TW201231509A - Photosensitive resin composition and method for producing same - Google Patents

Abstract

The present invention provides: a photosensitive transparent resin composition having excellent thermal shock resistance in the production of products with integrated electronic parts or of solid-state imaging elements that requires a reflow soldering process; and a microplastic lens or an optical-element molded product for liquid crystal polarizing plates that uses said photosensitive transparent resin composition. The photosensitive resin composition contains: 100 parts by mass of a polyorganosiloxane (a) having a polymerizable functional group and prepared according to a method of mixing an alkoxysilane compound represented by the following general formula (1), R1 aR2 bSi(OR3)4-a-b (wherein R1, R2, R3, a, and b are as defined in the Description), with a catalyst and polymerizing the alkoxysilane compound, wherein said polyorganosiloxane (a) includes a structure represented by the following general formula (2), =Si-O-X-Si= (wherein X is as defined in the Description), and the structure of said general formula (2) contains 5 to 60% of the Si atoms contained in said polyorganosiloxane (a); and 0.01 to 30 parts by mass of a photopolymerization initiator (b).

Description

201231509 VI. Description of the Invention: [Technical Field] The present invention relates to a photosensitive device for a semiconductor device, a plastic microlens (Microplastic Lens), a liquid crystal polarizing plate, an optical waveguide, etc., which are mainly used for optical purposes. A resin insulating film used for electrical and electronic materials such as a semiconductor device or a multilayer wiring board. More specifically, the present invention relates to a plastic mini lens for a camera module such as a mobile phone or a surveillance camera, and a peripheral material for a camera module. A plastic microlens for optical communication, CCD (Charge Coupled)

Device ’ CMOS (Complimentary Metal)

Oxide Semiconductor, complementary metal oxide semiconductor) plastic microlens for solid-state imaging devices such as image sensors, LED (Light_ Emitting Diode) encapsulant, photonic crystal for LED high-brightness, display A thin film transistor array (FUm Transistor Array) is used as a material for forming an antireflection film, and a material for an optical element for a polarizing plate for a liquid crystal projector is used for LSI (Large Scale Integration). Body circuit) A material of a buffer coating film or an interlayer insulating film of a wafer. [Prior Art] Since plastic lenses are easier and cheaper to form than glass, they are widely used in various optical articles. As the material, various transparent materials such as a thermoplastic resin such as polymethyl methacrylate or polystyrene, and a thermosetting plastic such as polydiethylene glycol bis(allyl carbonate) can be used. However, as shown in the patent document (4), the conventional material is improved in heat resistance, and most of the months are 159229.doc 201231509 200 °C or less, and reflow soldering at 260 °C cannot be guaranteed. Generally, a siloxane polymer having a 3Si-0-Si= structure has high heat resistance. Patent Document 3 discloses a polyoxyalkylene having a molecular weight of 3, 〇〇〇 or more, 1 Å or less, which is obtained by polymerizing a decanediol and an alkyl decyl decane in a two-step process. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a solid-state image sensor or an electronic component-integrated article for use in a reflow soldering step, which has been subjected to curing even after hardening - 4 (TC to 125. (: a photosensitive transparent resin composition which does not cause cracking or peeling resistance to temperature shock resistance, etc., a resin which can be used for the composition, and the use of the composition [Technical means for solving the problem] In order to solve the above problems, the inventors of the present invention conducted research on a photosensitive resin containing a siloxane, and found that only specific molecular weight is condensed = or a specific decane is used. The alcohol compound and the specific alkoxydecane compound are combined and condensed, and then a photopolymerization initiator is added to obtain a photosensitive resin excellent in temperature impact resistance. The present invention has been invented, and the present invention has been completed by the method of polymerizing a polyoxane. That is, the present invention is described in the following paragraph: π]. A photosensitive resin composition containing polyorganosiloxane. 100 parts by mass of the alkane (a), and 0.01 to 30 parts by mass of the photopolymerization initiator (b), and the above-mentioned oxygen-breaking (4) are represented by the following formula (1) to two kinds of anthracenite A compound having a polymerizable functional group, which is a method of polymerizing a compound, and a method of polymerizing the compound, which has a polymerizable functional group,

=): indicates the structure, and the polyorganism, oxygen chamber (4) has a number of Si atoms 5 to secret contained in the structure of the above formula (2) (4), R'aR^SiCOR3)^ (1) (wherein R1 is an organic group having a carbon bond of 2 to 17 and having at least one of a ketone group or a methacrylic group; and R2 is independently a carbon number which may have a substituent in the case where a plurality of R2 are present (IV) The aliphatic group, Han 3 is independently a f group or an ethyl group when there are a plurality of cases, respectively, or an integer, b is an integer of 〇~2, and a+b is 3 or less} —Si-0- (2) The photosensitive resin composition of [1], wherein the polyorganosiloxane (4) is obtained by the above-mentioned At least one of the compounds represented by the formula (1), which is obtained by a method of mixing and polymerizing at least one of the sulphuric acid compounds represented by the following formula (3), and the catalyst, R4R5Si (〇H) 2 (3) wherein R and R5 are an aliphatic group, an alicyclic group or an aromatic group having 3 to 1 carbon atoms which may have a substituent. [1] The photosensitive resin composition of [2], wherein the polyorgano oxyazepine (a) has ～40% of the number of si atoms contained in the above formula (2). ) within the structure represented. [4] A photosensitive resin composition comprising: polyorganosiloxane (a) 1 part by mass ' and a photopolymerization initiator (b) 0.01 to 30 parts by mass, the above polyorganosiloxane (a) It is obtained by a method in which at least one alkoxydecane compound represented by the following formula (1) and a catalyst are mixed and polymerized, and the source of the bond in the 丨H-NMR spectrum The ratio of the peak area of the self-reliant peak to the peak area of the vinegar-derived alcohol is reduced by 5 to 60% compared with the addition, ^ aK bSl(〇R )4ea b {formation, R, is the carbon number 2~17 The organic group containing a stimulating bond, at least one of R1 has a (tetra) fluorenyl group or a methyl propyl group, and r2 is present in plural plural:: independently, an aliphatic group having a carbon number which may have a substituent, and R3 has a plural number In each case, it is independently an integer of hydrogen, f-group or ethyl, ..., b is an integer of 0 to 2, and (iv) is 3 or less}. The photosensitive resin composition (a) as in [4] is obtained by mixing the above formula to: an organic oxime compound, and the following formula: And the method of polymerizing the obtained alcohol compound, and the angle R4R5Si(〇H)2 (3) wherein R and R are a substituent alicyclic group or an aromatic group. [6] The photosensitive resin composition of [4] or [5], wherein the polyorganosiloxane (a) is derived from a carboxyl bond in a 1H-NMR spectrum. The ratio of the peak area of the acid to the peak area of the ester bond derived from the alcohol is reduced by ι 〇 / / 4 ' 〇〇 / 〇 compared with the case of the addition. [7] A photosensitive resin composition containing: 100 parts by mass of the organic siloxane (a) and 0.01 to 30 parts by mass of the photopolymerization initiator (b), and the polyorganosiloxane (a) is at least represented by the following formula (1) An alkoxydecane compound, at least one stanol compound represented by the following formula (3), and a method in which a catalyst is mixed and polymerized, and is obtained by gel permeation chromatography (GPC). The area of the polystyrene-equivalent weight average molecular weight of 1,050 or more is 70% or more, RWbSKOR^.ab (!) {wherein, R is an organic group containing an ester bond of 2 to 17 carbon atoms, and at least one of Ri Having a propylene fluorenyl group or a methacryl fluorenyl group, and r2 is independently an aliphatic group having a carbon number of 1 to 1 可 which may have a substituent when there are a plurality of ❹, and R 3 is independently Methyl or ethyl, a is an integer of 1 or 2, b is an integer of 0 to 2, and a+b is 3 or less} R4R5Si(〇H)2 (3) {wherein R4 and R5 are substitutable The photosensitive resin composition of any one of [1] to [7], wherein the above formula ( 1) The alkoxydecane compound represented by the following formula (4) is at least one alkoxydecane compound, 159229.doc 201231509 H2C=C(R6)-(C=0)-〇.(CH2 n-SiR7c(OR8)d (4) {wherein, R6 is hydrogen or a fluorenyl group, and R7 is independently an aliphatic group having a carbon number of a substituent in the presence of a plurality of cases, and R8 is present. Multiple cases Independently methyl or ethyl, C is an integer of 〇~2, d is an integer of 1 to 3, c+d is 3 or less, and η is 1 to 14}. [9] as [2]' [3] And a photosensitive resin composition of any one of the above-mentioned items (5), wherein at least one of R4 and R5 in the above formula (3) is an alicyclic ring having a carbon number of 3 to 10 which may have a substituent [10] The photosensitive resin composition according to any one of [1] to [9] further comprising an ethylenically unsaturated addition polymerizable monomer with respect to 100 parts by mass of the polyorganosiloxane (a) ( c) 0.1 to 1 part by mass. [11] The photosensitive resin composition according to [10], wherein the ethylenically unsaturated addition polymerizable monomer is a compound containing an alicyclic group. [12] The photosensitive resin composition according to any one of [1] to [π], which further comprises an ultraviolet absorber selected from the group consisting of a light stabilizer, a light stabilizer, a polymerization inhibitor, a sensitizer, an antioxidant, and At least one additive selected from the group consisting of smoothness imparting agents. [13] The photosensitive resin composition according to any one of [1] to [12] wherein the alkali metal or alkaline earth metal concentration in the photosensitive resin composition is 0.1 to 500 ppm 14 [14] a polyorganosiloxane The method for producing an alkane, which comprises: 1) a compound of at least a (tetra) group 11 represented by the following formula (1), and an amount of a ruthenium 1 having a compound of the oxy-stone compound present in the reaction system The mixture of 〇.〇1~〇.5 equivalent of water and a catalyst is mixed and reacted at 159229.doc 201231509 130C for 0.1 to 20 hours, and the alcohol formed by the reaction is removed to the outside of the surface. The step of forming a poly(4-)oxygen (4), RWbSKOR^.b (1) wherein R1 is an organic group containing an ester bond having 2 to 17 carbon atoms, and at least y has a propylene fluorenyl group or a fluorenyl fluorenyl group. R2 is independently an aliphatic group having a carbon number 丨~(7) which may have a substituent in the case of a plurality of plural, and R3 is independently a methyl group or an ethyl group in the case of a plurality of cases, and a is an i or 2 An integer, b is an integer from 0 to 2, and a+b is 3 or less}; and ii) does not dissolve polyorganosiloxane The solvent is used to clean the polyorganooxane 0). [15] A method for producing a polyorganosiloxane, comprising: 1) at least one alkoxydecane compound represented by the following formula (1), or at least one represented by the following formula (3) The stanol compound and the catalyst are mixed and reacted at 20 to 130 ° C for 01 to 2 hours, and the alcohol formed by the reaction is removed to the outside of the system to form a polyorganosiloxane. (a) a step, R, R2bSi (〇RVa.b (1) {wherein, R1 is an organic group having an ester bond having 2 to 17 carbon atoms, and at least one of Ri has an acryloyl group or a fluorenyl fluorenyl group. When R2 is present in a plurality of cases, it is independently an aliphatic group having a carbon number of 丨~1〇 which may have a substituent, and the ruler 3 is independently a fluorenyl group or an ethyl group in the case of a plurality of cases, and a is 1 or 2, respectively. An integer, b is an integer of 0 to 2, and a+b is 3 or less} R4R5Si(〇H)2 159229.doc (3) 201231509 {wherein, R4 and R5 are carbon atoms 3 to 1 which may have a substituent An aliphatic group, an alicyclic group or an aromatic group of hydrazine and 11) a step of washing the polyorganosiloxane (a) with a solvent which does not dissolve the polyorganosiloxane. [16] The method of producing [14] or [15] wherein the catalyst is at least one compound selected from the group consisting of metal hydroxides and alkaline earth metal hydroxides. The method of any one of the above-mentioned, wherein the catalyst is Ba(OH)2 and/or a hydrate thereof. For example, in the method of manufacturing the article [17], the amount of the above-mentioned catalyst is 0.05 to 30 mol% with respect to the total number of moles of cerium (Si). [19] As in the manufacturing method of any of [14] to [18], the total amount of the above-mentioned catalyst relative to 矽(Si) is 〇. 〖~;! 〇莫耳0/〇 . [20] For example, in the manufacturing method of [(4) to intermediate-term, the above solvent is alcohol or acetonitrile. [21] A cured product obtained by the photosensitive resin composition of any one of [" to 至." or by a production method according to any one of [14] to [2] The photosensitive resin composition of the polyorganosiloxane (&) and the photopolymerization initiator sand) was obtained by photocuring. [22] A method for producing a molded article, comprising the steps of: or a photosensitive resin composition according to any one of [1] to [13], or containing any of [14] to [20] - a step of filling the photosensitive resin composition of the polyorgano-oxyalkane (a) and the photopolymerization initiator (b) obtained in the production method into a molding die, 159229.doc -10·201231509 Step of pressing the opening of the mold onto the substrate or the other mold: the photosensitive resin composition is obtained from the mold and/or the substrate side: a step of obtaining a photocured material, and the mold is peeled off from the substrate or will be located at two And the step of removing the mold from the step of removing the mold from the step of removing the photo-cured material or the step of heating the photo-cured material. , [23] - a hardened material obtained by the method of [22] [24] A polyorganism, which is at least dried by the following formula (1) - (IV) an oxy (tetra) compound, a method represented by the following formula (3), at least: a seed smelting alcohol compound, and a catalyst mixed and polymerized, and the polyorganic material has a blanking formula (7) The structure of the table, and 5 to 峨 of the 81 atomic number of the (4) oxy-combustion is contained in the structure represented by the above formula (2), 订 ordering (4) 3) "·, (1) (wherein, R1 is The carbon number 2 to 17 contains the organic group of (4), and R2 is independently a carbon number which can have a substituent in the case of a plurality of carbon atoms (7), and the aliphatic group 'R3 is present in a plurality of cases. Or an ethyl group, a is an integer of 1 or 2 'b is an integer of 〇~2, and the following} R4R5Si(OH)2 (3) where R4 and R5 are a carbon having a substituent (10) Group, alicyclic or aromatic group} sSi-〇-x_si= (2) l59229.d〇c -11 - 201231509 {wherein, X is an organic group having 1 to 15 carbon atoms}. Ri in I), [25] [24] A polyorganosiloxane having a propyl acrylate and/or a methacrylate group thereon. [Effect of the Invention] According to the present invention, a solid-state image sensor for a reflow soldering step or A resin or a photosensitive resin composition which has excellent properties such as temperature crack resistance which does not cause cracking or peeling even after a heat-and-heat cycle, and a photosensitive resin composition. [Embodiment] <Photosensitive resin Compositions The photosensitive resin composition of the present invention is obtained by a method in which a specific alkoxyline compound and a catalyst are mixed and polymerized, and contains the following formula (2) = Si-0-X-Si= (2) {wherein, X is an organic group having a carbon number of 1 to 15} of a polyorganosiloxane (a); and a photopolymerization initiator (b). The decane compound is at least one alkoxylated calcined compound represented by the following formula,

