoxy group. Among these, halogen atoms such as chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; and acetoxy group are preferable because of high reactivity of the condensation reaction at the time of polysiloxane compound synthesis. When there are a plurality of X ^{1 s} , they may be the same or different.

  Examples of the silane compound represented by the general formula (1) include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxy. Propyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (Aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N -(1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3- Ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane Vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-octanoylthio-1-propyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-triethoxysilyl-N -(1,3dimethyl-butylidene), 3-acryloxypropyltrimethoxysilane, N- (p-vinylbenzyl) -N- (trimethoxysilylpropyl) ethylenediamine hydrochloride, 3-glycidoxypropylmethyldimethoxysilane, Bis [3- (triethoxysilyl) propyl] disulfide, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltri Alkylchlorosilanes such as ethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, trimethylchlorosilane, dimethylchlorosilane, methyltrichlorosilane, dimethylchlorosilane, dichloromethylsilane, trichlorosilane , Chlorosilanes containing unsaturated hydrocarbon groups such as dimethylvinylchlorosilane, methylvinyldichlorosilane, vinyltrichlorosilane; Aromatic group-containing chlorosilanes such as lan, diphenylmethylchlorosilane, dimethylphenylchlorosilane, diphenyldichlorosilane, phenylmethyldichlorosilane, and phenyltrichlorosilane; dimethylcyclohexylchlorosilane, dicyclohexylmethylchlorosilane, dicyclohexyldichlorosilane, methylcyclohexyldichlorosilane, cyclohexyltrichlorosilane Aliphatic group-containing chlorosilanes such as dimethylcyclopentylchlorosilane, dicyclopentylmethylchlorosilane, dicyclopentyldichlorosilane, methylcyclopentyldichlorosilane, cyclopentyltrichlorosilane; acryloxypropyldimethylchlorosilane, acryloxypropylmethyldichlorosilane, acryloxypropyltrichlorosilane Emissions, methacrolein dimethylchlorosilane, methacrolein propyl methyl dichlorosilane, methacrolein propyl trichlorosilane, styryl dimethylchlorosilane, styryl methyldichlorosilane, styryl trichlorosilane and the like.

  The silane compound represented by the general formula (1) may be used alone, or may be used as a plurality of types of silane compounds, as well as control of fluidity before curing, refractive index, hardness, etc. This is preferable because it enables control.

  Moreover, it is preferable from a viewpoint of molecular weight increase to use at least the silane compound whose n1 is 1 among the silane compounds represented by the said General formula (1). Among the silane compounds represented by the general formula (1), it is preferable to use a silane compound in which n1 is 1 and a silane compound in which n1 is 2 from the viewpoint of crack resistance of the cured product. .

<Production of photosensitive silicon resin (A)>
Hereinafter, regarding the production of the photosensitive silicon resin (A), the case where the polysiloxane compound obtained from the silane compound represented by the general formula (1) and the metal oxide fine particles are used will be described. It is not limited.

The polysiloxane compound is preferably produced by adding water to one or more silane compounds represented by the general formula (1). The amount of water added is preferably in the range of 0.1 equivalents to 10 equivalents (on a molar basis) with respect to the total number of moles of X ¹ in the silane compound represented by the general formula (1), more preferably 0. .4 equivalents to 8 equivalents. When the amount of water added is 0.1 equivalent or more, the molecular weight of the polysiloxane compound is increased, and preferably 10 equivalents or less from the viewpoint of extending the pot life of the polysiloxane compound solution produced by the condensation reaction. preferable. When all X ^{1 of the} silane compound represented by the general formula (1) used for polycondensation is a hydroxyl group, it may be condensed without adding water.

  In the case of producing a polysiloxane compound by a condensation reaction in the presence of a catalyst, the hydrolysis and condensation rates are increased, which is preferable.

  Examples of the catalyst include acid catalysts, base catalysts, and metal alkoxides. Specifically, an inorganic acid and an organic acid are mentioned as an acid catalyst. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, and the like. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, benzoic acid, and p-amino. Examples include benzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, citraconic acid, malic acid, and glutaric acid. Examples of base catalysts include inorganic bases such as alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earths such as calcium hydroxide, strontium hydroxide, and barium hydroxide. Metal hydroxides; alkali metal or alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate; metal hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate; and the like. Examples of organic bases include trialkylamines such as ammonia, triethylamine, and ethyldiisopropylamine; N, N-dialkylaniline derivatives having 1 to 4 carbon atoms such as N, N-dimethylaniline and N, N-diethylaniline; pyridine, 2, Examples thereof include pyridine derivatives that may have an alkyl substituent having 1 to 4 carbon atoms, such as 6-lutidine. Examples of the metal alkoxide include trimethoxy aluminum, triethoxy aluminum, tri-n-propoxy aluminum, tri-iso-propoxy aluminum, tri-n-butoxy aluminum, tri-iso-butoxy aluminum, tri-sec-butoxy aluminum, Tri-tert-butoxyaluminum, trimethoxyboron, triethoxyboron, tri-n-propoxyboron, tri-iso-propoxyboron, tri-n-butoxyboron, tri-iso-butoxyboron, tri-sec-butoxyboron, Tri-tert-butoxyboron tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-iso- Toxisilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetramethoxygermanium, tetraethoxygermanium, tetra-n-propoxygermanium, tetra-iso-propoxygermanium, tetra-n-butoxygermanium, tetra-iso-butoxy Germanium, tetra-sec-butoxygermanium, tetra-tert-butoxygermanium, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetra-iso-propoxytitanium, tetra-n-butoxytitanium, tetra-iso- Butoxytitanium, tetra-sec-butoxytane, tetra-tert-butoxytitanium, tetramethoxyzirconium, tetraethoxyzirconium, tetra-n-pro Alkoxy zirconium, tetra -iso- propoxy zirconium, tetra -n-butoxy zirconium, tetra -iso- butoxy zirconium, tetra -sec- butoxy zirconium, tetra--tert- butoxy zirconium, and the like. These catalysts can be used alone or in combination of two or more. Further, the amount of catalyst used is an amount that adjusts the pH of the reaction system in the production of the polysiloxane compound to a range of 0.01 to 6.9, so that the weight average molecular weight of the polysiloxane compound is good. It is preferable because it can be controlled. Moreover, you may adjust pH with an acid or a base after manufacture of polysiloxane.

  The condensation reaction for producing the polysiloxane compound can be performed in an organic solvent. Examples of the organic solvent that can be used for the condensation reaction include alcohols, esters, ketones, ethers, aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, amide compounds, and the like.

  Examples of the alcohol include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol, and ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, B propylene glycol monopropyl ether, mono ethers of polyhydric alcohols such as propylene glycol monobutyl ether.

  Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, and γ-butyrolactone. Examples of the ketone include acetone, methyl ethyl ketone, and methyl isoamyl ketone.

  Examples of the ether include, in addition to the above monoethers of polyhydric alcohols, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol. Polyhydric alcohol ethers obtained by alkyl etherifying all hydroxyl groups of polyhydric alcohols such as dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran, 1,4-dioxane, anisole, propylene glycol monomethyl ether Acetate (hereinafter abbreviated as PGMEA) And the like.

  Examples of the aliphatic hydrocarbon compound include hexane, heptane, octane, nonane, decane, and the like.

  Examples of the aromatic hydrocarbon compound include benzene, toluene, xylene and the like.

  Examples of the amide compound include dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  These solvents may be used alone or in combination with a plurality of solvents. A preferred example is hydrolytic condensation under acidic conditions in an aqueous alcohol solution. Moreover, you may react in a bulk, without using the said solvent.

  The reaction temperature for producing the polysiloxane compound is not particularly limited, but is preferably in the range of −50 ° C. to 200 ° C., more preferably 0 ° C. to 150 ° C. By carrying out the reaction in the above range, the molecular weight of the polysiloxane compound can be well controlled.

  In addition, the polysiloxane compound may include an element that forms an oxide, such as titanium, zirconium, aluminum, germanium, boron, phosphorus, nitrogen, carbon, gallium, or chromium.

