WO2012050201A1 - Composition de résine photosensible et son procédé de production - Google Patents

Composition de résine photosensible et son procédé de production Download PDF

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WO2012050201A1
WO2012050201A1 PCT/JP2011/073704 JP2011073704W WO2012050201A1 WO 2012050201 A1 WO2012050201 A1 WO 2012050201A1 JP 2011073704 W JP2011073704 W JP 2011073704W WO 2012050201 A1 WO2012050201 A1 WO 2012050201A1
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group
polyorganosiloxane
general formula
resin composition
photosensitive resin
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PCT/JP2011/073704
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English (en)
Japanese (ja)
Inventor
徹 勝又
大和 齋藤
寛子 巌倉
長武 山崎
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旭化成イーマテリアルズ株式会社
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Priority to SG2013027719A priority Critical patent/SG189383A1/en
Priority to JP2012538732A priority patent/JPWO2012050201A1/ja
Priority to KR1020137009392A priority patent/KR20130066684A/ko
Priority to CN2011800495723A priority patent/CN103154053A/zh
Publication of WO2012050201A1 publication Critical patent/WO2012050201A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0017—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor for the production of embossing, cutting or similar devices; for the production of casting means
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers

Definitions

  • the present invention relates to a photosensitive resin composition useful as an electrical component such as a semiconductor device, a microplastic lens, a liquid crystal polarizing plate, and an optical waveguide mainly for optical applications, and electrical / electronics such as a semiconductor device and a multilayer wiring board.
  • the present invention relates to a resin insulating film used for a material.
  • the present invention relates to a plastic mini lens for a camera module such as a mobile phone or a surveillance camera, a peripheral material for the camera module, a micro plastic lens for optical communication, a micro plastic lens for a solid-state imaging device such as a CCD or CMOS image sensor , LED sealants, photonic crystals for LED brightness enhancement, thin film transistor arrays in the display field, materials for the formation of antireflection films, materials for optical elements for polarizing plates for liquid crystal projectors, buffer coating for LSI chips
  • the present invention relates to a material for forming an interlayer insulating film.
  • Plastic lenses are widely used in various optical products because they are easier to mold and cheaper than glass.
  • various transparent materials such as thermoplastic plastics such as polymethyl methacrylate and polystyrene and thermosetting plastics such as polydiethylene glycol bisallyl carbonate are used.
  • thermoplastic plastics such as polymethyl methacrylate and polystyrene
  • thermosetting plastics such as polydiethylene glycol bisallyl carbonate
  • Patent Documents 1 and 2 most of the conventional materials have a temperature of 200 ° C. or less even if the heat resistance is improved, and 260 ° C. solder reflow heat resistance has not been guaranteed.
  • Patent Document 3 discloses a polysiloxane having a molecular weight of 3,000 or more and 10,000 or less obtained by polymerizing silanediol and alkoxysilane in a two-stage process.
  • the present invention is useful for manufacturing a solid-state imaging device or an electronic component integrated product that requires a solder reflow process, and is resistant to cracking or peeling even after being subjected to a -40 ° C to 125 ° C cooling cycle after curing. It is an object of the present invention to provide a photosensitive transparent resin composition having excellent characteristics such as impact properties, a resin that can be used for the composition, and a cured product using the composition.
  • the inventors have studied a photosensitive resin containing siloxane, mixed only a specific alkoxysilane or a specific silanol compound and a specific alkoxysilane compound, and subjected to condensation polymerization. And it discovered that the photosensitive resin excellent in the temperature impact resistance was obtained by adding a photoinitiator.
  • the present inventors have invented a method for increasing the molecular weight of polysiloxane, and have completed the present invention. That is, the present invention is as follows.
  • R 1 is an organic group containing an ester bond having 2 to 17 carbon atoms, at least one of R 1 has an acryloyl group or a methacryloyl group, and when R 2 is present in plural
  • R 3 is independently a methyl group or an ethyl group when a plurality of R 3 are present, and a is 1 is an integer of 1 or 2
  • b is an integer of 0 to 2
  • a + b is 3 or less.