RiaR2bSi(〇R3)4_a_b (1) where R is an organic group containing an ester bond of 2 to 17 carbon atoms, and at least one of Ri has an acryloyl group or a fluorenyl fluorenyl group, and R2 is present in a plurality of cases. Independently, in any case, the carbon number of the substituent may be a hydrazine group, an alicyclic group or an aromatic group 'R3. In the case where there are a plurality of cases, the cleavage is independently methyl or B. Base, a is an integer of 1 or 2, b is an integer of 159229.doc • 12-201231509, and a+b is 3 or less}. As the polyorganosiloxane (a), from the viewpoint of storage stability, it is preferred to use at least a compound of the above formula (1), which is a compound of the formula A method in which the catalyst is mixed and polymerized. & In this case, the residual alcohol compound is at least one stanol compound represented by the following formula (3), R4R5Si(〇H)2 (3) wherein R and R5 are a carbon number which may have a substituent ~1〇 of an aliphatic group, an alicyclic group or an aromatic group}. The alkoxydecane represented by the above formula (1) is preferably at least one alkoxydecane compound represented by the following formula (5), more preferably having an acrylate and/or a mercapto acrylate. Compound, R9-(C=0)-〇-X.SiRi〇c(OR8)d (5) wherein R9 is an aliphatic group, an alicyclic group or an aromatic fluorenyl group having a carbon number of 丨15. And may have a substituent, at least one having an acrylate and/or methacrylate, X being an aliphatic group, an alicyclic group or an aromatic group having a carbon number of -15 -15, which may have a substituent, and RU may be present in plural In the case of an aliphatic group having a carbon number of 1 to 10, respectively, may have a substituent, and RS may be independently a methyl group or an ethyl group in the case of a plurality of cases, (^ is an integer of 0 to 2, and 4 is ^ An integer of ～3, c+d is 3 or less, and „为丨14 is a photosensitive property, and at least one alkoxydecane compound represented by the following general formula (4) is preferably used. , (4) H2C=C(R6)-(C=〇)-〇.(CH2)n-SiR7c(〇R8)d 159229.doc -13· 201231509 {wherein R6 is hydrogen or sulfhydryl' R7 When there are multiple cases An aliphatic group, an alicyclic group or an aromatic group which is independently a carbon number which may have a substituent, and R8 is independently a methyl group or an ethyl group in the case of a plurality of cases, and c is an integer of 〇~2 'd is An integer of ^3, e + d is 3 or less, and n is a b). As an example of the alkoxydecane compound represented by the formula (4), 3-methylpropenyloxypropyltrimethyl is exemplified. Oxygen sulphur, 3-methyl propyl methoxy propyl diethoxy sulphur, 3-methyl propyl methoxy propyl methyl decyl oxy decane, 3 · propylene methoxy propyl three曱oxydecane, 3-propenyloxypropyltriethoxydecane, 2-methylpropenyloxyethyltrimethoxyoxane 2-methylpropenyloxyethyltriethoxydecane, methyl Propylene oxyethyl methyl dimethoxy zeshi, 2-propene oxyethyl trimethyate = money: 2-propene oxyethyl triethoxy zebra, methacryl 醯 曱Dimethoxy (tetra), methacryloxymethyl triethoxy sulphur, sylvestre, methyl propylene, oxymethylmethyldimethoxy, oxime, propylene oxime #: A Oxyl money, propylene Oxymethyltriethoxy 7 or the like. It is also possible to use an alkoxydecane having an ester bond which does not have a polymerizable functional group such as 3-ethyloxypropane = A. · "-methoxy decane Further, at least one type of corpse compound represented by the following oxygen-cutting formula (1) is obtained as a compound of the above-mentioned alkoxy decane compound, in addition to the above-described alkoxy compound, __ group... An alkoxy decane which does not have a 3 ester bond of a polymerizable ruthenium b-belt, such as 3, ethoxypropyltrimethoxy decane, may be used, which is obtained by the following decane compound And the following: If at least the oxygen-burning substance and the catalyst are mixed and the method of at least the alcohol-alcoholization is not obtained, the polyorgano 矽 159229.doc *14· 201231509 罝= There is a structure represented by the general formula (7), and the polyorganic oxy-combustion gas = 5 to 6 G% of the U number is contained in the above-mentioned formula (7), RI'aR2bSi(〇R3)4.ab (1)

Wherein R has an organic group containing a S| bond of carbon number 2 to 17, and R2 is independently an aliphatic group having a carbon number of WG which may have a substituent in the case where a plurality of R2 are present, and R3 is present in plural cases. The time is independently methyl or ethyl, a is an integer of 1 or 2, b is an integer of 〇~2, and &+1) is 3 or less) R4R5Si(OH)2 (7) {wherein, R4 and R5 are An aliphatic group, an alicyclic group or an aromatic group having a carbon number of 3 to 1 Å having a substituent} - Si-OX-Si^ (2) wherein X is an organic group having 1 to 15 carbon atoms . By using the above polyorganosiloxane, a resin excellent in temperature impact resistance can be obtained. As the catalyst, the hydrolysis of the alkoxy group which promotes the alkoxydecane compound, and the condensation reaction of the stanols or the alkoxydecane and the stanol which are formed by the mixture can be used, and the ester hydrolysis reaction or ester is carried out during the polymerization. Exchange the compound of the reaction. As the catalyst used for the reaction of the alkoxylate compound and the shixi compound, a dealcoholization condensation reaction for promoting the alkoxy group of the stanol group of the stanol compound and the alkoxyhalide compound can be used in the polymerization. A compound which undergoes an ester hydrolysis reaction or a vinegar exchange reaction in the process. The catalyst may be an acidic compound or an inspective compound, and examples thereof include a metal 159229.doc 15- 201231509 a burned oxide, an inorganic acid, an organic acid, an inorganic test, an organic test, a nitrile compound, and the like. Among them, an alkali metal hydroxide or an alkaline earth metal hydroxide or an ammonium compound is preferable, and specific examples thereof include Ba(OH)2, Ca(OH)2, Mg(OH)2, KOH, and LiOH. NH3, NH4OH, NR4(OH) 'NR4C1 'NR4Br, NR4I, etc. In NR4(OH), NR4C1, NR4Br and NR4I, R is an aliphatic group, an alicyclic group or an aromatic group having 1 to 10 carbon atoms which may have a substituent. More preferably, it is an alkali metal hydroxide, an alkaline earth metal hydroxide or the like. Further, the catalyst is preferably an alkaline earth metal hydroxide, and specific examples thereof include Ba (〇H) 2, Ca(〇H) 2, and Mg(OH) 2 . Further, it is also possible to use a hydrate of Ba(〇H) 2 and Ca(〇H) 2 to improve the stability and shorten the reaction time, and to improve the reproducibility by shortening the reaction time in the uneven state. From the viewpoint of the reaction, it is more preferred to use Ba(〇H)2 · 8H2〇. Should be... "丨ώ 4 4 hydrolysis of poor jujubes, etc.", or S is an appropriate exchange reaction, .#,, ^ ^ The concentration of sputum, for example, relative to the addition of Si" The number is 0.05 to 30 ears. η, 4-phase and reaction controllability. It is preferably 0.1~20 mol 0/0, more (Μ~Η) mol%, especially good) 0H0 mol%. The pure compound number 乂 氧基 氧基 夕 夕 夕 与 与 与 与 与 与 与 与 与 与 与 与 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; How many moles of catalyst are added. With respect to the Si atom, as a viewpoint of the alcoholicity represented by the general formula (3), it is preferably a ruthenium and a < 2 D , and a 159,229 which is a stable substituent of the compound. .doc -16« 201231509 Aromatic or alicyclic. From the viewpoint of light resistance and heat resistance, at least one of R4 and hydrazine is a carbon number 3 which may have a substituent. : a compound of the lipid group. Further, from the viewpoint of more excellent transparency, dicyclohexyl sulphuric acid diol and dicyclopentyl sulphuric acid diol are preferred. The mixing ratio of the alkoxydecane compound represented by the formula (1) to the stanol compound represented by the formula is based on the oxime of the formula (3): 100 moles, the alkoxylate represented by the formula (1) The compound of the smoldering compound is 1 Torr, preferably 20 to 180 moles, more preferably 30 to 150 moles, still more preferably 40 to 120 moles, and the molecular weight and the obtained resin are 1; From the point of view, the best is 60~1〇〇. When the alkoxydecane compound represented by the formula (1) is mixed with the stanol compound represented by the formula (3) to carry out a reaction in the presence of a catalyst, the reaction temperature is 2 (TC). 〜13CTC, preferably 3〇~1〇 (rc, more preferably 40~8〇t, the reaction time is hour, preferably 0.2~10 hours, more preferably 〇.3~5 hours. Reactor The internal environment may be a nitrogen Q environment or an air environment. The water may be actively added to the reaction system or may not be actively added. Even in the case where water is not actively added, the water in the hydrated compound of the catalyst used or The water in the stanol may also be present in the reaction system. When only the alkoxydecane compound represented by the formula (1) is used, a minimum amount of water may be used, preferably with respect to the bond to the Si atom. The amount of the oxy group is from 0.001 to 0.5 equivalents. In order to reduce the linear expansion constant of the cured product and adjust the refractive index, fine particles such as cerium oxide, cerium oxide, and titanium oxide may be added to the reaction system. 201231509 <Alkoxydecane compound, or Reaction of a oxydecane compound with a squirrel alcohol compound > σ The alkoxy decane compound represented by the formula (1) and >, the alkoxylated compound represented by the formula (1) The oxy-alcohol compound represented by the formula (3) is mixed and allowed to react in the presence of a catalyst. = 1H-NMR of the reaction mixture at a certain time (for example, 15 minutes, 30 minutes, 60 minutes) In the spectrum measurement, the reduction ratio of the peak area derived from the side of the carboxylic acid of the ester bond of the alkoxydecane compound represented by the formula (1) is confirmed, and the reaction is carried out, for example, AC (=〇). In the case of the ester bond of -0_B, A is the side of the ester bond derived from the carboxylic acid, and B is the side derived from the alcohol of the ester bond. By hydrolysis or solvolysis of the ester, 1H_NMR The peak area of a proton derived from A is reduced, and the reduction rate of the peak area derived from the side of the carboxylic acid indicates that the peak area of the proton derived from A is a proton that does not change during the reaction. How much is reduced in the benchmark. The reduction rate can be determined by comparison with the NMR of the raw material. For example, use When 20(:(Μ+(00)-〇_(ί:Η2)3_8Κ〇Μβ)3 is used as a raw material, Si CH2 appears in the vicinity of 〇6 ppm in the initial, ie, the elbow spectrum of the raw material. · The peak of the proton, and the peak of the proton of H2C=C<, near the 5 5 claws and 6. The peaks of the peaks are 2: 2, and the ratio is 1. Relative to the 'ester linkage' In a polyorganosiloxane which is formed by condensation of a carboxylic acid and an alcohol but the carboxylic acid moiety of the ester bond disappears, the carboxylic acid moiety of the ester bond, that is, the peak area of H2C=C< and the alcohol moiety of the ester bond is = The ratio of the peak area of Si-CH2- is reduced by 'the ratio of the peak areas is 1 or less, and the ratio of the disappearance of the carboxylic acid moiety of the ester bond can be calculated. As a specific example, when the polyorganosiloxane is not shown in Figure 159229.doc -18·201231509, the sum of the peak areas of the two H2C=C< is 1.997, and the peak area of the Si-CH2- When it is 2.885, it can be seen that the peak area ratio is 1.997 ·· 2.885, that is, 0.69, and the peak area of the ester bond derived from the carboxylic acid is reduced by 31°/〇 as compared with the initial ratio of the peak area ratio of the raw material. The carboxylic acid moiety of the ester bond disappeared 31 〇 /. . Among them, the ιΗ·ΝΜΚ spectrum system set the peak of CHCI3 to 7.24 ppm as a reference. By reducing the amount of catalyst, time, temperature, pressure in the reaction vessel, etc., it is possible to control the reduction of the peak area derived from the carboxylic acid of the ester bond of the alkoxydecane compound represented by the formula (1). For example, by increasing the amount of catalyst, extending the time, and increasing the temperature, the rate of decrease can be increased. As a specific example, the alkoxy decane represented by the formula (1) is an alkoxy decane having a methacrylate, and Ba(OH) 2 and H 2 fluorene are used as a catalyst, and a commonly used catalyst is used. When the concentration is a molar ratio of Oi to the total amount of Si, even if the reaction temperature is 5 Torr and the reaction time is 2 hours, the peak area of the ester bond derived from the carboxylic acid does not decrease, but By increasing the amount of catalyst to 〇3 Q mol / (> reacting, the peak area of the carboxylic acid-derived ester bond can be reduced by about 30/. Polyorganosiloxane. Thus, by changing The amount of catalyst, temperature, and reaction time can reduce the peak area of the ester bond derived from the carboxylic acid only by the amount required. In the polyfluorene reaction, the ester bond in the alkoxydecane compound represented by the formula 〇) The amount of disappearance is from 5 to 60%, preferably from 7 to 50%, more preferably 10 40/, based on the amount of the compound of the compound of the compound of the formula (1).胄佳 is 15~35%. The disappearance ratio is, for example, as described above, and the vinegar bond of the alkoxylate compound represented by the formula (1) is derived from the ratio of the peak area of the acid 159229.doc -19·201231509. The peak of the carboxylic acid moiety of the bond and the decrease in the polymerization reaction by the formula (1) are due to the alkoxy group and the alkoxydecane compound represented by the formula (3). The presence of the condensation of the decyl alcohol moiety of the decyl alcohol of the produced alcohol (methanol or ethanol), etc. 1 The trace amount of water and the catalyzed transesterification reaction of the following reaction formula are carried out, and the hydrolysis reaction of the bond is not carried out. 1] r12oh