  The photosensitive silicon resin (A) includes at least one silane compound represented by the general formula (1) and / or a polysiloxane compound that is a hydrolysis condensation product of the silane compound, metal oxide fine particles, It is preferable that the complex of these is included. The composite of the polysiloxane compound and / or the silane compound represented by the general formula (1) and the metal oxide fine particles may be based on an interaction such as a hydrogen bond or a covalent bond. From the viewpoint of crack resistance of the product, the polysiloxane compound and / or the silane compound represented by the general formula (1) and the metal oxide fine particles are covalently bonded by a condensation reaction to form a condensation reaction product. Is preferred.

  The photosensitive silicon resin (A) is preferably (i) a method of reacting metal oxide fine particles with a polysiloxane compound that is a hydrolysis condensation product of the silane compound represented by the general formula (1), (Ii) A method of reacting metal oxide fine particles with a polysiloxane compound which is a hydrolysis-condensation product of the silane compound represented by the above general formula (1) and the silane compound represented by the above general formula (1) Or (iii) a method of reacting metal oxide fine particles with the silane compound represented by the general formula (1). In the method (i), after a polysiloxane compound is produced by hydrolytic condensation of a silane compound, the polysiloxane compound and metal oxide fine particles are reacted. In the method (ii), after a polysiloxane compound is produced by hydrolytic condensation of a silane compound, metal oxide fine particles and a silane compound are added to the reaction system, and these are subjected to a condensation reaction. In the method (iii), a polymer in which a metal oxide is introduced into a polysiloxane chain is produced by the presence of metal oxide fine particles at the time of hydrolytic condensation of a silane compound.

  From the viewpoint of crack resistance of the cured molded product, a photosensitive silicon resin (A) obtained by reacting a component containing a polysiloxane compound and metal oxide fine particles is preferable.

  In the condensation reaction, the metal oxide fine particles dispersed in the solvent can be reacted with the polysiloxane compound and / or the silane compound represented by the general formula (1). As the solvent, water, an organic solvent, or a mixed solvent thereof can be used. The type of organic solvent used varies depending on the dispersion medium of the metal oxide fine particles used. When the dispersion medium of the metal oxide fine particles used is an aqueous medium, the metal oxide fine particles are added to the polysiloxane compound and / or the above general formula after adding water and / or an alcohol solvent to the aqueous dispersion medium of the metal oxide fine particles. It may be reacted with the silane compound represented by (1), or the solvent in the aqueous solution of the metal oxide fine particles is once replaced with an alcohol solvent, and then the metal oxide fine particles are converted into the polysiloxane compound and / or the above general You may make it react with the silane compound represented by Formula (1).

  Examples of the alcohol-based solvent that can be used as a substitution solvent for the solvent and the metal oxide fine particles in the condensation reaction of the polysiloxane compound and / or the silane compound represented by the general formula (1) and the metal oxide fine particles include: , Methanol, ethanol, n-propanol, 2-propanol, n-butanol, methoxyethanol, ethoxyethanol and the like. These are preferred because they are easily mixed with water.

  When the dispersion medium of the metal oxide fine particles used is a solvent such as alcohol, ketone, ester, or hydrocarbon, water or a solvent such as alcohol, ether, ketone, or ester can be used. Examples of the alcohol include methanol, ethanol, n-propanol, 2-propanol, n-butanol and the like. Examples of the ether solvent include dimethoxyethane and PGMEA. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, ethyl formate, propyl formate, and γ-butyrolactone. Examples of the hydrocarbon solvent include hexane, heptane, octane, nonane, decane, benzene, toluene, xylene and the like.

  An example of a preferable solvent is an aqueous solution of an alcohol having 1 to 4 carbon atoms.

  The condensation reaction between the metal oxide fine particles and the polysiloxane compound and / or the silane compound represented by the general formula (1) may be performed in an acidic atmosphere or a basic atmosphere. As the pH range, a range of 1 to 10 is preferable, and a range of 3 to 9 is more preferable. It is preferable to perform the condensation reaction within the above range because the condensation reaction can proceed without causing gelation or white turbidity. A catalyst may be used in the condensation reaction. Examples of the acid catalyst, base catalyst, or metal alkoxide that can be used include the same catalysts as those used in the production of the polysiloxane compound. The catalyst may be removed after the production of the polysiloxane compound. However, when the metal oxide fine particles are reacted as they are without removing the catalyst after the production of the polysiloxane compound, the polysiloxane compound is reacted without adding the catalyst again. The reaction between the polysiloxane compound and the metal oxide fine particles can be performed with the catalyst used at the time. Further, a catalyst may be added again during the reaction between the polysiloxane compound and the metal oxide fine particles.

  In addition, when an acid catalyst is added when producing the polysiloxane compound, when reacting the metal oxide fine particles and the polysiloxane compound, a base catalyst is added to the polysiloxane compound to make it neutral or base side, A condensation reaction may be performed.

  The reaction temperature for producing the condensation reaction product of the polysiloxane compound and / or the silane compound represented by the general formula (1) and the metal oxide fine particles is not particularly limited, but is preferably −50 ° C. or higher and 200 ° C. The range is from 0 ° C. to 150 ° C., more preferably from 50 ° C. to 100 ° C. By carrying out the reaction within the above range, the condensation rate of the polysiloxane compound and / or the silane compound represented by the general formula (1) and the metal oxide fine particles (polysiloxane and / or silane-metal oxide fine particle condensation) Rate) can be controlled. The reaction can typically be carried out at atmospheric pressure.

  The water used in the condensation reaction between the polysiloxane compound and / or the silane compound represented by the general formula (1) and the metal oxide fine particles is added with a solvent selected from the above, for example, distillation or the like. The total content of water and solvent in the condensation reaction product is preferably 0.0001% by mass to 5% by mass, more preferably 0.0001% by mass to 3% by mass. More preferably, the content is 0.0001% by mass or more and 1% by mass or less. It is preferable for the total content of moisture and solvent to be in the above range because shrinkage is reduced and cracks are less likely to occur when the photosensitive resin composition of the present invention is cured. The water content can be measured by, for example, a gas chromatogram or the Karl Fischer method, and the solvent content can be measured by using, for example, a gas chromatogram.

  After the condensation reaction at the time of synthesizing the polysiloxane compound and / or after the condensation reaction of the polysiloxane compound and / or the silane compound represented by the general formula (1) and the metal oxide fine particles, washing by distillation, extraction, or It is preferable to adjust the pH of the photosensitive silicon resin (A) to 6 or more and 8 or less by removing the catalyst by a method such as ion exchange. It is preferable for the pH to be in the above range because the pot life of the photosensitive silicon resin (A) is increased.

The photosensitive silicon resin (A) of the present invention has the following calculation formula (2) from the peak area measured by ²⁹ Si NMR method:
Silanol amount ratio = (D1 × 1 + T1 × 2 + T2 + Q1 × 3 + Q2 × 2 + Q3) / [M1 + (D1 + D2) × 2 + (T1 + T2 + T3) × 3 + (Q1 + Q2 + Q3 + Q4) × 4]
{In the formula, M0 is a peak area of a Si atom having one Si—O—Si bond among Si atoms having one bond bonded to an O atom, and M1 is O Of the Si atoms having one bond bonded to an atom, the peak area of one Si-O-Si bond is D0, and D0 is a bond bonded to an O atom. The peak area of zero Si—O—Si bond among Si atoms having two numbers, and D1 is the number of Si atoms having two bonds that are bonded to O atoms. Among them, the peak area of one Si-O-Si bond is D2, and D2 is the Si-O-Si bond among the Si atoms having two bonds that are bonded to the O atom. It is the peak area of two things, and T0 is a Si atom having three bonds bonded to an O atom. The peak area of the i-O-Si bond is 0, and T1 is one Si-O-Si bond among the Si atoms having three bonds bonded to the O atom. T2 is the peak area of two Si-O-Si bonds out of Si atoms having three bonds bonded to O atoms, and T3 Is the peak area of three Si-O-Si bonds among Si atoms having three bonds bonded to O atoms, and Q0 is bonded to O atoms. Of the Si atoms having four bond hands, the peak area of zero Si-O-Si bond is Q1, and Q1 is the number of bond bonds with O atoms being four. Of the Si atoms, the peak area of one Si—O—Si bond is Q 2. The peak area of two Si—O—Si bonds among Si atoms having four bond hands, Q3 is the number of bond bonds to four O atoms. Among the Si atoms, the peak area of three Si—O—Si bonds is present, and Q4 is the Si— of the Si atoms having four bonds bonded to the O atoms. This is the peak area of four O-Si bonds. The silanol content ratio of the photosensitive silicon resin obtained in the above formula is preferably 0.2 or less from the viewpoint of obtaining a cured product having a small thermogravimetric decrease and a low water absorption, and more preferably 0.15. Or less, more preferably 0.1 or less. In addition to the Si—OH, the silanol group referred to here is, for example, Si—X ¹ in the above formula (1) (when X ¹ is an alkoxy group or an acetoxy group), and the hydrogen of the silanol group is substituted. Includes structure.