  • a photosensitive resin composition comprising: the polyorganosiloxane (a): 100 parts by mass; and the photopolymerization initiator (b): 0.01 to 30 parts by mass contained in the structure represented by:
  • the polyorganosiloxane (a) includes at least one alkoxysilane compound represented by the general formula (1), the following general formula (3): R 4 R 5 Si (OH) 2 (3) ⁇ In the formula, R 4 and R 5 are an aliphatic group, an alicyclic group or an aromatic group having 3 to 10 carbon atoms which may have a substituent. ⁇
  • R 1 is an organic group containing an ester bond having 2 to 17 carbon atoms, at least one of R 1 has an acryloyl group or a methacryloyl group, and when R 2 is present in plural
  • R 1 is an organic group containing an ester bond having 2 to 17 carbon atoms, at least one of R 1 has an acryloyl group or a methacryloyl group, and when R 2 is present in plural
  • R 3 independently represents hydrogen, a methyl group or an ethyl group, a is an integer of 1 or 2, b is an integer of 0 to 2, and a + b is 3 or less.
  • the polyorganosiloxane (a) includes at least one alkoxysilane compound represented by the general formula (1), the following general formula (3): R 4 R 5 Si (OH) 2 (3) ⁇ In the formula, R 4 and R 5 are an aliphatic group, an alicyclic group or an aromatic group having 3 to 10 carbon atoms which may have a substituent. ⁇
  • the photosensitive resin composition as described in [4] which is obtained by the method of mixing and polymerizing at least one silanol compound and a catalyst.
  • the ratio of the peak area derived from the ester bond carboxylic acid to the peak area derived from the ester bond alcohol in the 1 H-NMR spectrum is 10 to 40% compared to the charged state.
  • R 1 a R 2 b Si (OR 3 ) 4-ab (1)
  • R 1 is an organic group containing an ester bond having 2 to 17 carbon atoms, at least one of R 1 has an acryloyl group or a methacryloyl group, and when R 2 is present in plural
  • R 1 is an organic group containing an ester bond having 2 to 17 carbon atoms, at least one of R 1 has an acryloyl group or a methacryloyl group, and when R 2 is present in plural
  • a polyorganosiloxane (a) obtained by mixing and polymerizing at least one type of silanol compound and a catalyst, and having a weight average molecular weight in terms of standard polystyrene in gel permeation chromatography (GPC) measurement
  • the polyorganosiloxane (a) having an area of not less than 1,050 and not less than 70%: 100 parts by mass; and a photopolymerization initiator (b): 0.01 to 30 parts by mass .
  • the alkoxysilane compound represented by the general formula (1) is represented by the following general formula (4): H 2 C ⁇ C (R 6 ) — (C ⁇ O) —O— (CH 2 ) n —SiR 7 c (OR 8 ) d (4) ⁇
  • R 6 is hydrogen or a methyl group
  • R 7 is each independently an aliphatic group having 1 to 10 carbon atoms which may have a substituent when a plurality of R 7 are present.
  • R 8 each independently represents a methyl group or an ethyl group
  • c is an integer of 0 to 2
  • d is an integer of 1 to 3
  • c + d is 3
  • n is 1-14.
  • the photosensitive resin composition according to any one of [1] to [7], which is at least one alkoxysilane compound represented by the formula:
  • At least one of R 4 and R 5 in the general formula (3) is an alicyclic group having 3 to 10 carbon atoms which may have a substituent, [2], [3] And the photosensitive resin composition according to any one of [5] to [8].
  • at least one additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, an adhesion assistant, a polymerization inhibitor, a sensitizer, an antioxidant, and a smoothness-imparting agent.