-Si—〇χΎ1 + r12〇yr11 0 (6) , RM is an organic having a carbon number of 〇15 and R12 is a methyl group, an ethyl group or (wherein X is an organic group having a carbon number of 1 to 15' X and The sum of the carbon numbers of R11 is 1 to 16, hydrogen). The hydrolysis reaction by the hydrazone bond and the transesterification of the parent-reversed reaction 'depletion of the carboxylic acid-derived portion' are derived from the residue of the alcohol. Further, the alcohol produced by (4) 4 is produced by an alcohol exchange reaction with an alkoxy group of the alkoxy compound of the formula (1) and a nucleophilic group of the cerium alcohol compound represented by the formula (7). The cross-linking reaction represented by the formula (7), [Chemical 2]

X -0H I - έ卜 I

OR12 I —Si— I

I OSi - l / r - Si-X II HOR12 (7) (wherein X is an organic group having a carbon number of 1 to 15, preferably an organic group having a carbon number of 2 to 1 Å) more preferably a carbon number of 3~ 5 organic base 'in terms of heat resistance and crack resistance 159229.doc -20- 201231509 point, the best carbon number is 3, and Rl2 is sulfhydryl, ethyl or gas, ie, forbearance a part or all of the alkanediol or the stearyl alcohol which is formed by the disappearance of the ester moiety, and the alkoxydecane compound represented by the formula (1), the phenolic compound represented by the formula (3) or the like At least one type of condensation polymer is crosslinked to obtain a polyorganosiloxane (a). By the crosslinking reaction, high molecular weight can be obtained. Therefore, a structure represented by the above formula (2) can be obtained. By the structure of the above formula (2), it is excellent in temperature impact resistance. In the above formula (2), X can have an aromatic group in the main chain. The base is further preferably a substituted base or a base group. Specifically, as -X-0- ', a structure represented by the following formula can be cited, [Chemical 3]

• One (C Η 2) "Ο

—(CHs)

(CH2)n-〇—(8) (wherein 1 is 1 to 15 ′ to 9 ′ 〇 is 〇 ～9, and n+m<9). Further, from the viewpoint of light resistance, the base is preferably exemplified. From the viewpoint of heat resistance, the carbon number of ruthenium is preferably from 2 to 1 Torr, more preferably from 3 to 5, most preferably 3. Further, the structure represented by the above formula (7) can be confirmed by, for example, ^-NMR and i3c_NMR spectrum measurement. When the H2c=c(CH3)-(C=〇)-〇((CH2)3-Si(OCH3)3 is used in the case of the alkoxy 7-burning compound represented by the formula (1), the above-mentioned overnight (), Ό is formed as EHCH2_CH2 CH2_Sb, in the H spectrum, the vinegar bond does not disappear H2C=C(CH3)_(C where 0 CH2-CH2_CH2_ 仏 structure under the proton peak appears in 3.9 ~4.2 PPm, I59229.doc 201231509 In contrast, the peak of protons in the underlined portion of the structure ==0-0-CH2-CH2-CH2-Si= appears in the vicinity of 3.4 to 3.9 ppm. Further, in the 13C-NMR spectrum, The carbon peak of the underlined portion of the H2C=C(CH3)-(C=0)-0-CH2-CH2-CH2-Sis structure appears near 66.5 ppm, whereas the above reaction formula (6) is generated. The carbon peak of the underlined portion of the HO-CH2-CH2-CH2-S^ structure appears near 62.0 ppm, and the underlined portion of the ESi-0-CH2-CH2-CH2-SiE structure formed by the above reaction formula (7) The peak of carbon appears near 64.5卩卩111 (where the 111"^^^11 pedigree will be (:11 (the peak of 13 is aligned with 7.24卩?111, 13(:"^]\«1 pedigree will be € 0 (: 13 center of the peak is aligned with 77.0 ppm The 13C-NMR spectrum was determined in the NNE mode; see Fig. 1 and Fig. 3). The peaks can be identified by two-dimensional NMR spectrum measurement. Figure 7 is HH COSY (HH correlation spectroscopy, HH correlation spectrum). Spectra, Fig. 8 is a CH C0SY (CH correlation spectroscopy) spectrum. Generally, in HH COSY, the peaks of the hydrogen atoms bonded to each of the two carbon atoms in abutting relationship show correlation, in CH In COSY, the carbon atoms of the bonded carbon and the peak of the hydrogen atom show a correlation. In the HH COSY spectrum shown in Fig. 7, it is found that the peak of 3.4 to 3.9 ppm is related to the peak near 1.0 ppm, and further to around 1.0 ppm. The peak is related to the peak near 〇·〇ppm. Further, according to the CH COSY spectrum shown in Fig. 8, it is found that the peak of 64.5 ppm in 13C_NMR is related to the peak of 3.4~3·9 ppm in 1Η-NMR. These comprehensive judgments can be used to identify each peak (in COSY, the reference of the peak in the 1H NMR spectrum corrects the peak on the highest magnetic field side to 0 ppm, compared with the actual 1H NMR spectrum, 159229.doc -22 - 201231509 The overall southward magnetic field side is offset by 〇·6 ppm . By the above identification, the existence ratio of the structure of the above formula (2) can be calculated. Specifically, when H2C=C(CH3Mc=〇)〇(cH2^SKOCH3)3 is used as the alkoxydecane compound represented by the general formula (1), the 13C NMR spectrum shown in Fig. 3 is obtained, H2C = c (CH3) (c=〇)_〇CHrCHrCHrSb structure under the underlined part of the carbon peak area is 0.853, the HO-CH2-CH2-CH2-Sb structure under the underlined part of the carbon peak area is 0.099, under the qi-O-CHrCHrCHrSb structure underline The partial carbon peak area is 0.415. If the alkoxydecane compound represented by the above formula (I) = is substituted with the stanol compound represented by the above formula (3) at 50:5, for Ki-O- In the CiVCHrCHrSb structure, 30% of the Si atoms in the polymer are calculated to form a bond of the structure represented by the above formula (2). Further, even if the addition ratio of the alkoxydecane compound or the stanol compound is not known, the si atom content can be calculated by adding the internal standard 29Si NMR spectrum to calculate the vinegar by adding the internal standard 1H NMR spectrum. The content of the structure is determined by C NMR spectrum (NNE Mode), HH COS Y, and CH COSY spectrum, and the content of asSi-〇-x_si5 is calculated. The NMR spectrum was measured using JNM-GSX400. The 1 η NMR spectrum was measured at 400 MHz, and the ^cnmR line was measured at 1 〇〇 MHz. The ratio of the bond forming the structure represented by the above formula (2) in the number of Si atoms of the polyorganosiloxane is preferably from the viewpoints of the cracking property, the ease of handling, and the photocurability. 5 to 60%, more preferably 7 to 50%, further preferably 10 to 40%, most preferably 15 to 35 Å/〇. 159229.doc -23· 201231509 VIII As a method of maintaining the amount of the crosslinkable functional group (and finding the molecular weight) and increasing the molecular weight, a method of adding a boron compound or a method of adding a phosphorus compound and a peroxide may be used. Further, the (tetra) material is dissolved, and the polyorgano 7 oxonium obtained in the reaction step is washed by a solvent having a solvent to remove low molecular weight (for example, a polymer, a trimer 'tetramer, etc.). In the washing step, as the solvent which does not depolymerize the organic solvent, water is used, and alcohol (for example, methanol or ethanol), acetonitrile, etc., as a washing step, is a polyorganismite obtained in the reaction step. Burning = adding solvent that does not dissolve the polyorgano 7 oxygen, or adding the polyorganosiloxane obtained in the reaction step to the solvent which does not dissolve the polyorganosiloxane, and then stirring the mixture. Stirring is continued in the state, and then left to stand: after being separated into a polyorganosiloxane layer and a solvent layer, a polyorgano-oxygen-fired layer can be collected or the solvent layer can be removed, thereby performing cleaning. The residual catalyst can be reduced. The amount of residual catalyst in the resin composition is preferably from 0. l to 50 〇 ppm from the viewpoint of the stability of the polymer and the resin composition. <Polyorganooxane High molecular weight > + photosensitive resin composition of the present invention (4) Oxygen-fired (4) is obtained by mixing and agitating the alkoxy 7-burning compound represented by the above formula (1), the above-mentioned formula (3), and the catalyst of the above-mentioned formula (3), and the catalyst. In the gel permeation chromatography (GPC), the weight average molecular weight in terms of standard polystyrene is 1〇5〇 or more, and the area is more than or equal to the above. The molecular weight evaluation method (GPC measurement) is as follows. 159229.doc 24· 201231509 Using HLC-8020 manufactured by Tosoh, using a differential refractometer (RI, Refractive Index) as a detector, the tube system is connected by G5000HHR, G4000HHR, G3000HHR, G2500HHR manufactured by Tosoh Co., Ltd. In the case of 40 ° C, polystyrene (TSK standard manufactured by Tosoh, molecular weight 1,090,000, 706,000, 355,000, 190,000, 96,400, 37,900, 18,100, 9,100, 5,970, 2,630, 1 , 056, 500) As a standard polystyrene, a calibration curve 'measured at a flow rate of 1 mL/min' using THF (Tetrahydrofuran, tetranitrofuran) as a solvent. The above stanol compound, the above alkoxydecane compound The catalyst, the reaction conditions, and the like are the same as described above. The polymerization can be achieved by forming the structure represented by the above formula (2). Therefore, in order to control the molecular weight, it is only necessary to control the above formula (2). The structure represented by the above reaction formulas (6) and (7) may be omitted. The reactions may be controlled by changing the reaction temperature, the reaction time, the reaction pressure, the amount of the catalyst, and the type of the catalyst. <Production Method of Polyorganooxane> The method for producing (a) of the polyorgano oxysulfide comprises the following steps: i) at least one alkoxydecane compound represented by the above formula (1) And the catalyst is mixed 'in 20C~130C, preferably 3〇~1〇〇〇c, more preferably 40~8 (at the temperature of TC, the reaction time is 〇. 2 2 hours, preferably 0.2 to 1 hour, more preferably 0 to 3 to 5 hours, and the alcohol formed by the reaction is removed to the outside of the system. The step of producing a polyorganosiloxane (a) is performed. The step of washing the polyorganic 159229.doc -25- 201231509 oxane (a) by dissolving the solvent of the polyorganic sand olefin. It is also possible to add water to the reaction system, and it is preferred to have an oxygenate in the reaction system. ·〇]~"When: ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ M~〇.4 equivalent stability and reactivity. The manufacturing method of Qianxuan (4) includes the following steps in sequence: upper = at least "' morphological oxygen compound represented by general formula (1), θ human _ a compound of a stanol, and a catalyst

22 is in the heart ~ 13 ° ° c, preferably in the heart (four), more preferably 4. Book C = lower, the reaction time is hour, preferably 〇 2~1 〇 small ^ more preferably 〇 · 3 ~ 5 hours to react, and one side of the alcohol formed by the reaction is removed to the outside of the system' The step of producing a polyorganismite (4) is carried out, and the step of washing the polyorganusite (a) with a solvent which does not depolymerize the organic ♦ oxygen is formed. In the production method of the polyorganismite (4), it is preferred to remove the alcohol by performing a pressure reduction at a temperature of 30 to 80 C in the above production step i). That is, the method for producing polyorganisms (4) is characterized in that, when the reaction temperature is above the point of the generated alcohol, it is generated under normal pressure at a normal temperature and under a reduced pressure when the reaction temperature is below the point of the Buddha. The alcohol is discharged to the outside of the system and allowed to react. As a result, the amount of alcohol in the reactor is reduced, and the controllability of the reaction is improved (i.e., the ester cut becomes slow and becomes easy to control). As a catalyst used in the polymerization process, a dealcoholization condensation reaction for alkoxy groups of a decyl alcohol group and an alkoxydecane compound which promotes decyl alcohol compound 159229.doc •26·201231509 can be used and esterification is carried out during the polymerization. A compound of a hydrolysis reaction or a transesterification reaction. The acidic compound or the test compound may be mentioned, and examples thereof include a metal oxide, an inorganic acid, an organic acid, an inorganic base, an organic base, and a phosphazene compound. Among them, an alkali metal hydroxide or an alkaline earth metal hydroxide, an ammonium compound or the like is preferable. As a specific example, Ba(OH) 2 and Ca(OH) 2 may be mentioned.