  The photosensitive silicon resin (A) in the present invention is a mixture containing metal oxide fine particles: 20% by mass to 95% by mass, and the total of the polysiloxane compound and the silane compound: 5% by mass to 80% by mass. Or it is preferable that it is a condensation product of this mixture. The content of the metal oxide fine particles is preferably 20% by mass or more from the viewpoint of increasing the refractive index of the cured product, and preferably 95% by mass or less from the viewpoint of the viscosity of the condensation reaction product. The content of the metal oxide fine particles is more preferably 25% by mass or more and 85% by mass or less, and further preferably 30% by mass or more and 80% by mass or less.

  The mass average molecular weight of the photosensitive silicon resin (A) is preferably in the range of 1,000 to 200,000, more preferably 1,000 to 100,000. A mass average molecular weight can be calculated | required by standard polymethylmethacrylate conversion, for example with gel permeation chromatography (GPC). When the mass average molecular weight of the photosensitive silicon resin (A) is 1,000 or more, the cured product has high heat resistance and further increases the pot life. When the mass average molecular weight is 200,000 or less, the viscosity can be lowered, so that the mold filling property is improved and the shape transfer property is improved.

<Photoradical polymerization initiator (B)>
The photosensitive resin composition according to the present invention contains a photoradical polymerization initiator (B) for the purpose of imparting photosensitivity. Photoradical polymerization of the photosensitive resin composition can be advanced by the photoradical polymerization initiator (B). Preferred examples of the radical photopolymerization initiator (B) include the following compounds that absorb light having a wavelength of 365 nm.

(1) Benzophenone derivatives: for example, benzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone, etc.
(2) Acetophenone derivatives: for example, trichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl) Propionyl) -benzyl] -phenyl} -2-methylpropan-1-one, methyl phenylglyoxylate, (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -Phenyl} -2-methyl-propan-1-one) (IRGACURE (registered trademark) manufactured by BASF Corporation 127) etc.
(3) Thioxanthone derivatives: For example, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, etc.
(4) benzyl derivatives: for example, benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, etc.
(5) Benzoin derivatives: for example, benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc.
(6) Oxime compounds: for example, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2 -(O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl) Oxime)] (IRGACURE (registered trademark) OXE01 manufactured by BASF Corporation), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE (registered trademark) OXE02 manufactured by BASF Corporation), etc.

(7) α-hydroxy ketone compounds: for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane, etc.
(8) α-aminoalkylphenone compounds: for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE (registered trademark) 369 manufactured by BASF Corporation), 2- Dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one, etc.
(9) Phosphine oxide compounds: for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN (registered trademark) TPO manufactured by BASF Corporation), etc.
(10) Titanocene compound: for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, etc.
(11) Benzoate derivatives: for example, ethyl-p- (N, N-dimethylaminobenzoate)
(12) Acridine derivative: For example, 9-phenylacridine and the like.

  Among the above-mentioned photo radical polymerization initiators, the above (2) acetophenone derivative, (8) α-aminoalkylphenone compound, and (9) phosphine oxide compound are preferable from the viewpoint of high sensitivity. Furthermore, in terms of high transparency and high sensitivity of the cured product, the above (9) phosphine oxide compound is preferable, and among them, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN (manufactured by BASF Corporation) (Registered trademark) TPO) is more preferred.

  The amount of the radical photopolymerization initiator (B) is 0.01 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the photosensitive silicon resin (A). The amount is appropriately set in consideration of the amount of other components of the photosensitive resin composition. The amount is preferably from 0.05 parts by weight to 10 parts by weight, and more preferably from 0.1 parts by weight to 5 parts by weight. When the amount is 0.01 parts by mass or more, active species sufficient for photopolymerization to sufficiently proceed at the time of exposure are supplied, and curing of the exposed part sufficiently proceeds, so that a practical cured molded product is obtained. be able to. When the amount is 50 parts by mass or less, when the coating film of the photosensitive resin composition is formed on the substrate, the exposure absorption near the coating film surface does not become too large, and the exposure light beam reaches the vicinity of the substrate surface. And the photopolymerization becomes uniform in the film thickness direction, so that a practical cured molded product can be obtained, and there is little coloring after photocuring or baking after heat.

<Compound (C) having a photoradical reactive group>
The photosensitive resin composition according to the present invention has excellent characteristics such as an improvement in refractive index, an improvement in curability, an improvement in adhesion, an improvement in flexibility of a cured molded product, and an improvement in handling properties due to low viscosity. For the purpose of providing a photosensitive resin composition, one or more compounds (C) selected from the group consisting of monomers and oligomers having a photoradical reactive group in the molecule (in this disclosure, “photoradical reactive group” It is preferable that the compound (also referred to as “compound (C)” or “compound (C)”). Compound (C) may be used alone or as a mixture of two or more. Examples of the photoradical reactive group in the compound (C) include a group having an unsaturated carbon bond, and examples thereof include a (meth) acryloyl group, a vinyl ether, a mercapto group, and a styryl group. A hydrogen atom or a part of the main chain skeleton of these various hydrocarbon groups is a hydrocarbon group, an ether bond, an ester group (or bond), a hydroxyl group, a thioether group, a carbonyl group, a carboxyl group, a carboxylic anhydride bond, Thioether bond, sulfone group, aldehyde group, amino group, substituted amino group, amide group (or bond), imide group (or bond), imino group, urea group (or bond), urethane group (or bond), isocyanate group, It may be substituted with a substituent selected from a polar group (or polar bond) such as a cyano group, or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom. From the viewpoint of curability, a (meth) acryloyl group is preferable, a styryl group is more preferable from the viewpoint that the refractive index can be further increased, and a mercapto group is preferable from the viewpoint of low curing shrinkage.

  The amount of the compound (C) is preferably 0.1 parts by mass or more and 900 parts by mass or less, and more preferably 5 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the photosensitive silicon resin (A). preferable. In particular, by adding a compound having a (meth) acryloyl group in the molecule to the photosensitive silicon resin (A) in an amount within the above range, cracking due to temperature impact can be prevented. If the amount of the compound having a photoradical reactive group in the molecule, particularly preferably a (meth) acryloyl group, is 900 parts by mass or less with respect to 100 parts by mass of the photosensitive silicon resin (A), the cured molded product is more It can have excellent high refractive index, high transparency, and high heat resistance.

  Use of a compound having a carbocycle and / or a heterocycle as the compound (C) is preferable from the viewpoints of maintaining the refractive index, improving the Abbe number, reducing the shrinkage rate, and improving the hardness of the cured molded product.