  • R 1 is an organic group containing an ester bond having 2 to 17 carbon atoms, at least one of R 1 has an acryloyl group or a methacryloyl group, and when R 2 is present in plural
  • R 3 is independently a methyl group or an ethyl group when a plurality of R 3 are present, and a is 1 is an integer of 1 or 2
  • b is an integer of 0 to 2
  • a + b is 3 or less.
  • R 1 is an organic group containing an ester bond having 2 to 17 carbon atoms, at least one of R 1 has an acryloyl group or a methacryloyl group, and when R 2 is present in plural
  • R 3 is independently a methyl group or an ethyl group when a plurality of R 3 are present, and a is 1 is an integer of 1 or 2
  • b is an integer of 0 to 2
  • a + b is 3 or less.
  • the photosensitive resin composition according to any one of [1] to [13], or the polyorganosiloxane obtained by the production method according to any one of [14] to [20] ( a step of filling a mold for molding a photosensitive resin composition containing a) and a photopolymerization initiator (b); Pressing the mold opening against the substrate or another mold; A step of exposing the photosensitive resin composition from the mold and / or the substrate side to obtain a photocured product, Peeling the mold from the substrate or peeling the mold on both sides, and heating the photocured material alone or together with the photocured material, A method for producing a molded product comprising
  • R 1 ′ is an organic group containing an ester bond having 2 to 17 carbon atoms, and when there are a plurality of R 2 s , each independently represents an optionally substituted carbon number. 1 to 10 aliphatic groups, and when there are a plurality of R 3 s , each independently represents a methyl group or an ethyl group, a is an integer of 1 or 2, and b is 0 to 2 And a + b is 3 or less.
  • the present invention it is useful for manufacturing a solid-state imaging device or an electronic component integrated product that requires a solder reflow process, and has excellent characteristics such as thermal shock resistance such that cracking or peeling does not occur even through a thermal cycle.
  • the resin which has it, or the photosensitive resin composition can be provided.
  • FIG. 5 is a diagram showing a 1 H-NMR chart of polyorganosiloxane according to another embodiment of the present invention. Is a diagram showing 1 H-NMR chart of the polyorganosiloxane in still another embodiment of the present invention. It is a figure which shows the GPC chart of the polyorganosiloxane in another embodiment of this invention. It is a figure which shows the HH COSY spectrum of the polyorganosiloxane in embodiment of this invention. It is a figure which shows the CH COSY spectrum of the polyorganosiloxane in embodiment of this invention.
  • the photosensitive resin composition in the present invention is obtained by a method in which a specific alkoxysilane compound and a catalyst are mixed and polymerized, and the following general formula (2) ⁇ Si—O—X—Si ⁇ (2) (Wherein X is an organic group having 1 to 15 carbon atoms) and a photopolymerization initiator (b).
  • the alkoxysilane compound has the following general formula (1): R 1 a R 2 b Si (OR 3 ) 4-ab (1) ⁇ Wherein R 1 is an organic group containing an ester bond having 2 to 17 carbon atoms, at least one of R 1 has an acryloyl group or a methacryloyl group, and when R 2 is present in plural Each independently represents an aliphatic group, alicyclic group or aromatic group having 1 to 10 carbon atoms which may have a substituent in any case, and when R 3 is present in plural Each independently represents a methyl group or an ethyl group, a is an integer of 1 or 2, b is an integer of 0 to 2, and a + b is 3 or less. ⁇ Is at least one kind of alkoxysilane compound.
  • a polyorganosiloxane (a) obtained by mixing and polymerizing at least one alkoxysilane compound represented by the above general formula (1), a specific silanol compound, and a catalyst. It is preferable from the viewpoint of stability.
  • the silanol compound has the following general formula (3): R 4 R 5 Si (OH) 2 (3) ⁇ In the formula, R 4 and R 5 are an aliphatic group, an alicyclic group or an aromatic group having 3 to 10 carbon atoms which may have a substituent. ⁇ Is at least one kind of silanol compound.