Mg(OH)2, KOH, LiOH, NH3, NH4OH, NR4(OH), NR4C1, NR4Br, NR4I, and the like. In NR4 (〇H), NR4CM, NR4Br and NRd, 'R is an aliphatic group, an alicyclic group or an aromatic group which may have a carbon number of a substituent. More preferably, it is an alkali metal hydroxide, an alkaline earth metal hydroxide or the like. Further, the catalyst is preferably an alkaline earth metal hydroxide, and specific examples thereof include Ba(0H)2, Ca(〇H)2, and Mg(〇H)2. Further, it is also possible to use a hydrate of Ba(OH)2, Ca(OH)2, and Mg(OH)2 for stability and shortening of reaction time, and can be reproduced by shortening the reaction time in an uneven state. From the viewpoint of performing the reaction well, Ba(0H)2.8H20 is more preferably used. The amount of the catalyst added is preferably the concentration of water such as hydration water contained in the catalyst #, or the concentration of the replacement reaction, for example, the molar amount of the added sand of the phase material is G.05 to 30 mol%. In terms of transparency and reaction controllability, it is preferably (M~2〇% by mole, more (4) Q1~iq% by mole%. 2~1〇% by mole. The so-called addition of Si atom number means The compound of the formula (1) and the alcohol compound of the formula (3) are in the reaction system, and the other moles of the condensable money compound are the number of moles of the so-called catalyst amount. Indicates how much molar catalyst is added relative to the mail atom = 159229.doc -27· 201231509. In the case of the reaction process t or the drying process (4), it is preferred to dissolve the obtained polyorganisms and not It dissolves the solvent of the catalyst, for example, when the medium is a metal oxide such as Ba(0H)2 or the shape of the metal oxide of the earth metal, it can be dissolved only by using cyclohexane and a port. The oxygen is burned (4), and then the catalyst is removed. In this case, the added solvent is slowly reduced under reduced waste and heating conditions. After the drying, the temperature is about 13 Gt, preferably thief to 13 generations, (4) is less than ^ a, preferably 15 hPa or less, and the drying time is 1 () minutes or more, preferably 30. More than a minute, more preferably! hours. The low molecular weight body can be reduced by washing the obtained fire (4) with a solvent which does not dissolve the polyorganosiloxane. As a solvent, as described above, according to the generated aggregate For example, methanol, ethanol, acetonitrile, dimethyl hydrazine, water, etc. can be used. [Because the solubility of the low molecular weight body varies depending on the solvent used, it can be repeated several times until the desired molecular weight is removed. The body is low-oxygen r(a); the body enthalpy method, as described above, is also described by adding a solvent to the polyorgano hydrazine or adding a polyorganic acid to the solvent (4) to dissolve the low molecular weight body in the solvent. In the middle, the necessary Si4 is allowed to stand 'by separating the polymer layer from the solvent layer. Thereafter: two

Si sub: The polyorganic (4) layer is recovered, whereby it can be separated separately; the polyorganosiloxane (a) with a low knife weight. After the solvent is removed under reduced pressure and heating, the 159229.doc -28 · 201231509 machine gas (o) is separately dried after separation, thereby obtaining a polyorganosiloxane having a reduced molecular weight. Alkane (a). <Photopolymerization initiator contained in the photosensitive resin composition> The photopolymerization initiator (b) used in the photosensitive resin composition of the present invention is preferably the following compound. (1) Benzophenone derivatives: for example, benzophenone, phthalic acid methyl ketone, 4-phenylhydrazine-4,-methyldiphenyl ketone, dibenzyl ketone, anthrone (2) Acetophenone derivatives: for example, 2,2,-diethoxyacetophenone, 2-hydroxy-2-nonylpropiophenone, 2,2-dimethoxy-ι, 2·diphenyl Ethane-1-one (Ciba

Manufactured by Specialty Chemicals, IRGACURE 6M), 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, IRGACURE 184), 2-mercapto 444-(methylthio)phenyl]-2-morpholinylpropane 1-one (manufactured by Ciba Specialty Chemicals, 'IGGACURE 907), 2-carbyl-l-{4-[4-(2-hydroxy-2-mercaptopropyl)phenyl]-2-} Acetylene-1 Ketone (manufactured by Ciba Specialty Chemicals, IRGACURE 127), methyl phenylglyoxylate (3). Sebutone derivatives: for example, thioxanthone, 2-mercaptothioxanthone, 2-isopropylthioxanthone, diethylthioxanthene (4) benzoin derivative: for example, benzoin, benzo醯 dimethyl ketal, benzo-β-methoxyethyl benzoin (5) benzoin derivatives: such as benzoin, benzoin methyl ether, 2_hydroxy _ 2 methyl 1 base propyl _1__ (dba Manufactured by Specialty Chemicals, DAROCURE 1173) (6) Lanthanide compounds: for example, κ phenyl-butanedione 2 _(〇_methoxycarbonyl 159229.doc -29- 201231509 肟), 1-phenyl-1,2 -propanedione-2-(0-methoxycarbonyl)indole, iota-phenyl-1,2-propanedione-2-(0-ethoxycarbonyl)anthracene, 1-phenyl-anthracene, 2-propanedione_2-(〇-phenylhydrazinyl)anthracene, diphenylpropanetrione-2-(0-ethoxycarbonyl)anthracene, 1-phenyl-3-ethoxypropanetrione -2·(0-phenylhydrazinyl)anthracene, 1_[4-(phenylthio)-1,2-octanedione 2-(0-benzylidene fluorene*)] (manufactured by Ciba Specialty Chemicals) IRGACURE OXEOl), l-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone l-(〇-acetamidine) (ciba Specialty Chemicals Manufacture, IRGACURE OXE02) (7 Α-hydroxyketone-based compound: 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-methylpropenyl)benzyl]phenyl b-2-mercaptopropane (8 An α-aminoalkylphenone compound: for example, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (manufactured by Ciba Specialty Chemicals, IRGACURE 3) 69), 2-Dimethylamino-2-(4-mercaptobenzyl)-1-(4-morpholin-4-ylphenyl)butan-1-one (manufactured by Ciba Specialty Chemicals, IRGACURE) 379) (9) A phosphine oxide-based compound: for example, bis(2,4,6-trimercaptophenyl) phenylphosphine oxide (manufactured by Ciba Specialty Chemicals, Inc., IRGACURE 819), bis(2,6-dioxin) Oxybenzhydryl)_2,4,4-tridecyl-pentylphosphine oxide, 2,4,6-trimercaptophenylenyl-diphenyl-phosphine oxide (manufactured by BASF, Lucirin (registered) Trademark), TPO) (ίο) Titanocene compound: for example, bis(115_2,4_cyclopentadiene-indole- bis-bis(2,6-a-gas-3-(1)-l-l-yl)phenyl) Titanium (ciba Specialty Chemicals 159229.doc * 30. 201231509, manufactured by the company, IRGACURE 784) When these photopolymerization initiators (b) are used, they may be used singly or in combination of two or more. In the above photopolymerization initiator (b), the benzoin derivative of (5) or the phosphine oxide compound of (9) is more preferable in terms of sensitivity and transparency. The amount thereof is 0.01 to 30 parts by mass, preferably 1 to 5 parts by mass, more preferably parts by mass, more preferably 0.3 to 1 part by mass, per part by mass of the polyorganosiloxane (a). . The amount of the photopolymerization initiator (b) to be added is 〇〇1 part by mass or more, and from the viewpoint of transparency, it is 3 parts by mass or less from the viewpoint of obtaining a practical hardening pattern. <Equivalent-saturated addition polymerizable monomer contained in the photosensitive resin composition> Further, the photosensitive resin composition of the present invention preferably contains an ethylenically unsaturated addition polymerizable monomer (4) (hereinafter) , also known as "single". As the monomer to be added to the photosensitive resin composition, a compound containing an acrylonitrile group or a methyl methacrylate group can be used from the viewpoint of improving crack resistance, heat resistance and hardness. Specific examples of the monomers that can be used are disclosed below. - A monomer having a polyalkyl ether chain or an oligomeric alkyl ether chain represented by the following formula (9), which is a monomer which increases the cracking property of 4, H2C C(R)-(c = 〇)_〇_(P〇)mi_(E〇n=〇)_c(R)=cH2 (9) (wherein R is hydrogen or methyl, PO is propylene oxide, and E is epoxy B Alkyl group, W is less than 30, n is less than 3 于 in the presence of both p〇 and 〇, and it can exist in a random manner or in a block manner, 159229.doc -31 - 201231509 m'+n' is less than 6〇}. For example, as a monomer, it can be listed. 〇〇』芈. Polyethylene glycol diacrylate [Ethylene glycol is 2~20] Poly(1) dimethyl dimethyl acrylate (the number of ethylene glycol units is 2 to 20), poly (1,2 propylene glycol) di acrylate, 2 propylene glycol units 2 to 2 〇], and Poly(1,2-propylene glycol) dimethacrylate [1,2-propanediol unit number is 2 to 20]. As the monomer for improving heat resistance, a compound having an alicyclic group is preferable, for example, the following formula (10) The monomer having an alicyclic group and the polycyclic ring represented by the following formula (12) Monomer, C(R)(CO)-OY -X'-Y2-〇-(c=〇)-C(R)=CH2 (10) {wherein R is hydrogen or methyl, γ\ Γ2 is an organic group containing a carbon number of an oxiranyl group and/or an oxypropylene group, and X is a substituent having a cyclohexyl group represented by the following formula (U)} χ,= 〇—οκ&gt; [化5] r

(12) In the formula, γ and x&quot; are hydrogen, or an organic group containing an alkyl group, an oxiranyl group or an propylene oxide group, and at least one of Y, and X, is an acryloxy group, A Alkyl oxime oxy, propylene oxime oxime or methacryloxymethyl}. Examples of the monomer represented by the above formulas (10) and (12) include 1,4-cyclohexanedicarboxylate, 14-cyclohexanedicarboxylate, and 159229.doc-32- 201231509 Oxylated (hydrogenated bisphenol A) diacrylate [ethylene glycol unit number is 2~3〇], ethoxylated (hydrogenated bisphenol A) dimethacrylate [the number of ethylene glycol units is 2~30], tricyclodecane dimethanol dimethacrylate, tricyclodecane dimethanol diacrylate, dicyclopentanyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, Dicyclopentyl methacrylate, and dicyclopentenyloxyethyl methacrylate. Examples of the monomer for increasing the refractive index include a monomer having a benzene ring represented by the following formula (13), and f% H2c=c(R)-(c=〇).〇.YLX....Y2 〇.(c=〇)_C(R)=CH2 {wherein R is hydrogen or methyl, Y is &amp; Y2 is a carbon number 1 to 90 containing an oxiranyl group and/or an oxypropylene group The organic group, and χ&quot;, represents a general formula (a substituent having an aromatic group represented by one sentence) [Chemical 6] X·&quot;

(14)