Examples of compounds having a (meth) acryloyl group in the molecule suitable as the compound (C) include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-ethylhydroxyethyl phthalate 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl phthalate, benzyl (meth) acrylate, EO-modified cresol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl ( (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, ethoxylated phenyl (meth) acrylate, isobornyl (meth) acrylate , Paracumylphenoxyethylene glycol (meth) acrylate, ECH modified phenoxy (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate , Tricyclodecane dimethanol di (meth) acrylate, paraphenylphenoxyethyl (meth) acrylate, paraphenylphenyl (meth) acrylate, phenylglycidyl ether (meth) acrylate, phenol modified with 3-15 moles of ethylene oxide ( Meth) acrylate, cresol (meth) acrylate modified with 1-15 moles of ethylene oxide, 1-20 moles Nonylphenol (meth) acrylate modified with tylene oxide, nonylphenol (meth) acrylate modified with 1 to 15 moles of propylene oxide, bisphenol A di (meth) acrylate modified with 1 to 30 moles of ethylene oxide, 1 to Bisphenol A di (meth) acrylate modified with 30 mol of propylene oxide, bisphenol F di (meth) acrylate modified with 1 to 30 mol of ethylene oxide, and bisphenol F modified with 1 to 30 mol of propylene oxide Di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . ^0,13 ] pentadecane dimethylol di (meth) acrylate, dicyclopentanyl dimethylol di (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, di (meth) acrylation Isocyanurate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, imide (meth) acrylate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, etc. Is mentioned.

  Among these, a (meth) acrylate compound having a carbocycle and / or a heterocycle is preferable from the viewpoints of improvement in refractive index and Abbe number and availability. In particular, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate And at least one compound selected from the group consisting of isobornyl (meth) acrylate is preferred.

  The compound (C) having a photoradical reactive group in the molecule may be the above-described reactive monomer or the following reactive oligomer. Examples of the reactive oligomer include unsaturated polyester, polyene / thiol, polybutadiene, and polystyrylethyl methacrylate. These reactive oligomers include monofunctional unsaturated compounds and polyfunctional unsaturated compounds, but one or both of monofunctional unsaturated compounds and polyfunctional unsaturated compounds can be used, and multiple compounds can be mixed. You may use it. It is preferable to set the usage-amount in the case of using the said reactive oligomer according to the quantity of the other component of the photosensitive resin composition, and 0.1 mass with respect to 100 mass parts of photosensitive silicon resin (A). Part or more and 900 parts by mass or less are preferable, and 5 parts by mass or more and 300 parts by mass or less are more preferable. If the amount is 0.1 parts by mass or more, the crack resistance is good, and if it is 900 parts by mass or less, the cured molded product can have more excellent high permeability and high heat resistance. .

<Stabilizer (D)>
From the viewpoint of improving heat resistance and light resistance, the photosensitive resin composition according to the present invention comprises at least one stabilizer (D) selected from the group consisting of an antioxidant and an ultraviolet absorber (in this disclosure, “ Antioxidants and / or ultraviolet absorbers (D) ”) may also be included. Examples of the antioxidant and / or the ultraviolet absorber (D) include the following substances.

(1) Hindered phenol antioxidant: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert) -Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionamide], benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, 3, 3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-trii ) Tri-p-cresol, calcium diethylbis [[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -o -Cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5 -Reactivity of triazine-2,4,6- (1H, 3H, 5H) -trione, N-phenylbenzenamine and 2,4,4-trimethylpentene 2,4,6-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, 2,4-dimethyl-6- (1-methyl) Pentadecyl) phenol, etc.
(2) Phosphorus heat stabilizer: tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorus Acids, etc.
(3) Sulfur-based heat stabilizer: didodecyl 3,3′-thiodipropionate, dioctadecyl 3,3′-thiodipropionate, etc.
(4) Benzotriazole UV absorber: 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl- 1-phenylethyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2,2'-methylenebis [6 -(2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], methyl 3- (3- (2H-benzotriazol-2-yl) ) -5-tert-butyl-4-hydroxyphenyl) propionate and ethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, etc.
(5) Cyanoacrylate UV absorber: 2,2-bis {[2-cyano-3,3-diphenylacryloyl] methyl} propane-1,3-diyl bis (2-cyano-3,3-diphenylacrylic) Rat), ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like.

(6) Triazine ultraviolet absorber: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, etc.
(7) Benzophenone ultraviolet absorbers: octabenzone, 2,2′-dihydroxy-4,4′-dimethoxybenphenone, 2,2′-4,4′-tetrahydrobenphenone, etc.
(8) Hindered amine photothermal stabilizer: dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine And N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5 -Triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] , Polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, olefin (C20-C24), maleic anhydride, 4-amino-2,2,6,6 -Tetramethyl pipette Lysine copolymer, bis (1,2,2,6,6-pentamethyl-4-piperidine) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (2,2,6,6- Tetramethyl-4-piperidyl) sebacate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N′-diformylhexamethylenediamine, etc.
(9) Other thermal stabilizers: 3,4-dihydro-2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) -2H-benzopyran-6-ol, 2 ′, 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide, etc.
(10) Other ultraviolet absorbers: 2-ethylhexyl-4-methoxycinnamate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and the like.

  As the antioxidant and / or ultraviolet absorber (D), from the viewpoint of solubility in the photosensitive resin composition, the above (1) hindered phenol-based antioxidant and (7) hindered amine-based photothermal stabilizer are more preferable. Ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (IRGANOX (registered trademark) 245 manufactured by BASF Corporation) is more preferable.

  Antioxidants and / or ultraviolet absorbers (D) may be used alone or in combination of two or more.

  The amount of the antioxidant and / or the ultraviolet absorber (D) can be set according to the amount of other additive components, but 0.1 parts by mass or more with respect to 100 parts by mass of the photosensitive silicon resin (A). 50 mass parts or less are preferable, 0.1 mass part or more and 5 mass parts or less are more preferable, 0.1 mass part or more and 2 mass parts or less are more preferable.

  By adding the antioxidant and / or the ultraviolet absorber (D) in an amount within the above range, the thermal stability under an air atmosphere is improved in addition to the thermal stability under a nitrogen atmosphere.

<Other ingredients>
The photosensitive resin composition may contain, for example, the following additional components in addition to the components (A) to (D) described above.

  The photosensitive resin composition may further contain a photopolymerization initiation assistant, a sharpening agent, a thermal radical initiator, and the like. Examples of thermal radical initiators include various peroxides such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters. Can be used.

  The photosensitive resin composition may contain an adhesion assistant for the purpose of improving the adhesion to various supporting substrates. Examples of the adhesion assistant include a silane coupling agent. More specifically, for example, an alkoxysilane containing a hydrogen atom directly bonded to a silicon atom, an alkoxysilane containing an epoxy group or a thiol group, a vinyl group, etc. Organic alkoxysilane compounds such as alkoxysilanes containing an unsaturated bond, compounds obtained by hydrolyzing some or all of these organic alkoxysilane compounds, and condensates thereof. For example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxy Propyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxy Lan, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) Propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyl Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, vinyltris (2-methoxyethoxy) silane Vinylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-octanoylthio-1-propyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3dimethyl-butylidene), 3 -Acryloxypropyltrimethoxysilane, N- (p-vinylbenzyl) -N- (trimethoxysilylpropyl) ethylenediamine hydrochloride, 3-glycidoxypropylmethyldimethoxysilane, bis [3- (triethoxysilyl) propyl] Disulfide, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3-aminop Examples include propyltriethoxysilane.

  The addition amount of the silane coupling agent can be set according to the amount of other additive components, and is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the photosensitive silicon resin (A). 0.05 parts by mass or more and 5 parts by mass or less is more preferable. The addition amount of the silane coupling agent is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the photosensitive silicon resin (A) from the viewpoint of improving adhesiveness, and 10 parts by mass or less from the viewpoint of storage stability. Is preferred.

  Moreover, a solvent can further be added to the photosensitive resin composition of this invention, and a viscosity can also be adjusted. Suitable solvents include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, tetrahydrofuran, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclohexane Pentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether, PGMEA, methyl ethyl ketone, methyl isobutyl ketone , Anisole, ethyl acetate, ethyl lactate, butyl lactate and the like, and these can be used alone or in combination of two or more. Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, and PGMEA are particularly preferable. These solvents can be appropriately added to the photosensitive resin composition depending on the desired coating film thickness and viscosity, but in the range of 0 to 900 parts by mass with respect to 100 parts by mass of the photosensitive silicon resin (A). It is preferable to use in.

  The photosensitive resin composition according to the present invention can further contain a sensitizer for improving photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylaminobenzylidene) cyclohexanone. 2,6-bis (4′-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) chalcone, 4,4′-bis (diethylamino) chalcone, 2- (4′-dimethylaminocinnamylidene) indanone, 2- (4′-dimethylaminobenzylidene) indanone, 2- (p-4′-dimethylaminobiphenyl) benzo Thiazole, 1,3-bis (4-dimethylaminobenzyl) Den) acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethyl Aminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, N, N-bis (2-hydroxyethyl) aniline, 4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, 4-diethylaminobenzoic acid Amyl, benztriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3,4-tetrazole, 1- ( tert-butyl) -5-mercapto-1,2,3,4-tetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2 -(P-dimethylaminostyryl) naphtho (1,2-p) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like.

  These compounds may be used alone or as a mixture of two or more. Although the addition amount of a sensitizer can be set according to the quantity of another additive component, it is preferable that it is 0-10 mass parts with respect to 100 mass parts of photosensitive silicon resins (A), and 1-5 masses. More preferably, it is a part.

  The photosensitive resin composition according to the present invention can further contain a polymerization inhibitor for the purpose of improving the stability of storage viscosity and photosensitivity. Examples of the polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2, 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N -Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis ( 4-hide Carboxymethyl-3,5-di-tert- butyl) can be used phenyl methane. Although the addition amount of a polymerization inhibitor can be set according to the amount of other additive components, it is preferably 0 to 5 parts by mass with respect to 100 parts by mass of the photosensitive silicon resin (A). More preferably, it is ˜1 part by mass.

  The photosensitive resin composition of the present invention may further contain a lubricant, an antistatic agent, a release agent, a foaming agent, a nucleating agent, a coloring agent, a crosslinking agent, a dispersion aid, a plasticizer, a flame retardant, and the like. These materials are mixed with the photosensitive silicon resin (A) and any other components using a known method such as centrifugation, and the resulting mixture is foamed by a known method such as vacuum defoaming. It is preferable to remove.

  The photoradical reactive group equivalent of the photosensitive resin composition according to the present invention is preferably 0.2 mmol / g or more, more preferably 1.0 mmol / g or more from the viewpoint of crack resistance. More preferably, it is 2 mmol / g or more. Further, the photoradical reactive group equivalent of the photosensitive resin composition is preferably 10 mmol / g or less, more preferably 8 mmol / g or less, more preferably 5 mmol / g or less from the viewpoint of volume shrinkage during curing by light irradiation. g or less is more preferable, and 3.5 mmol / g or less is most preferable.

  Here, the radical photoreactive group equivalent is the number of moles of radical photoreactive groups per gram of the photosensitive resin composition. The photoradical reactive group is derived from the photosensitive silicon resin (A) and the compound (C) having a photoradical reactive group in the molecule. The photoradical reactive group equivalent derived from the photosensitive silicon resin (A) is obtained by calculating the molar amount of the photoradical reactive group in the raw material used when the photosensitive silicon resin (A) is produced. It can be calculated by dividing by the weight of the silicon resin (A), and the photoradical reactive group equivalent derived from the compound (C) having a photoradical reactive group in the molecule is the photoradical reaction in the molecule of the compound (C). It can be calculated by dividing the number of sex groups by the molecular weight. The photoradical reactive group equivalent of the photosensitive silicon resin (A) is X (A), and the photoradical reactive group equivalent of the compound (C) having a photoradical reactive group in the molecule is X (C). When the weight ratio of the photosensitive silicon resin (A) in the resin composition is Y (A) and the weight ratio of the compound (C) having a photoradical reactive group in the molecule is Y (C), the photosensitive resin. The radical photoreactive group equivalent in the composition can be calculated by X (A) × Y (A) + X (C) × Y (C).

<Manufacture of photosensitive resin composition>
In order to obtain the photosensitive resin composition of the present invention, the photosensitive silicon resin (A), the photo radical polymerization initiator (B), and a compound having a photo radical reactive group in the molecule as an optional component ( C) and antioxidants and / or ultraviolet absorbers (D) are introduced into glass containers, plastic containers, etc., such as web rotors, magnetic stirrers, motor-driven stirrers and stirring blades, etc. Can be uniformly mixed using a stirring device known in the art.

  The mixing temperature is preferably 20 ° C or higher and 80 ° C or lower. It can mix uniformly at 20 degreeC or more, and can prevent deterioration of each mixing component at 80 degreeC or less.

A preferred embodiment of the present invention is a method for producing a photosensitive resin composition as described above, and includes the following steps:
The following general formula (1):
R ¹ _n1 SiX ¹ _4-n1 (1)
{Wherein R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, n1 is an integer of 0 to 3, and X ¹ is a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms. And a group selected from the group consisting of an acetoxy group, and when there are plural groups, n1, R ¹ and X ¹ may be the same or different. } The metal oxide fine particles having a refractive index of 1.6 or more at least at any time before, during, and after the hydrolysis condensation Is added to the reaction system and condensed to obtain a photosensitive silicon resin (A), and
A second step of mixing the obtained photosensitive silicon resin (A) and the radical photopolymerization initiator (B);
The manufacturing method of the photosensitive resin composition containing this is provided. The first step can be performed as described above for the production of the polysiloxane compound and the condensation reaction product. The second step can be performed using a stirring device as described above.

  In the first step, it is preferable to hydrolyze and condense one or more silane compounds represented by the general formula (1) in an aqueous alcohol solution under acidic conditions.

  In the first step, 5 mass% to 80 mass% of the polysiloxane compound obtained by hydrolytic condensation and 20 mass% to 95 mass% of the metal oxide fine particles in an alcohol aqueous solution having 1 to 4 carbon atoms. The photosensitive silicon resin (A) is preferably obtained by condensation at a pH of 3 to 9, 50 ° C. to 100 ° C. and atmospheric pressure. In the first step, the obtained photosensitive silicon resin (A) has a boiling point of 100 at least one selected from the group consisting of alcohol, ketone, ester, ether, and hydrocarbon solvent at 100 atm. After adding a solvent having a temperature not lower than 200 ° C. and not higher than 200 ° C., the solvent component is removed by distillation, whereby the total content of water and solvent in the photosensitive silicon resin (A) is 0.0001% by mass to 5% by mass. It is preferable to include.

  In the second step, it is preferable to further mix one or both of the compound (C) having a radical photopolymerizable group in the molecule and the antioxidant and / or the ultraviolet absorber (D).

[Cured product]
The cured product can be a molded body having various shapes. As a method for obtaining a molded body, for example, a photosensitive resin composition is contained in a mold having an arbitrary cavity shape and made of a transparent material such as polydimethylsiloxane, fluorine-based transparent resin, cycloolefin-based transparent resin, or glass. A method of obtaining a molded product by removing a mold, and applying a photosensitive resin composition by a known method on a glass or Si substrate or sheet, for example. There is a method of performing a polymerization reaction by light irradiation to obtain a molded body formed on a substrate or a sheet.

  For light irradiation, light having a wavelength region of preferably 200 to 500 nm, more preferably 300 to 450 nm, and particularly preferably light having a dominant wavelength in the above wavelength region can be used. Examples of the light having the above wavelength region include a xenon flash lamp, a xenon short arc lamp, an ultrahigh pressure UV lamp, a high pressure UV lamp, a deep UV lamp, a low pressure UV lamp, a KrCl or XeCl excimer lamp, and a metal halide lamp. There is no restriction | limiting in the irradiation time of the light which has said wavelength range, For example, the photosensitive resin composition of this invention can be hardened by irradiation in the range of about 1 second-20 minutes.