Examples of the monomer represented by the above formula (9) include a bis-A diglycidyl ether-acrylic acid addition product, a bisphenol A diglycidyl ether-methacrylic acid addition product, and an ethoxylation (tetra) propylene return. The number of acid (tetra) ethylene glycol units is 2 bone ethoxylated bis-octane octamethyl acrylate (the number of B is 2 to 30). As a monomer for improving hardness and photosensitivity, it is possible to feed a monomer having three or more propylene or methyl propyl groups in the formula (15), (H2C=C(R)-(C=〇 )-〇-Y)n_x ...丨(15) 159229.doc -33- 201231509 {wherein, R is hydrogen or methyl, and γ is a carbon number 1 containing an oxiranyl group and/or an oxypropylene group. The organic group of 90, X&quot;&quot; is an η-valent organic group having a carbon number of 1 to 6, and η is 3 or 4}. Examples of the monomer represented by the above formula (15) include pentaerythritol tripropionate, pentaerythritol tetraacrylate, trihydroxydecyl propane triacrylate acrylate, and ethoxylated tris(tetra)propylpropane tripropylene. Acid [the number of ethylene glycol units is 2 20] - methacrylic acid trimethacrylate, tris(2_ylethyl)isocyanuric acid triacrylate, tris(2-hydroxyethyl)isocyanuric acid Trimethacrylate, bis(trihydroxydecylpropane)triacrylate, bis(trihydroxymethylpropane)tetrapropene I from Japan, dipentaerythritol pentaacetic acid vinegar, dipentaerythritol hexaacrylate acid vinegar, and the like. In addition, when the above-mentioned monomers are used, they may be used singly or in combination of two or more kinds as needed. In view of the crack resistance, the heat resistance, the refractive index, and the viscosity (operability), a specific example in which the monomer 4 having an alicyclic group is a monomer having an alicyclic structure is exemplified, and examples thereof include: Tricyclohexane dimethanol dimethyl propylene 8 fat, tricyclohexan dimethanol dipropylene dilute, dicyclopentyl (tetra) acid vinegar,: cyclopentyl methacrylate vinegar, hydrogenation, etc. Moreover, the number of phenolic oxime-modified bismuth acrylate (diox) units is reduced, and the hydrogenated bismuth oxime oxime modified methyl group, dilute (the number of epoxidized units is 10), etc. From the viewpoint of cracking, it is completed, and it is preferable to use δ, and further preferably, in addition to the alicyclic soil, and then use a monomer having an extended alkyl group. Specific examples of the monomer may be: polyethylene glycol #400 acrylate of the general formula (9) (m = 〇, η = 9), non-acid vinegar (tetra),, polyethylene glycol _,;: _ Propylene 7-based acrylate (m = 〇, 159229.doc -34 &gt; 201231509 n = 9), polyethylene glycol #6 methacrylate (m = hydrazine, etc.. The above-mentioned ethylenic unsaturated addition polymerization property The amount of the substance (c) (i.e., one or more compounds selected from the group consisting of acrylic or methyl acetonate) is O.^WOO mass relative to 100 parts by mass of the polyorganosiloxane (a). The portion is preferably 1 to 500 parts by mass, and more preferably 2 to 2 parts by mass, and is preferably 5 to 1 part by mass in terms of heat resistance. &lt;Other additives&gt; A photosensitive resin composition having properties excellent in light resistance of a molded article after curing is provided, and the photosensitive resin composition of the present invention may further comprise a group selected from the group consisting of an ultraviolet absorber and a light stabilizer containing a hindered amine. At least one compound, in the case of addition, the total amount of the additive is preferably set to be the amount of the stomach in the case of the polyoxygen (4) (10) f, which is better in terms of transparency and thermal weight loss. It is set to 0.01 to 20 parts by mass. In the case of containing a UV absorber or a light-stable amine containing a hindered amine (4) ο = addition amount _ in the poly (4) oxygen appearance (4) _ mass part is preferably set to Jin 50 quality reading, More preferably, it is set to i, the mass part. If the amount is added to the quality Therefore, it is possible to effectively improve the weather resistance of the cured product and the light resistance = the amount of addition to the amount of 5 Gf or less, and the high transmittance of the photosensitive material and the cured molded product after the addition can be maintained, and the light resistance and the resistance are improved. : A photosensitive resin composition which maintains a high adhesion to an inorganic material substrate such as glass or metal, and a subsequent additive such as a decane coupling agent may be added to a combination of a resin and a resin. 35- 201231509 Especially in terms of price or harmfulness, 3-glycidoxypropyltrimethoxydecane (Shin-Etsu Chemical Co., Ltd. kbm_403), 3-methylpropenyloxypropyl group is preferred. Trimethoxy decane (Shin-Etsu Chemical Co., Ltd. KBM-503), 3-aminopropyltriethoxy zeshi (Shin-Etsu Chemical Co., Ltd. KBE-903). In the case where the decane coupling agent is contained, the amount of addition is preferably 100 parts by mass, more preferably 10 to 50 parts by mass, based on 100 parts by mass of the polyorgano oxyazepine (a). When the amount of addition is i parts by mass or more, a cured molded article which retains excellent adhesion to an inorganic material substrate such as glass or metal can be obtained. A sensitizer for improving the sensitivity may be added to the photosensitive resin composition of the present invention as needed. Examples of such a sensitizer include, for example, rice ketone, 4,4,-bis(diethylamino)benzophenone, and 2,5-bis(4,2-diethylamino) Benzyl)cyclopentanone, 2,6-bis(4,-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4,-dimethylaminobenzylidene)·4· Methylcyclohexanone, 2,6-bis(4,2-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone 4 '4-Bis(monoethylamino)chalcone, 2-(4'-dimethylamino cinnamic acid) 茚, 2-(4'-dimethylaminobenzylidene) fluorenone , 2_(p-_4,_didecylaminobiphenyl)benzoindole, bis(4)dimethylaminosuccine) propionium, 1,3_bis(4-diethylamino) Benzylene)acetone, 3,3, carbonyl bis(7-diethylaminocoumarin), 3-ethoxyphenyl_7-dimethylamino coumarin' ethoxycarbonyl-7-di Methylamino coumarin, 3-benzyloxycarbonyl-7-dimethylamine glucoside, 3-methoxycarbonyl-7-diethylamino coumarin, 3-ethoxycarbonyl Ethylamine coumarin, N-phenyl-N-ethylethanolamine, N-phenyl I59229.doc -36 - 20123 1509 Diethyl-alcoholamine, phenyldiethanolamine, hydrazine-phenylethanolamine, hydrazine, hydrazine-bis(2-hydroxyethyl)aniline, 4·morpholinylbenzophenone, bistrioxyl benzene Acid isotonic vinegar, 4-diethylaminobenzionic acid isotonic vinegar, benzotrisodium, 2_mercaptobenzimidazole, 〗-phenyl-5-whale base 152,3,4_tetraindole Ο When the base is like 4·, 〖-(t-butyl)~-cut, 4·= base t is basic and (4), 2-(p-dimethylamino stupidyl) benzo-sit, 2_ ( p-Dimethylaminophenylvinyl)benzopyrene, 2-(p-dimethylaminophenylethyl)naphthoquinone (1,2·Ρ) vomiting, 2_(p-dimethylamino benzene A brewed base) styrene and the like. Further, these compounds may be used singly or in the form of a mixture of two or more. The amount of addition in the case where the sensitizer is added depends on the amount of the other additive component, but is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, based on the polyorgano oxysulfuric acid (4). In the photosensitive resin composition of the present invention, a polymerization inhibitor may be added as needed to improve stability during storage or sensitivity. As such a polymerization inhibitor, for example, it is possible to use: p-benzoic acid, hydrazine-nitroso-diphenylamine, p-butylene phthalate, sputum p, ν_phenyl ceamine, ethylenediamine Tetraethyl acid,", 2_cyclohexanediaminetetraacetic acid, ethylene glycol guanidine diamine tetraacetic acid, 2:6-di-t-butyl-p-methyl benzene, % nitroso _8_ , "Asia ^ Cai Rin 2 nitroso-naphthol, 2-nitroso-5-(Ν-ethyl-Ν-sulfopropyl 2 amine group) stupid, Ν _ nitroso Ν phenyl (four) (four) ^基和amp;amine salt, Ν_nitroso_ν_(ι_naphthyl) via amine ammonium salt, bis(4_open^3,5·di-t-butyl) phenyl ketone, etc. Addition polymerization The amount of the inhibitor + is preferably 0.001 to 5 parts by mass, more preferably 0.0 W by mass, based on 100 parts by mass of the polyorganisms (4). 159229.doc -37- 201231509 The photosensitive resin of the present invention In the composition, an antioxidant may be added in order to improve the thermal stability in the presence of oxygen. Examples of such an antioxidant include hindered phenol, phosphorus, lactone, vitamin E, and sulfur. Illustratively, it can be exemplified: triethylene glycol bis[3-(3-tert-butyl-5-- Methyl-4-hydroxyphenyl)propionate] (IRGANOX 245, manufactured by BASF Corporation), 1,6-hexanedialdehyde bis[3-(3,5-di-t-butyl-4-hydroxyphenyl) Propionate KBASF company IRGANOX 259), 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-three Plowing (IRGANOX 565, manufactured by BASF), pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (IRGANOX 1010, manufactured by BASF), 2,2-sulfur Diethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (IRGANOX 1035, manufactured by BASF), 3-(3,5-di-3rd Octadecyl 4-hydroxyphenyl)propanoate (IRGANOX 1076, manufactured by BASF Corporation), hydrazine, Ν1-hexamethylene bis(3,5-di-t-butyl-4-hydroxyphenylpropanamide) (IRGANOX 1098 manufactured by BASF Corporation), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (1 〇8 1^00 295 manufactured by 8 8 8 Company), 1, 3 , 5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene (IRGANOX 1330 manufactured by BASF Corporation), three (3,5-two third) Butyl-4-hydroxybenzyl)isocyanurate (I manufactured by BASF) RGANOX 3114), octylated diphenylamine (IRGANOX 5057 manufactured by BASF Corporation), 2,4-bis[(octylthio)methyl] o-cresol (IRGANOX 1520L manufactured by BASF Corporation) ' 3-(3 , 5-di-t-butyl-4-hydroxyphenyl)propionic acid isooctyl ester (IRGANOX 1135, manufactured by BASF Corporation), 2,4-bis(dodecylthiomethyl)-6-methylphenol (IRGANOX 1 726 manufactured by BASF Corporation), 2,5,7,8-tetramethyl-2- 159229.doc • 38 - 201231509