  The atmosphere for the polymerization reaction is preferably 1% by volume or less, more preferably 5000 ppm or less, as the oxygen concentration. Specifically, it can be performed under an atmosphere of an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide gas, under reduced pressure or under pressure. These gases can be used as 1 type, or 2 or more types of mixed gas.

  In a preferred embodiment, it is preferable to further perform a baking step when forming the cured product. The baking process can be performed at 130 ° C. or higher and 300 ° C. or lower, for example. The baking process is typically performed following the light irradiation described above. Such baking (heating) is preferable because optical characteristics such as refractive index and transmittance can be stabilized. Although there is no restriction | limiting in particular as baking time, Usually, the range of about 1 minute-10 hours is preferable.

  Another aspect of the present invention provides a cured product obtained by the method as described above. The cured product is a plastic lens material (surface) used for mobile phones, LEDs, plastic lenses for automobiles, replica materials, optical sheets for backlights such as liquid crystal displays, lighting, various sensors, printers, copiers, etc. The covering material) can be suitably used as an optical semiconductor sealing material, and can be optimally used for the purpose of improving the light extraction efficiency of the LED.

  The plastic lens as an example of the cured product of the present invention is the photosensitive resin composition of the present invention after the photosensitive resin composition of the present invention is filled in a metal mold or resin mold having a lens shape, or on a roll or a plate. After the product is applied and the above-described mold is pressed and transferred, the photosensitive resin composition is cured by light irradiation as described above, and then released from the mold. The photosensitive resin composition filled in the mold is covered with a plastic film, a glass wafer, a metal plate, etc., and the use of an inert gas, decompression, pressurization, etc. Setting the oxygen concentration in the atmosphere during the curing reaction to 1% or less is preferable in terms of improving the curing reaction rate. In order to cure the photosensitive resin composition by light irradiation, it is necessary for light to pass between the light source and the photosensitive resin composition. For that purpose, it is necessary to irradiate light from a transparent medium side (transparent resin mold, plastic film, glass wafer, or no substrate, etc.) that transmits light of a light source necessary for curing. In order to improve releasability from the mold, it is preferable to apply a mold release agent to the mold, or to include a mold release agent or a mold release component in the mold and / or the photosensitive resin composition. The plastic lens produced by using the photosensitive resin composition of the present invention can be optimally used as a lens for a mobile phone, an LED, an in-vehicle use or the like.

  The replica material, which is another example of the cured product of the present invention, is filled with the photosensitive resin composition of the present invention into a metal mold or resin mold having a desired shape, and is the same method as described above for the production of a plastic lens. And you can get it. The obtained replica material has a characteristic of high hardness, and durability can be improved by further performing Ni electroforming as necessary. Examples of the shape include a lens, a line & space, a cylinder, a cone, a prism, a pyramid, a honeycomb, and the like, and can be selected according to the application and purpose.

  The surface coating material, which is another example of the cured product of the present invention, takes advantage of its high hardness as a cured product. For example, the photosensitive resin composition of the present invention is applied to the surface or inside of a substrate having a laminated structure. Then, it can be used for hard coat applications by curing. Alternatively, the surface covering material can be formed in the form of a film, a sheet, or a plate.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these.

<Manufacture of photosensitive resin composition>
[Example 1]
To a 300 mL eggplant-shaped flask, 4.82 g (20.76 mmol) of 3-methacryloxypropyl (methyl) dimethoxysilane (hereinafter abbreviated as MEDMO) and methyltrimethoxysilane (hereinafter abbreviated as MTMS) 2. 83 g (20.76 mol) and 2.1 g of ethanol were added and stirred. Separately, 3.74 g of distilled water and 1.12 μL of 10 mass% hydrochloric acid were placed in a container, mixed, and then added dropwise to the 300 mL eggplant flask over 1 minute using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 80 ° C. for 2 hours using an oil bath to obtain a reaction solution 1 containing a polysiloxane compound.

  After cooling the 300 mL eggplant flask containing the reaction solution 1 to room temperature, 81.4 g of ethanol was added over 5 minutes using a dropping funnel. Next, 51.6 g of ultrafine zirconia sol # 1 (average primary particle diameter of about 10 nm, water-dispersed zirconia particles made by Nissan Chemical Industries, Ltd., 10 mass% concentration) using a dropping funnel was stirred in the solution in the eggplant flask. However, it was put in over 5 minutes. After the dropping, a cooling tube was set and refluxed at 80 ° C. for 4 hours.

  After refluxing, 50 g of PGMEA was added, a distillation column was set, ethanol and water were removed, and a PGMEA solution was obtained. Then, PGMEA was removed by heating under reduced pressure to obtain polymer 1 as a photosensitive silicon resin (A).

  To 99.3% by mass of the obtained polymer 1, 0.5% by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide as a radical photopolymerization initiator (B) (LUCIRIN (registered trademark) manufactured by BASF Corporation) TPO), 0.2% by mass of ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] as an antioxidant (IRGANOX (registered trademark) manufactured by BASF Corporation) ) 245) was added and stirred until uniform to prepare a photosensitive resin composition (P-1).

[Example 2]
93% by mass of polymer 1 obtained in the same manner as in Example 1, 5% by mass of tricyclodecane dimethanol diacrylate as compound (C), and 0.5% by mass as radical photopolymerization initiator (B) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 0.2% by weight of ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl as antioxidant) ) Propionate] was added and stirred until uniform to prepare a photosensitive resin composition (P-2).

[Example 3]
To a 300 mL eggplant-shaped flask, 4.82 g (20.76 mmol) of MEDMO, 5.16 g (20.76 mol) of 3-methacryloxypropyltrimethoxysilane, and 2.1 g of ethanol were added and stirred. Separately, 3.74 g of distilled water and 1.12 μL of 10 mass% hydrochloric acid were placed in a container, mixed, and then added dropwise to the 300 mL eggplant flask over 1 minute using a dropping funnel. After completion of dropping, a cooling tube was set and refluxed at 80 ° C. for 2 hours using an oil bath to obtain a reaction solution 6 containing a polysiloxane compound.

  After cooling the 300 mL eggplant flask containing the reaction liquid 6 to room temperature, 81.4 g of ethanol was added over 5 minutes using a dropping funnel. Then, using a dropping funnel, 51.6 g of ultrafine zirconia sol # 1 was added over 5 minutes while stirring the solution in the eggplant flask. After the dropping, a cooling tube was set and refluxed at 80 ° C. for 4 hours.

  After refluxing, 50 g of PGMEA was added, a distillation column was set, ethanol and water were removed, and a PGMEA solution was obtained. Then, PGMEA was removed by heating under reduced pressure to obtain polymer 3 as a photosensitive silicon resin (A).

  In 94.3 mass% of the obtained polymer 3, 5 mass% of tricyclodecane dimethanol diacrylate as the compound (C) and 0.5 mass% of 2,4,6- as the radical photopolymerization initiator (B). Trimethylbenzoyl-diphenyl-phosphine oxide, 0.2% by weight of ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] as an antioxidant, It stirred until it became uniform and the photosensitive resin composition (P-3) was prepared.

[Example 4]
To a 300 mL eggplant-shaped flask, 4.65 g (20.75 mmol) of p-styryltrimethoxysilane (hereinafter abbreviated as StTMS), 5.07 g (20.75 mol) of diphenyldimethoxysilane, and 113.9 g of ethanol are charged. , Stirred. Then, using a dropping funnel, 72.0 g of ultrafine zirconia sol # 1 was added over 5 minutes while stirring the solution in the eggplant flask. Separately, 3.74 g of distilled water and 2.24 μL of 10% hydrochloric acid were placed in a container, mixed, and then added dropwise to the 300 mL eggplant flask using a dropping funnel over 1 minute. After completion of dropping, a cooling tube was set and refluxed at 80 ° C. for 4 hours using an oil bath.