(4,8,12-trimethyltridecyl)chroman-6-ol (11^ into 1^〇 and £201 by BASF), 5,7-di-t-butyl-3-( 3,4-Dimethylphenyl) benzofuran-2(3H)-one (IRGANOX HP-136), tris(2,4-di-t-butylphenyl) phosphite (IRGAFOS 168, manufactured by BASF) ), three [2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[山,[1,3,2]diphosphoranecycloheptane-6- Alkyloxy]ethyl]amine (manufactured by BASF Corporation, IRGAFOS 12), bis(2,4-di-tert-butyl-6-nonylphenyl)ethyl phosphite (IRGAFOS 3 8 manufactured by BASF Corporation) , 3,3-thiobispropanoic acid di-dodecyl ester (IRGANOX PS800 manufactured by BASF Corporation), 3,3-thiobispropanoic acid di-octadecyl ester (IRGANOX PS802 manufactured by BASF Corporation) ,3,9-bis[2·[3-(3·t-butyl-4-transyl-5·nonylphenyl)propenyloxy]-l,l-dimethylethyl]- 2,4,8,10-Tetraoxaspiro[5,5]undecane (SUMILIZER GA-80, manufactured by Sumitomo Chemical Co., Ltd.), 2,2'-arylene di(6-tert-butylfluorenyl) Phenol) (SUMILIZER MDP-S by Sumitomo Chemical Co., Ltd.), 4,4'-butylidene bis(6-tert-butyl-3-methyl Phenol) (SUMILIZER BBM-S, manufactured by Sumitomo Chemical Co., Ltd.), 4,4'-thiobis(6-tert-butyl-3-methylbenzoquinone, hydrazine, phenol) (manufactured by Sumitomo Chemical Co., Ltd.) SUMILIZER WX-R), quaternary tetraol tetrakis(3-lauryl thiopropionate) (SUMILIZER TP-D manufactured by Sumitomo Chemical Co., Ltd.), 2-mercaptobenzopyrene (SUMILIZER MB manufactured by Sumitomo Chemical Co., Ltd.) ), biphenyl-4,4'-diylbis[bis(2,4-di-t-butyl-5-nonylphenoxy)phosphine] (GSY-P1 01 manufactured by Osaki Industries Co., Ltd.), etc. It is not limited to these. Further, the antioxidants may be used singly or in the form of a mixture of 2 Torr or more. The amount of the antioxidant added is preferably 0.001 to 30 parts by mass, more preferably 159 to 229 parts by weight, more preferably 159 to 229 parts by weight, based on 100 parts by mass of the polyorganosiloxane (a). In the photosensitive resin composition of the present invention, various additives such as a coating film smoothness imparting agent and inorganic fine particles may be appropriately added as needed, as long as the properties of the photosensitive resin composition of the present invention are not inhibited. &lt;Solvent&gt; The solvent may be added to the photosensitive resin composition of the present invention to adjust the viscosity. Preferred examples of the solvent include N,N_: methylformamide and N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP (N_Methyl_2_ py 1^4〇116)"),]^-B.基-2-'1 比嘻院_,四氢吱0南' team; ^-dimethylacetamide (hereinafter, also known as "DMAc(N, N-dimethyl • tamide)") , hexamethylphosphoniumamine, acridine, cyclopentanone, γ-butyrolactone (hereinafter, also referred to as "GBL (y_butyr〇lact〇ne)"), α_乙乙基丁内西,四Methylurea, 1,3-dimethyl-2-imidone, Ν-cyclohexyl-2-pyrrolidone, propylene glycol monoterpene ether, propylene glycol monomethyl ether acetate, hydrazine methyl ethyl ketone, methyl isobutyl Ketone, methyl ether, ethyl acetate, milk Sic, butyl lactate, etc., which may be used singly or in the form of two or more. Among these, N-mercapto-2-pyrrolidone or γ-butane s day and propanol monoterpene ether acetate are particularly preferable. The solvent may be appropriately added to the photosensitive resin composition in accordance with the thickness and viscosity of the coating film, but it is preferably used in an amount of from 0 to 200 parts by mass based on 100 parts by mass of the polyorganosiloxane (a). . &lt;Cured product&gt; 2 In one embodiment of the present invention, the photosensitive resin resin of the present invention or the method for producing the polyorganosiloxane is used to obtain 159229.d〇 (201231509) The photosensitive resin composition of the organic siloxane (a) and the photopolymerization initiator (b) is photocured to obtain a cured product. <Method for Producing Molded Article> Hereinafter, the photosensitive resin composition using the present invention is used. For the molded article, for example, a plastic microlens or an optical element for a liquid crystal polarizing plate is used. In the present specification, a plastic microlens discloses a minute plastic having a diameter of usually several millimeters or less. In the CCD image sensor or LCD (liquid crystal display) projector, a microlens array in which a plurality of microlenses having a diameter of several tens μπ 1 are disposed in order to improve light use efficiency is used in the optical communication connector. Or a microlens having a diameter of several hundred pm or the like in a camera module of a mobile phone. Also, an optical element for a liquid crystal polarizing plate is used as a liquid crystal projector or liquid. A structure on a polarizing plate (polarizing plate) of one of the display members. Usually, in the liquid crystal panel, a set of polarizing mirrors (polarizing plates) is disposed on the back surface of the transparent substrate on which the liquid crystal is sealed, and only a certain polarization direction is polarized. The liquid crystal polarizing plate can be produced by extending the film to align the composition, etc., but can also be formed as a polarizing mirror by forming a specific structure on the substrate at a distance of 〜2 to 3 μηι. The optical element for the plastic microlens and the liquid crystal polarizing plate differs only in the size and type of the mold, and the manufacturing method of the two is the same. Specifically, the manufacturing method of the molded article of the present invention includes the following steps: 1) sensitizing the present invention The resin composition or the photosensitive 159229.doc -41 - 201231509 resin composition containing the polyorganosiloxane (a) and the photopolymerization initiator (b) obtained by the above production method are filled into a molding die a step of 2) exposing the σ portion (4) of the mold to the substrate or another mold, 3) exposing the photosensitive resin composition from the mold and/or the substrate side And obtaining the photo-cured material, 4) removing the mold from the substrate or peeling the mold on both sides, and 5) adding only the photo-cured material to the substrate, or bonding the photo-cured material to the substrate And the step of heating. 1) a step of filling the photosensitive resin composition into a molding die, filling the photosensitive resin composition into the molding die from the opening of the molding die, or dropping the photosensitive resin composition into the substrate or the mold, The substrate or the mold is pressed so as to become a substrate/photosensitive tree gambling composition/mold or a mold/photosensitive resin composition/mold, and the photosensitive resin composition is filled in a molding die. In the case of being applied to the opening of the molding die, the photosensitive resin composition may be dropped onto the opening of the molding die by using a dropper or a dispenser. Further, when applied to the substrate side, a dropper or a dispenser is used for dropping, or a spin coater, a bar coater, a knife coater, or a curtain coater is used. The film is applied by a printing machine or the like, or spray-coated by a spray coater or the like to apply a photosensitive resin composition onto a substrate subjected to pretreatment as necessary to form a film of the photosensitive resin composition. The thickness of the photosensitive resin composition is preferably from 0 to 10 mm, more preferably from 5 to 1 mm, still more preferably from 1 to 500 μm. When the photosensitive resin group is coated, it may be diluted with a solvent such as hydrazine. However, in this case, the step of removing the solvent used by heating by I59229.doc -42·201231509 becomes the photosensitive property of the coated substrate. The film formation of the resin composition is faced with:: 吏; as a heating device, as long as it is an oven or a device capable of heating far-infrared rays, it is possible to use 5, rc, 15 (rc, preferably 100 t ^ conditions). υ &lt; 围, 1 minute ~ 8:, preferably 5 minutes ~ 10 minutes. In addition, even if the solvent is not used: the photosensitive resin composition is diluted, the substrate and the photosensitive Ο tree are improved. From the viewpoint of the adhesion of the substance, the step of heating each substrate can be arbitrarily added. As the device used in this case, the heating plate 0 is preferably used as a pretreatment for the substrate, in order to impart a substrate. The adhesion of the decane coupling agent may be applied to the substrate as appropriate. When the barrier of the decane coupling agent is applied, the hairpin coupling agent is diluted with an organic solvent such as NMP, and coated by a spin coater or a bar coat. Cloth machine, knife coating machine After coating with a curtain coater, a screen printer, etc., the solvent to be used is removed by heating, and the heating is carried out by using a known person such as an oven, a far-infrared furnace, or a heating plate. The chemical species of the mixture is preferably 3-glycidoxypropyltrimethoxydecane (Shin-Etsu Chemical Co., Ltd. kbm_4〇3), 3-mercaptopropenyloxypropyltrimethoxydecane (Shin-Etsu Chemical) Industrial Co., Ltd. ΚΒΜ-503), 3-propenyloxypropyltrimethoxydecane (Shin-Etsu Chemical Co., Ltd. ΚΒΜ-5103), 3-aminopropyltriethoxydecane (Shin-Etsu Chemical Industry Co., Ltd.) ΚΒΕ-903), etc. As the substrate, for example, a copper substrate such as a glass substrate, a quartz substrate, a tantalum substrate, or a copper box laminate can be used. The mold for molding is a material that does not transmit light 159229.doc -43- 201231509 In the case of a glass substrate or a quartz substrate, 2) a step of pressing the opening of the molding die onto the substrate or another mold, for example, a mold for molding, for example, a mold for a microlens or an optical element for a liquid crystal polarizing plate. The opening of the mold is formed on the substrate or the film on the other mold. At this time, it is also possible to pressurize as needed. As a material for the mold for molding, rubber, glass, and polydimethyl sulphur oxide are mentioned. It is preferable to use a resin such as a resin or a metal such as a transparent resin. In the case of the method for producing a molded article of the present invention, when the opening of the mold is pressed against the substrate, it is preferable to add it before the step. The step of applying a decane coupling agent to the substrate, in the step of pressing the opening of the mold onto the substrate, preferably, the opening of the mold is pressed against the surface of the substrate coated with the decane coupling agent. The step of exposing the photosensitive resin composition to the mold and/or the substrate side to obtain a photocured material is such that the photosensitive resin composition is sandwiched between the substrate and the molding die, and the exposure light can be obtained from the molding die or the substrate. The side of the transmissive material is exposed to ultraviolet light. If necessary, the ultraviolet rays may be irradiated from both sides of the laminate in a state in which the substrate and the molding die or the mold are sandwiched with the photosensitive resin composition. From the viewpoint of the resolution and workability of the pattern of the photocurable resin, the wavelength of the exposure light source is preferably x-ray. 4) The step of peeling the mold from the substrate or peeling off the mold on both sides After the ultraviolet curing, the molding die is peeled off from the substrate or the molds on both sides are peeled off. 5) Only heat the photo-cured material, or heat the photo-cured material together with the substrate. 159229.doc -44 · 201231509 (PEB (P〇st exp0SUre bake)) at 15 (TC~) Heating at a temperature of 270 t for 5 seconds to 5 hours, whereby the remaining reactive groups are bonded to obtain a molded article excellent in heat resistance, for example, an optical element for a plastic microlens or a liquid crystal polarizing plate, and a heating plate or a supply box can be used for heating. The temperature can be set to a temperature-increasing oven. The ambient gas during heating can be air, preferably an inert gas such as nitrogen gas argon. Further, the heating step is to increase the molded object such as a plastic microlens. Or the step of arbitrarily adding the hardness of the optical element for the liquid crystal polarizing plate. The molded article of the present invention can be obtained by performing the above-described steps. &lt;Method for forming hardened concave-convex pattern and polyorganosiloxane film&gt; Hereinafter, an example of a method of forming a cured concavo-convex pattern using the photosensitive resin composition of the present invention will be described. The method for producing a cured concavo-convex pattern includes the following steps: 1) Coating the hair The photosensitive resin composition or the photosensitive resin composition containing the polyorganosiloxane (a) and the photopolymerization initiator (b) obtained by the method for producing a polyorganosiloxane of the present invention is coated. a step of sputum, 2) a step of irradiating the coating film with actinic light to photoharden the exposed portion, 3) a step of removing the uncured portion of the film using a developing solution, and 4) heating the hardened portion together with the substrate The steps. 1) Step of obtaining a coating film by applying the photosensitive resin composition of the present invention First, the photosensitive resin composition of the present invention is applied to a silicon wafer, a ceramic substrate, an aluminum substrate, and the like. Needed on a variety of substrates. As the coating device or the coating method, a spin coater, a die coater, a spray coater, a dipping, a printing, a knife coater, a roll coating method, or the like can be used. The coated substrate was soft baked for 10 seconds to 1 hour at 159229.doc -45·201231509 80~200°c. 2) The step of irradiating the coating film with the active light to harden the exposed portion is performed by using an exposure projection device such as a contact aligner, a mirror projection, or a stepper, and irradiating the active light through a desired mask. As the active light, X-rays, electron beams, ultraviolet rays, visible rays, and the like can be used, but in the present invention, it is preferred to use a wavelength of 200 to 500 nm. From the viewpoint of resolution and operability of the pattern, the wavelength of the light source is particularly preferably uv_i ray (365 nm) as an exposure projection device, which is particularly preferably a stepping machine. After step 2), in order to increase the sensitivity and the like, it may be necessary to perform a post-exposure bake in any combination of temperature and time (preferably temperature 4 (rc~2〇(rc, time 1 〜 to 3 〇 minutes)). Bake (PEB, Post exposure bake) or pre-development bake. 3) Step of removing the uncured portion of the film using a developing solution This step can be carried out by a dipping method, a liquid coating method, or a rotary spray method. As the developer, a good solvent of the photosensitive resin composition of the present invention or a good solvent and a poor solvent may be used as appropriate. Examples of the good solvent include N-methyl-2-pyrrolidone. N_acetamido_2_pyrrolidone' N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulphur, P-butyrolactone, α-ethinyl-γ _butyrolactone, cyclopentanone, cyclohexanone, propylene glycol monoterpene ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl _, etc. "As a poor solvent, methanol, ethanol , isopropyl alcohol, water, etc. After the development is completed, the eluent is used for cleaning, and the developer is removed, thereby obtaining a bump map. As the eluent, it may be used alone or as appropriate 159229.doc 46· 201231509 in combination with distilled water 'decanol, ethanol, isopropanol, propylene glycol monomethyl ether, etc., or may be used in combination in stages. The step of heating the hardened portion together with the substrate ((final) heating step, PEB treatment) has a concave-convex pattern obtained at 150 to 260 in the manner as described above. (: It can be converted into a hardened concave-convex pattern. This heat-hardening can be carried out using a heating plate, an oxidation-free oven, a temperature-increasing oven capable of setting a temperature program, etc. as heat hardening.