  After the reflux, 70 g of PGMEA was added, a distillation column was set, ethanol and water were removed, and a PGMEA solution was obtained. Then, PGMEA was removed by heating under reduced pressure to obtain a polymer 4 as a photosensitive silicon resin (A).

  The resulting polymer 4 (77.3% by mass) was mixed with 22% by mass of tricyclodecane dimethanol diacrylate as the compound (C) and 0.5% by mass of 2,4,6- (6) as the radical photopolymerization initiator (B). Trimethylbenzoyl-diphenyl-phosphine oxide, 0.2% by weight of ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] as an antioxidant, It stirred until it became uniform and the photosensitive resin composition (P-4) was prepared.

[Example 5]
In a 300 mL eggplant-shaped flask, 4.65 g (20.75 mmol) of StTMS, 3.78 g (20.76 mol) of phenylmethyldimethoxysilane, and 95.0 g of ethanol were added and stirred. Next, 59.3 g of ultrafine zirconia sol # 1 was added over 5 minutes while stirring the solution in the eggplant flask using a dropping funnel. Separately, 3.74 g of distilled water and 2.24 μL of 10 mass% hydrochloric acid were placed in a container, mixed, and then added dropwise to the 300 mL eggplant flask using a dropping funnel over 1 minute. After completion of dropping, a cooling tube was set and refluxed at 80 ° C. for 4 hours using an oil bath.

  After refluxing, 61 g of PGMEA was added, a distillation column was set, ethanol and water were removed, and a PGMEA solution was obtained. Then, PGMEA was removed by heating under reduced pressure to obtain a polymer 5 as a photosensitive silicon resin (A).

  The resulting polymer 5 (77.3% by mass) was mixed with 22% by mass of tricyclodecane dimethanol diacrylate as the compound (C) and 0.5% by mass of 2,4,6- Trimethylbenzoyl-diphenyl-phosphine oxide, 0.2% by weight of ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] as an antioxidant, It stirred until it became uniform and the photosensitive resin composition (P-5) was prepared.

[Comparative Example 1]
A reaction solution 1 was obtained in the same manner as in Example 1. After refluxing, 60 g of PGMEA was added, a distillation column was set, ethanol and water were removed, and polymer 6 was obtained.

  94.3% by mass of the obtained polymer 6 is 5% by mass of tricyclodecane dimethanol diacrylate and 0.5% by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide as a photopolymerization initiator, 0.2% by mass of ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] was added and stirred until uniform, and the photosensitive resin composition ( P-6) was prepared.

[Comparative Example 2]
A reaction solution 1 was obtained in the same manner as in Example 1.

  After cooling the 300 mL eggplant flask containing the reaction solution 1 to room temperature, 40 g of ethanol was added over 5 minutes using a dropping funnel. Then, using a dropping funnel, 25.8 g of PL-1SL (an average primary particle size of 12 nm, water-dispersed silica particles having a concentration of 20% by mass, manufactured by Fuso Chemical Industries) was added while stirring. After stirring, a condenser tube was set and refluxed at 80 ° C. for 4 hours in the atmosphere.

  After refluxing, 60 g of PGMEA was added, a distillation column was set, ethanol and water were removed, and polymer 7 was obtained.

  To 94.33% by mass of the obtained polymer 7, 5% by mass of tricyclodecane dimethanol diacrylate and 0.5% by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide as a photopolymerization initiator, 0.2% by mass of ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] was added and stirred until uniform, and the photosensitive resin composition ( P-7) was prepared.

<Production of cured product>
[Production of cured molded product]
A spatula is placed at the center of the obtained photosensitive resin composition (P-1) on a non-alkali glass (thickness 0.7 mm, vertical and horizontal 5 cm × 10 cm, manufactured by Corning) that has been surface-treated with a release agent comprising a fluorine compound. Applied. At this time, two polycarbonate films (thickness 1 mm, length and width 0.5 cm × 5 cm) are laid on both sides of the alkali-free glass, and the surface is covered with a release agent made of another fluorine compound on the photosensitive resin composition. The treated alkali-free glass was placed and fixed, and the dropped photosensitive resin composition was sandwiched between two sheets of alkali-free glass, so that oxygen curing inhibition was negligible. Then, from one alkali-free glass surface, a metal halide lamp (CV-110Q-G made by Fusion UV Systems Japan Co., Ltd., main wavelength: about 380 nm) was irradiated with ultraviolet light at a light intensity of 3000 mJ / cm ² , and the film thickness was 1 mm. A cured molded product was produced and designated as a cured molded product 1-1.

  Regarding the photosensitive resin compositions (P-2) to (P-7), cured molded products were prepared in the same manner as described above, and the cured molded products 2-1 to 7-1 were obtained, respectively.

[Preparation of cured film]
A spatula is placed at the center of the obtained photosensitive resin composition (P-1) on a non-alkali glass (thickness 0.7 mm, vertical and horizontal 5 cm × 10 cm, manufactured by Corning) that has been surface-treated with a release agent comprising a fluorine compound. Applied. At this time, two polyethylene terephthalate films (thickness 50 μm, length and width 0.5 cm × 5 cm) are laid on both sides of the alkali-free glass, and surface treatment is performed with a release agent made of a fluorine compound on the photosensitive resin composition. The alkali-free glass was placed and fixed, and the dropped photosensitive resin composition was sandwiched between two alkali-free glasses, so that oxygen curing inhibition was negligible. Thereafter, from one alkali-free glass surface, a metal halide lamp (CV-110Q-G manufactured by Fusion UV Systems Japan Co., Ltd., main wavelength: about 380 nm) was irradiated with ultraviolet light at a light intensity of 3000 mJ / cm ² , and the film thickness was 50 μm. A cured film was produced. The obtained cured film was designated as cured film 1-2.

  For the photosensitive resin compositions (P-1) to (P-7), cured films were prepared in the same manner as described above, and cured films 2-2 to 7-2 were obtained, respectively.

  The mass percentage of each component of the photosensitive resin composition of (P-1) to (P-7) and the photoradical reactive group equivalent are shown in Table 1 below:

  Cured molded product 1-1 to cured molded product 7-1 produced using the photosensitive resin compositions (P-1) to (P-7) produced in Examples 1 to 5 and Comparative Examples 1 and 2, Table 2 below shows the results of measurement and evaluation of samples of the cured film 1-2 to the cured film 7-2 according to the following (1) to (5).

(1) Refractive index evaluation The refractive index in wavelength 589nm of the produced cured film 1-2-2 cured film 7-2 was measured using the multi-wavelength Abbe refractometer DR-M2 by Atago Co., Ltd.

(2) Evaluation of heat shrinkage The film thickness of the produced cured molded article 1-1 to cured molded article 7-1 was measured, baked under conditions of 150 ° C. for 3 hours in a nitrogen atmosphere, and then again cured molded article 1-1. -The film thickness of the cured molded product 7-1 was measured. The film thickness before baking at 100 ° C. for 3 hours in a nitrogen atmosphere was defined as 100%, the film thickness after baking was calculated as a percentage, and 98% or more was evaluated as ◯, and less than 98% was evaluated as ×.

(3) Measurement of linear expansion coefficient The produced cured films 1-2 to 7-2 were cut into a width of 3 mm, and the sample length was 15 mm and the load was 5.0 g by a tensile measurement method using TMA-60 manufactured by Shimadzu Corporation. The measurement was carried out up to 300 ° C. under the condition of the temperature rising rate of 10 ° C./min, and the value measured for the second time using the same sample was adopted. The average expansion from 30 ° C. to 70 ° C. was calculated, and evaluation was made with ○ less than 70 ppm / ° C. and x greater than 70 ppm / ° C.

比較例１は、金属酸化物微粒子を含まないため、熱収縮と線膨張係数が劣っている。比較例２は、屈折率１．６以上の金属酸化物微粒子を含まないため、屈折率が低い。

Since Comparative Example 1 does not contain metal oxide fine particles, the thermal shrinkage and the linear expansion coefficient are inferior. Since the comparative example 2 does not include metal oxide fine particles having a refractive index of 1.6 or more, the refractive index is low.

  Optical materials that are cured products of the photosensitive resin composition of the present invention include, for example, cellular phones, LEDs, plastic lenses for in-vehicle use, replica materials, optical sheets for backlights such as liquid crystal displays, illumination, various sensors, printers, It can be suitably used as various plastic lens materials, optical semiconductor sealants and the like used for copy machines and the like.

Claims (22)

Photosensitive resin containing 100 parts by mass of photosensitive silicon resin (A) containing metal oxide fine particles having a refractive index of 1.6 or more and a photoradical reactive group, and 0.01 to 50 parts by mass of photoradical polymerization initiator (B) a composition, a photo-radical reactive group equivalent contained in the photosensitive resin composition is Ri 0.2~10mmol / g der,
From the peak area when the photosensitive silicon resin (A) is measured by ²⁹ Si NMR method, the following calculation formula (2):
Silanol content ratio = (D1 × 1 + T1 × 2 + T2 + Q1 × 3 + Q2 × 2 + Q3) / [M1 + (D1 + D2) × 2 + (T1 + T2 + T3) × 3 + (Q1 + Q2 + Q3 + Q4) × 4] (2)
{Where,
M1 is the peak area of one Si-O-Si bond among Si atoms having one bond bonded to an O atom,
D1 is a peak area of one Si atom having two Si—O—Si bonds out of two Si atoms bonded to an O atom;
D2 is a peak area of two Si-O-Si bonds among Si atoms having two bonds bonded to O atoms,
T1 is the peak area of one Si-O-Si bond among Si atoms having three bonds bonded to O atoms,
T2 is the peak area of two Si-O-Si bonds among Si atoms having three bonds bonded to O atoms,
T3 is a peak area of three Si-O-Si bonds among Si atoms having three bonds that are bonded to O atoms,
Q1 is the peak area of one Si atom having four Si—O—Si bonds out of four Si atoms bonded to O atoms,
Q2 is a peak area of two Si-O-Si bonds among Si atoms having four bonds bonded to O atoms,
Q3 is the peak area of three Si atoms with four Si—O—Si bonds out of four Si atoms bonded to O atoms, and
Q4 is the peak area of four Si-O-Si bonds among Si atoms having four bonds bonded to O atoms. }
The photosensitive resin composition whose silanol content ratio calculated by is 0.2 or less .   The photosensitive resin composition of Claim 1 which further contains 0.1-900 mass parts of 1 or more types of compounds (C) chosen from the group which consists of a monomer and oligomer which have a radical photoreactive group in a molecule | numerator. The photosensitive silicon resin (A) has the following general formula (1):
R ¹ _n1 SiX ¹ _4-n1 (1)
{Wherein R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, n1 is an integer of 0 to 3, and X ¹ is a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms. And a group selected from the group consisting of an acetoxy group, and when there are plural groups, n1, R ¹ and X ¹ may be the same or different. } The photosensitive resin composition of Claim 1 or 2 containing the polysiloxane compound which is a hydrolysis-condensation product of 1 or more types of silane compounds represented by these.   The photosensitive silicon resin (A) is one or both of one or more silane compounds represented by the general formula (1) and a polysiloxane compound that is a hydrolysis condensation product of the silane compound, and the metal oxide. The photosensitive resin composition of Claim 3 containing the condensation reaction material with microparticles | fine-particles.   The photosensitive resin composition according to claim 4, wherein the condensation reaction product has an aromatic hydrocarbon group.   The photosensitive resin composition of any one of Claims 3-5 in which the radical photoactive group in the said photosensitive silicon resin (A) originates in the said polysiloxane compound.   The photosensitive silicon resin (A) contains the metal oxide fine particles: 20% by mass or more and 95% by mass or less, and the total of the polysiloxane compound and the silane compound: 5% by mass or more and 80% by mass or less, or The photosensitive resin composition of any one of Claims 3-6 which is a condensation product of this mixture.   The said polysiloxane compound is a hydrolysis-condensation product of the condensation raw material containing the silane compound whose n1 is 1 among the silane compounds represented by the said General formula (1), Any one of Claims 3-7 The photosensitive resin composition according to item.   The said radical photopolymerization initiator (B) contains at least 1 sort (s) chosen from the group which consists of an acetophenone derivative, an (alpha) -aminoalkyl phenone type compound, and a phosphine oxide type compound, The any one of Claims 1-8. The photosensitive resin composition as described in 2.   The photosensitive resin composition of any one of Claims 1-9 in which the said metal oxide microparticles | fine-particles contain at least 1 sort (s) chosen from the group which consists of Al, Ti, Zn, Zr, Nb, and Sn.   The photosensitive resin composition according to claim 1, wherein the metal oxide fine particles have a band gap of 3.0 eV or more. The optical radical reactive group is a (meth) acryloyl group, at least one group selected from the group consisting of styryl group, and a mercapto group, a photosensitive resin composition according to any one of claims 1 to 11 object. The photosensitive resin composition according to any one of claims 1 to 12 , further comprising 0.1 to 50 parts by mass of at least one stabilizer (D) selected from the group consisting of an antioxidant and an ultraviolet absorber. object. The average primary particle diameter of the metal oxide fine particles is 1nm or more 100nm or less, the photosensitive resin composition according to any one of claims 1 to 13. It is a method of manufacturing the photosensitive resin composition of Claim 3, Comprising: The following processes:
The following general formula (1):
R ¹ _n1 SiX ¹ _4-n1 (1)
{Wherein R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, n1 is an integer of 0 to 3, and X ¹ is a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms. And a group selected from the group consisting of an acetoxy group, and when there are plural groups, n1, R ¹ and X ¹ may be the same or different. } The metal oxide fine particles having a refractive index of 1.6 or more at least at any time before, during, and after the hydrolysis condensation Is added to the reaction system and condensed to obtain a photosensitive silicon resin (A), and
A second step of mixing the obtained photosensitive silicon resin (A) and the radical photopolymerization initiator (B);
Only including,
In the first step, the obtained photosensitive silicon resin (A) has at least one selected from the group consisting of alcohols, ketones, esters, ethers, and hydrocarbon solvents, and has a boiling point at 100 ° C. of 100 ° C. After adding a solvent having a temperature of 200 ° C. or lower and then distilling off the solvent component by distillation, the total content of water and solvent in the photosensitive silicon resin (A) is 0.0001% by mass to 5% by mass. The manufacturing method of the photosensitive resin composition further including making it . The method for producing a photosensitive resin composition according to claim 15 , wherein the hydrolysis and condensation in the first step is performed in an aqueous alcohol solution under acidic conditions. In the first step, 5 mass% to 80 mass% of a polysiloxane compound, which is a hydrolysis condensation product of the silane compound, and 20 mass of the metal oxide fine particles added to the reaction system after the hydrolysis condensation % and 95 wt% inclusive, obtained aqueous alcohol having 1 to 4 carbon atoms, PH3～9,50 ° C. or higher 100 ° C. or less, and condensed at atmospheric pressure photosensitive silicon resin (a), claim 15 The manufacturing method of the photosensitive resin composition of description. In the second step, at least one compound (C) selected from the group consisting of monomers and oligomers having a photoradical reactive group in the molecule, and at least selected from the group consisting of an antioxidant and an ultraviolet absorber. The manufacturing method of the photosensitive resin composition of Claim 15 which further mixes one or both of 1 type of stabilizers (D). The photosensitive resin composition according to any one of claims 1-14, comprising the step of the main wavelength is irradiated with light is 200 to 500 nm, the production method of the cured product. The manufacturing method of the hardened | cured material of Claim 19 which further includes the baking process at 130 to 300 degreeC. Comprises producing the cured product I by the method for producing a cured product according to claim 19, a method of manufacturing an optical semiconductor sealing agent. Comprises producing the cured product I by the method for producing a cured product according to claim 19, the manufacturing method of a plastic lens.