At the time of the ambient gas, the atmosphere (air) may be used, and an inert gas such as nitrogen or argon may be used as needed. The hardened concavo-convex pattern obtained by the above-described manufacturing method is used as a surface protective film selected from a semiconductor device formed on a substrate such as an a-day a 15 , an interlayer insulating film, a micro-structure such as an X-ray shielding film or a microlens array, and a package thereof Any one of the groups of the support (separation wall) between the materials, and further, other steps in the manufacturing method of the well-known semiconductor device, whereby various optical components including CMOS image sensors can be manufactured Further, in the semiconductor device, an electronic component or a semiconductor device including a coating film of a resin obtained by curing the photosensitive resin composition can be obtained. [Embodiment] The scope of the invention is not limited thereto. 1] The photosensitive resin composition is added to a 2 L separable roasting ketone as a decyl alcohol compound of dicyclopentyl decanediol 1.37 mol (275 裒 ^ 1 乍 is an oxodecane compound eve ( CH3〇)3-Si-(CH2)3-〇-(c=〇)_c(CH, (H3)=CH2 1.37 Mo (341 159229.doc -47- 201231509 g), and Ba as a catalyst 〇H)2 · h20 0.00858 Mo (1.63 g), installed In a state where the Liebig condenser for removing the produced alcohol is removed, the pressure reduction of 5 〇〇hpa in an oil bath is gradually increased from room temperature to 5 (rc, and the reaction solution becomes after the reaction starts. When it is transparent (that is, the dicyclopentyl decanediol is dissolved), the pressure is reduced to 25 〇 hPa. In this state, stirring is continued, and the thus-produced collagen is cooled and liquefied by a Liebig cooling tube, and the removal is started until the system is confirmed. After this state, the reaction was further continued for 2 hours. Then, the degree of vacuum was slowly lowered at the same temperature as the time of the depressurization so as not to cause a bump, and the reaction was continued while removing the decyl alcohol at 8 to 15 hPaT. Finally, the reaction was resumed to normal pressure to complete the removal of methanol. The obtained white turbid viscous liquid was dissolved in cyclohexane, filtered, and the solvent was removed by an evaporator, and then vacuum-extracted at 8 (rc for 3 minutes). After standing to cool, after returning to room temperature, methanol was added, stirring was carried out, the supernatant was removed, and the above operation was repeated three times. The obtained methanol-insoluble portion was obtained at 60 ° C using an evaporator. After removal, it was dried at 8 Torr &lt;&gt;c for 1 to 5 hours. The obtained polyorganosiloxane had a weight average molecular weight of 5,329. Among the obtained polyorganosiloxanes, the number of Si atoms was 3〇. % is contained in the structure represented by the above formula (2) (wherein, X is -(CH2)3·) (determined by 13C-NMR). The peak of the carboxylic acid-derived ester moiety in the iH_NMR is 31. °/., in the GPC chart, the weight average molecular weight is ι, and the area above 〇5〇 is 83°/〇 (Fig. 1, Fig. 2 and Fig. 3). 2 parts by mass of a photoradical polymerization initiator DAROCURE 1173 (manufactured by Ciba Co., Ltd.) was added to 100 parts by mass of the polyorganosiloxane to obtain a photosensitive resin composition. 159229.doc -48 - 201231509 The reduction rate of the ester-derived peaks from the ester sites is based on the comparison of (CH30)3-Si-(CH2)3-0-(C=0)-C in the 1H-NMR spectrum. CH3)=CH2 is calculated by -C=CH2 and Si-CH2-. [Example 2] The photosensitive resin composition was replaced with (CH30)3-Si-(CH2)3-0-(C=0)-CH=CH2 instead of (CH30)3-Si-(CH2)3 of Example 1. -0-(C=0)-C(CH3)=CH(CH3), reacting

The synthesis of the polyorganosiloxane was carried out in the same manner as in Example 75 except that acetonitrile was used instead of methanol as the cleaning solvent for the obtained polyorganosiloxane. The polyorganosiloxane obtained had a weight average molecular weight of 1,582. In the obtained polyorganosiloxane, "the 27% of the atomic number is contained in the structure represented by the above formula (2), and the oxime is (the ester moiety in the Η-NMR is determined by 13C-NMR). The peak of the carboxylic acid is reduced by 29% (Fig. 4). The photoradical polymerization initiator Lucirin (registered trademark) tp〇 (manufactured by Basf Co., Ltd.) is added to 1 part by mass of the obtained polyorganosiloxane. The photosensitive resin composition was obtained in an amount of 2 parts by mass. The reduction rate of the peak derived from the carboxylic acid of the ester moiety was obtained by comparing (CH30)3-Si-(CH2)3-〇- in the h _ n Μ r spectrum. C=〇)-CH=CH2 _CH=CH2 (5.80 ppm, 6.10 ppm, peak near 6.37 ppm) and 8丨 even_2 (peak near 0.65 ppm) were calculated. [Example 3] Photosensitive The resin composition was carried out in the same manner as in Example 2 except that the reaction time of Example 2 was set to 6 Torr. The weight average of the obtained polyorganisms was = the amount = ... In the financial oxygenation, the number of atoms (1) is contained in the structure represented by the above formula (7), and Μ 159229.doc •49· 201231509 -(CH2)3-(determined by 丨3C_NMR) The peak of the carboxylic acid-derived ester at the ester site was reduced by 22% in 1H-NMR. [Example 4] The photosensitive resin composition was the same as Example 2 except that the reaction time of Example 2 was 45 minutes. The weight average molecular weight of the obtained polyorganosiloxane is 1,380. In the obtained polyorganosiloxane, the number of atoms of &amp; 12 ° / is contained in the above formula (2) In the structure indicated and X is -(CH2)3. The peak of the carboxylic acid derived from the ester moiety in the 1H-NMR is reduced by 13%. [Example 5] The photosensitive resin composition except the reaction time of Example 2. The reaction was carried out in the same manner as in Example 2 except that the weight average molecular weight of the obtained polyorganosiloxane was 1,260. Among the obtained polyorganosiloxanes, the number of atoms was & 9% is contained in the structure represented by the above formula (2), and χ is -(CH2)3·(determined by 13C-NMR). The peak of the carboxylic acid-derived peak at the iH_NMRt ester site is reduced by 9°/〇. [Example 6] Photosensitive resin composition After the photosensitive resin of Example 1 was cooled to room temperature, photoradical polymerization was added thereto. At the same time as the initiator, the same treatment as in Example 进行 was carried out, except that 5 mass% of A_600 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and A_DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.) were added in an amount of 45 mass%. The photosensitive resin composition was obtained. [Example 7] Photosensitive resin composition After cooling the photosensitive resin of Example 2 to room temperature, it was added with the light free 159229.doc • 50-201231509-based polymerization initiator. The same treatment was carried out to obtain photosensitivity, except that A-600 (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added in an amount of 1% by mass and A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.). Resin composition β [Example 8]. (CH30)3-Si-(CH2)3-〇-(C=〇)-CH=CH2 was added as alkoxydecane compound in a 2 L separable flask. 0.2 mol (49.8 g), Ba(OH)2 · H2 〇 0.001 mol (0·19 g) as a catalyst, and leeches 18 moir (3.24 phantom, used to remove the alcohol produced In the state of the Liebig cooling tube, decompression at 250 hPa in an oil bath, slowing from room temperature Warmed to 50 ° C. Stirring was continued in this state, and the methanol thus produced was cooled and liquefied by a Liebig cooling tube, and the removal was started until the outside of the system. After confirming this state, the reaction was further continued for 2 hours. Thereafter, the reaction temperature was slowly raised to 8 (TC, and thereafter, after further reacting for 2 hours, the degree of vacuum was slowly lowered so as not to cause a bump, and the methanol was removed at 8 to 15 hpaT 〇$. - The surface was further reacted for 2 hours. Finally, the reaction was returned to normal pressure to complete the removal of methanol. The obtained white turbid viscous liquid was dissolved in the ring hexagram, and after the hydrazine was removed, the solvent was removed at 8 〇. Vacuum evacuation was carried out for 3 minutes at t. After cooling, return to room temperature, add methanol, stir the mixture, remove the supernatant, and repeat the above operation three times. The obtained methanol-insoluble HMGC was used. After partial removal, it is dried under the machine for 1.5 hours. The polyorgano 7 oxygen obtained by the weight average molecular molecule of the obtained polyorganosiloxane is obtained in the above formula (2). Within the structure indicated, and X is _(ch2)3- 159229.doc 51 201231509 (determined by ^C-NMR). The peak of the carboxylic acid-derived peak of the brewed portion was reduced by 16% in 1H-NMR. 1] A photosensitive resin composition is added to a 300 mL separable flask Dicyclopentyl decanediol of a stanol compound 0.1 50 mol (3 〇.〇g) '(CH30)3-Si-(CH2)3-0-(C=0)- as an alkoxydecane compound C(CH3)=CH2 0.15 Molar (37.2 g), and Ba(OH)2.H2〇〇〇〇〇3 Moer (〇〇945 g) as a catalyst, useful for installation to remove the alcohol produced In the state of the Liebig cooling tube, the decompression of 500 hPa was carried out in an oil bath. The king, the dish was softly opened to 50 ° C, and the reaction solution became transparent after the reaction started (ie, dicyclopentyl decane II). When the alcohol was dissolved, the pressure was reduced to 25 〇 hPa. In this state, the stirring was continued, and the methanol produced by the use of a Liebig cooling tube was cooled and liquefied, and the removal was started outside the system. After confirming this state, the reaction was further carried out for 2 hours. Then, at the same temperature as the depressurization time, the degree of vacuum was gradually lowered so as not to cause a bump, and the reaction was further continued for 2 hours while removing methanol at 8 to 15 hPa. Finally, the pressure was returned to normal pressure. And the sterol removal is completed. The obtained white turbid viscous liquid is dissolved in cyclohexane, and the evaporator is used after filtration. After removing the solvent, vacuum suction was carried out for 30 minutes at 80 ° C. The weight average molecular weight of the obtained polyorganosiloxane was L002. Among the obtained polyorganosiloxanes, the number of Si atoms was less than 1%. Included in the structure represented by the above formula (2), and X is -(CH2)3- (by i3c_R/贞丨疋). The peak of the carboxylic acid derived from the ester moiety in 1 Η·ΝΜΙΙ The reduction rate is 1% or less. In comparison with 100 parts by mass of the obtained polyorganosiloxane, 2 皙, μ &amp; photoradical polymerization initiator Lucirin (registered trademark) 159229.doc -52 - 201231509 TPO ( A photosensitive resin composition was obtained by the BASF company. [Performance Comparison Result 1] Hardening obtained by sandwiching the resin compositions obtained in Examples 1 to 8 and Comparative Example 1 with a glass substrate and exposing 3000 mJ/cm 2 with a diameter of 10 mm and a thickness of 500 μm The properties of the film are shown in Table 1 below. Temperature shock resistance (cracking, peeling) was evaluated by using TSE-11 manufactured by Aspcs to visually inspect the thermal cycle test (alternately repeated in an environment of +125 ° C for 15 minutes at -40 ° C environment In the test for 15 minutes, the presence or absence of cracks generated in the resin formed on the glass substrate and the presence or absence of film peeling were observed. The resin was cracked and the film was peeled off even after 100 cycles of heat and cold, and the resin was cracked and the film was peeled off after 10 cycles of heat and cold, but cracking and film peeling occurred after 10 times. The case is set to B, and the cracking and film peeling of the resin after 10 cycles of hot and cold cycles are set [Table 1].

Example 1 Example 2 Example 3 Example 4 Formation in Si bond = ratio of Si-〇-X_Sis bond (%) 30 27 21 12 W-NMR spectrum reduction rate of peak area derived from carboxylic acid (%) 31 29 22 13 Temperature shock resistance AAAB 159229.doc -53- 201231509 201231509 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Formation in Si bond = ratio of Si-〇-XS-bond (%) 9 30 27 14 &lt;1 b-NMR spectrum reduction rate of peak area derived from carboxylic acid (%) 9 31 29 16 &lt;1 ^temperature shock resistance* person jj· m person.a Ben-~ΓΓΓ-:- BAABC Cold and heat cycle test: A indicates &gt; 1 time, B indicates 10 to 100 times, and C indicates &lt; 10 times. [Example 9] The photosensitive resin composition was changed to 95 in Example 1 in each case. In the same manner as in the first embodiment, the reaction pressure was changed to the normal pressure, the reaction time was changed to 3 minutes, the drying temperature was changed to 130 ° C, and the drying time was changed to 3 minutes. . The weight average molecular weight of the obtained polyorganosiloxane was 7,830. In the obtained polyorganosiloxane, 48% of the number of _ subunits is contained in the structure represented by the above formula (2), and -(CH2)3-. The peak of the carboxylic acid derived from the vinegar moiety in iH-NMR was reduced by 54. /. 'The molecular weight is i in the GPC chart, and the area above the coffee is _ (Fig. 5, Fig. 6) 〇 [Example 10] Photosensitive resin composition After the photosensitive resin of Example 1 was cooled to room temperature, light was added thereto. At the same time as the radical polymerization initiator, 513AS of dicyclopentadienyl acrylate was added, and the product was manufactured by Hitachi Chemical Co., Ltd., limited to 5 mass%, and the same treatment as in Example 1 was carried out, and the sensory light was obtained. Resin composition. [Comparative Example 2] Method for obtaining a photosensitive resin by a method of synthesizing the photosensitive resin composition 1 The method of using the composition according to Patent Document 3 is the same as that of Example 1. 159229.doc 54. 201231509 [Performance comparison result 2] The resin compositions obtained in Examples 1, 6, 9, and 10 and Comparative Example 2 were respectively held by a glass substrate, and were 10 mm in diameter and thickness. The properties of the cured film obtained by subjecting 500 μm to 3000 mJ/cm 2 were shown in Table 2 below. The evaluation of temperature resistance (cracking, peeling) was carried out by visual inspection of the thermal cycle test (alternately repeated in a +125 ° C environment for 15 minutes, and in a -40 ° C environment for 15 minutes) The presence or absence of cracks in the resin on the glass substrate and the presence or absence of film peeling. In the case where the resin was not cracked and the film was peeled off even after 100 cycles of the heat and cold cycle, the resin was cracked and the film was peeled off after 100 times of the heat cycle. [Table 2] Table 2

Example 1 Example 6 Example 9 Example 10 Comparative Example 2 Molecular weight 5329 5329 7830 5329 6629 High molecular weight content υ 83% 83% 89% 83% 67% Temperature shock resistance a AAAAB ※Cold and heat cycle test: A indicates &gt 100, B represents a polymer content of &lt;100 υ, and represents an area of a portion having a weight average molecular weight of 1,050 or more in a graph of an RI detector of GPC. [Example 11] Photosensitive resin composition Further, an antioxidant IRGANOX 245 (manufactured by BASF Corporation), 0.28 parts by mass, and an antioxidant GSY-P101 (manufactured by Osaki Industries Co., Ltd.) 0.11 were further added to the photosensitive resin composition of Example 7. The same treatment as in Example 7 was carried out, except that the photosensitive resin composition was obtained. A cured film obtained by sandwiching the composition of the resin 159229.doc • 55· 201231509 obtained in Examples 7 and 11 with a glass substrate and exposing at 3000 mJ/cm 2 with a thickness of 500 μm, The glass substrate was peeled off to prepare a sample. The obtained sample is subjected to heat treatment at 150 ° C for 1 to 3 hours in nitrogen or oxygen atmosphere at a concentration of 7% (the nitrogen is set to A1, and the oxygen is set to 7% in the environment). The transmittance at a wavelength of 400 nm at a wavelength of 400 nm at a wavelength of 400 nm when the heat-treated sample is subjected to heat treatment at 260 ° C for 1 〇 3 times or 3 times at 260 ° C. Table 3 below. The transmittance of the cured film was measured using an ultraviolet-visible spectrophotometer V-550 manufactured by JASCO Corporation, based on an untreated glass substrate. The photosensitive resin composition of Example 10 to which an antioxidant was added was found to have improved thermal stability in the presence of oxygen. [Table 3] Table 3 Example 7 Transmittance (%) Example 11 Transmittance (%) Heat treatment (A1) 96 97 Heat treatment (A1) + (B) 96 96 Heat treatment (A2) 83 94 Heat treatment ( A2) + (B) 78 93 [Industrial Applicability] According to the present invention, heat-resistant photosensitive light for use in manufacturing of a solid-state image sensor or an electronic component integrated product requiring a reflow step of 260 ° C can be obtained. Since the transparent resin is obtained, an optical element for a liquid crystal polarizing plate suitable for a plastic lens or a projector which requires heat resistance can be obtained. [Simple description of the map]

Fig. 1 is a view showing a chart of 1H-NMR 159229.doc - 56 - 201231509 of a polyorganosiloxane according to an embodiment of the present invention. Fig. 2 is a view showing a Gpc chart of a polyorganooxynitane according to an embodiment of the present invention. Fig. 3 is a view showing a C3C_NMR chart of a polyorganococcal oxynitride according to an embodiment of the present invention. Fig. 4 is a view showing an ιΗ_NMR chart of a polyorganismite according to another embodiment of the present invention. Fig. 5 is a view showing a η· NMR chart of a polyorganophosphorus oxide according to still another embodiment of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a GPC chart of a polyorganotoxime according to still another embodiment of the present invention. Fig. 7 is a view showing a COSY spectrum of a polyorgano-oxygenated gas according to an embodiment of the present invention. Fig. 8 is a view showing a COSY spectrum of a polyorgano-oxygen atmosphere according to an embodiment of the present invention. ❹ 159229.doc •57-

Claims (1)

201231509 VII. Patent application scope: 1 . A photosensitive resin composition comprising: polyorganosiloxane (a) 100 parts by mass, and photopolymerization initiator (b) 0.01 to 30 parts by mass, Ο ο The organosiloxane (a) is a polymerizable functional group obtained by a method in which at least one alkoxydecane compound represented by the following formula (1) and a catalyst are mixed and polymerized, and the polymerization is carried out. The organic oxime (&amp;) contains a structure represented by the following formula (2), and 5 to 60% of the number of Si atoms of the polyorganosiloxane (a) is represented by the above formula In the structure, R'aR^SiCOR3), .^ (1) wherein R1 is an organic group having an ester bond of 2 to 17 carbon atoms, and at least one of Ri has an acrylonitrile group or a mercapto propylene group. When R2 is present in a plurality of cases, it is independently an aliphatic group of the carbon number which can have a substituent (7). R3 is independently a methyl group or an ethyl group in the case of a plurality of cases, and a is an integer of 1 or 2. , b is an integer of 〇~2, and a+b is 3 or less} = Si-0-X-Si= (2) {wherein X is an organic group having 1 to 15 carbon atoms}. 2. The photosensitive resin composition of claim 1, wherein the polyorganooxime (a) is at least one of the amphoteric compounds represented by the above formula (1), and the following formula (3) The method of obtaining and polymerizing at least one stanol compound and a catalyst, RR Si(〇H)2 (3) (wherein R4 and R5 are carbon atoms which may have a substituent 3~ 1. A photosensitive resin composition according to claim 1 or 2, wherein the polyorgano-oxyalkane (a) has the above-mentioned aliphatic 159229.doc 201231509. ～40% of the number of si atoms is contained in the structure represented by the above formula (2). 4. A photosensitive resin composition containing 100 parts by mass of polyorganosiloxane (a) and photopolymerization The initiator (b) is 0.01 to 30 parts by mass, and the polyorganosiloxane (a) is obtained by mixing and polymerizing at least one alkoxydecane compound represented by the following formula (〇) and a catalyst. Obtained by the method, and the ester bond derived from the carboxylic acid in the H-NMR spectrum is derived from the peak region of the carboxylic acid and the peak derived from the ester bond. The ratio of the area is reduced by 5 to 60% compared with the case of addition, R'aR^SiCOR3)^^, (1) where R1 is an organic group having an ester bond of 2 to 17 carbon atoms, and at least one of Ri has an acrylonitrile Or a methacryloyl fluorenyl group, and R2 is independently an aliphatic group which may have a carbon number of a substituent in the case where a plurality of groups are present, and R3 is independently hydrogen, methyl or Ethyl, a is an integer of 1 or 2, "an integer of ο~2, and (4) is the following.) 5. The photosensitive resin composition of claim 4, wherein the above-mentioned polyorganismite (4) is R4R5Si(OH)2 (3) obtained by the method of mixing the p(tetra)oxy compound represented by the above formula (1), at least the mercapto compound represented by the following formula (7), and a catalyst, and polymerizing the same. In the formula, R 4 and R 5 are an aliphatic group which may have a substituent group, an alicyclic group or an aromatic group. The photosensitive resin composition of claim 4 or 5, wherein the above oxyalkylene (4) The ester bond in the H-NMR spectrum is derived from the peak area of the hard warming and the area of the alcohol-derived material from the oxime bond. It is reduced by 1 〇 to 4 〇% compared with the case of addition. 7.1. A photosensitive resin composition containing: Ο ο polyorganosiloxane (a) 100 parts by mass, and a photopolymerization initiator (b) 0.01 to 30 parts by mass, ^ 聚聚 (4) Oxygen (4) is represented by the following formula (1): a compound of the formula; τ, at least one of the formulas represented by the formula (3) In the gel permeation chromatography (Gpc) measurement, the area of the weight average molecular weight of the standard polystyrene conversion is 7 G% or more, and the RWbSHOR^ is obtained by the method of mixing and polymerizing the alcohol compound and the catalyst. .ab (1) wherein R1 is an organic group having an ester bond of 2 to 17 carbon atoms, and at least one of R1 has an acryloyl group or a fluorenyl fluorenyl group, and R2 may independently have a plurality of cases. The aliphatic group of the carbon number of the substituent 丨~1〇, R3 is independently a fluorenyl group or an ethyl group in the case of a plurality of cases, and the ugly is an integer of 1 or 2 'b is an integer of 〇~2, and a+ b is 3 or less} R4R5Si(〇H)2 (3) {wherein 'R and R5 are aliphatic groups having 3 to 1 carbon atoms which may have a substituent Alicyclic group or an aromatic group}. 8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the above-mentioned 159229.doc 201231509 is a compound of the formula (1), and the at least one alkoxy group represented by the following formula (4) A decane compound, H2C=C(R6Hc=〇)〇(CH2)n_siR7j〇R8h (4) R is hydrogen or a methyl group, and R7 is independently an aliphatic group which may have a substituent and a carbon number in the presence of a plurality of The base, R8, is independently methyl or ethyl in the presence of a plurality of cases. It is 〇~2. 9. 10. Π. 12. 13. 14. When the number 'd is an integer from i to 3, it is 3 or less, and n is a call. The photosensitive resin composition according to any one of the items 2, 3, and 5 to 8, wherein at least one of the above formula (3) is a carbon having a carbon number of 3 to 1 可 which may have a substituent Ring base. The photosensitive resin composition according to any one of the items 1 to 9 further comprising an ethylenically unsaturated addition polymerizable monomer (C) 〇1 to 1000 parts by mass based on 100 parts by mass of the polyorganosiloxane (4). . The photosensitive resin composition according to the item 1G, wherein the ethylenically unsaturated addition polymerizable monomer (4) is a compound containing an alicyclic group. The photosensitive resin composition according to any one of claims 1 to 11, further comprising an ultraviolet ray absorbing agent, a light stabilizer, a auxiliaries, a poly-inhibitor, a sensitizer, an antioxidant, and a smoothness imparting At least one additive of the group consisting of the agents. The photosensitive resin composition according to any one of claims 1 to 12, wherein the metal or soil-measuring metal concentration in the photosensitive resin composition is from 0.1 to 500 ppm. A method for producing a polyorganosiloxane, comprising: hydrating at least a oxy group represented by the following formula (1): 159229.doc 201231509, relative to an alkoxy decane compound present in the reaction system The water having a R3Si equivalent of 0.01 to 〇5 equivalents and a catalyst are mixed and reacted at 20 to 130 ° C. The step of removing the alcohol formed by the reaction to the external alkane (a) , 1~20 hours, and one side will borrow, one side of polyorgano-oxygen R 丨aR2bSi (〇R3) "_b (1) 15. In the formula, R1 is an organic group having an ester bond having 2 to 17 carbon atoms, at least one of R1 has an acryloyl group or a fluorenyl fluorenyl group, and R2 is independently a plurality of cases, and each may independently have a substituent. The aliphatic group of carbon number, R3 is independently a fluorenyl group or an ethyl group in the case of a plurality of cases, a is an integer of 1 or 2, b is an integer of 〇~2, and a+b is 3 or less.丨^ and π) a step of washing the polyorganophthalocyanine (a) with a solvent which does not dissolve the polyorganosiloxane. A method for producing a polyorganosiloxane, comprising: i) at least one type of sulphur-based compound represented by the following formula (1), at least one of the following formula (3) The compound and the catalyst are mixed and reacted at 20 to BOX: (M to 20 hours, and the alcohol formed by the reaction is removed to the external organooxane (a). PolyR aR2bSi(〇R3)4 ab (1) (wherein R1 is an organic group having an ester bond of 2 to 17 carbon atoms, at least one of r1 has an acryloyl group or a methacryloyl group, and R2 is present in a plurality of The form is independently a carbon number diester which can have a substituent = soil, and R is independently a methyl group or an ethyl group in the case of a plurality of cases, 159229.doc 201231509 a is an integer of 1 or 2, and b is 0. An integer of ～2, and a+b is 3 or less} R4R5Si(〇H)2 (3) {wherein R4 and R5 are an aliphatic group, an alicyclic group or an aromatic group of a carbon number kiO having a substituent Base}; and 11) using a solvent that does not dissolve the polyorgano oxy- smoldering solvent. The polyorgano # ^ alkane oxime is followed by a cleaning step. The production method according to claim 14 or 15, wherein the catalyst is at least one compound selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides. The production method according to any one of claims 14 to 16, wherein the above catalyst is Ba(〇H)2&amp;/or a hydrate thereof. The production method according to any one of claims 14 to 17, wherein the amount of the above catalyst is 0.05 to 30 moles per gram relative to the total number of moles of cerium (Si). The manufacturing method according to any one of claims 14 to 18, wherein the amount of the above catalyst relative to the total number of moles of cerium (Si) is 〇 丨〇 丨〇 〇 〇. The manufacturing method of any one of the items 14 to 19 wherein the above solvent is an alcohol or acetonitrile. a cured product obtained by the photosensitive resin composition of any of the items _ to i 3 or containing the method of the method of any one of the items U to 2 The photosensitive resin composition of the organic money house (4) and the photopolymerization initiator (b) is obtained by photocuring. A method of producing a molded article, comprising the steps of: the photosensitive resin composition according to any one of items 1 to 13, or 3, by any one of claims 14 to 20 159229.doc 201231509 The photosensitive resin composition of the polyorganosiloxane (a) and the photopolymerization initiator (b) is filled in a molding die, and the opening of the die is pressed to the substrate. Or a step on the other mold, the step of exposing the photosensitive resin composition from the mold and/or the substrate side to obtain a photocured material, the step of peeling the mold from the substrate or peeling off the mold on both sides And a step of heating only the photocured material or heating the photocured material together with the substrate. A hardened material obtained by the manufacturing method of claim 22. 24. The above-mentioned polyorganosiloxane, which is represented by the following formula (1), which is represented by the following formula (1), at least one stanol represented by the following formula (3) The compound and the catalyst are obtained by a method of mixing and polymerizing the same, and the polyorganic money is contained in the structure represented by the following formula (2), and the polyorganosiloxane has 5 of the Si atoms. ～6〇% is contained in the structure represented by the above formula (2), (I) RWbSUOR3)^ where R1 is an organic group having a carbon number of 2 to 17 and containing a bond, and r2 is present in plural (4) _ 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立An integer of ～2, and a+b is 3 or less} R4R5Si(OH)2 159229.doc (3) 201231509 {Formula, m R5 &amp; This is a fatty group having a carbon number of 3 to 10 which may have a substituent暴 曰 曰 或 或 或 或 或 或 或 或 或 或 或 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 25. The polyorganocene oxime of claim 24, wherein the ruthenium of the above formula (1) is a group having an acrylate and/or a methacrylate. 159229.doc