  • Examples of the alkoxysilane represented by the general formula (1) include the following general formula (5): R 9 — (C ⁇ O) —O—X—SiR 10 c (OR 8 ) d (5) ⁇
  • R 9 is an aliphatic group, alicyclic group or aromatic group having 1 to 15 carbon atoms, which may have a substituent, and at least one kind thereof is an acrylate ester and / or Has a methacrylic acid ester
  • X is an aliphatic group having 1 to 15 carbon atoms, an alicyclic group or an aromatic group, may have a substituent
  • R 10 is present in plural Each independently represents an aliphatic group having 1 to 10 carbon atoms and may have a substituent.
  • C is an integer from 0 to 2
  • d is an integer from 1 to 3
  • c + d is 3 or less
  • n is from 1 to 14.
  • R 6 represents hydrogen or a methyl group
  • R 7 independently represents an aliphatic group having 1 to 10 carbon atoms which may have a substituent, when present in a plurality.
  • c is an integer of 0 to 2
  • d is 1 to An integer of 3
  • c + d is 3 or less
  • n is 1-14.
  • alkoxysilane compound represented by the above it is preferable to use at least one kind of alkoxysilane compound represented by the above from the viewpoint of UV sensitivity.
  • alkoxysilane compound represented by the general formula (4) include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-acryloxypropyltrimethoxy.
  • Silane 3-acryloxypropyltriethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-methacryloxyethylmethyldimethoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acrylic Roxyethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethylmethyldimethoxysilane, acryloxymethyltrimethoxysilane Include acryloxymethyl triethoxysilane.
  • R 1 ′ is an organic group containing an ester bond having 2 to 17 carbon atoms, and when there are a plurality of R 2 s , each independently represents an optionally substituted carbon number.
  • R 3 s each independently represents a methyl group or an ethyl group, a is an integer of 1 or 2, and b is 0 to 2 And a + b is 3 or less.
  • R 4 R 5 Si (OH) 2 (3) At least one alkoxysilane compound represented by the following general formula (3): R 4 R 5 Si (OH) 2 (3) ⁇ In the formula, R 4 and R 5 are an aliphatic group, an alicyclic group or an aromatic group having 3 to 10 carbon atoms which may have a substituent.
  • the at least one alkoxysilane compound represented by the general formula (I) in addition to the alkoxysilane compound shown above, 3-acetoxypropyltrimethoxy Only an ester bond-containing alkoxysilane having no polymerizable functional group such as silane may be used.
  • the catalyst is a compound that accelerates the hydrolysis of the alkoxy group of the alkoxysilane compound and the condensation reaction between the silanols produced thereby or the alkoxysilane and silanol, and the ester hydrolysis reaction or transesterification reaction during the polymerization. Advancing compounds can be used.
  • the catalyst used for the reaction with the alkoxysilane compound and the silanol compound is a compound that promotes the dealcoholization condensation reaction between the silanol group of the silanol compound and the alkoxy group of the alkoxysilane compound, and an ester hydrolysis reaction or Compounds that undergo transesterification can be used.
  • the catalyst may be an acidic compound or a basic compound, and examples thereof include metal alkoxides, inorganic acids, organic acids, inorganic bases, organic bases, and phosphazene compounds. Among them, alkali metal hydroxides or alkaline earth metal hydroxides, ammonium compounds and the like are preferable. Specific examples include Ba (OH) 2 , Ca (OH) 2 , Mg (OH) 2 , KOH, LiOH, NH 3 , NH 4 OH, NR 4 (OH), NR 4 Cl, NR 4 Br, NR 4 I and the like can be mentioned.
  • R is an aliphatic group, alicyclic group or aromatic group having 1 to 10 carbon atoms which may have a substituent. It is. More preferably, an alkali metal hydroxide, an alkaline earth metal hydroxide, etc. are mentioned. More preferably, the catalyst is an alkaline earth metal hydroxide, and specific examples include Ba (OH) 2 , Ca (OH) 2 , and Mg (OH) 2 . Also, Ba (OH) 2 , Ca (OH) 2 , Mg (OH) 2 hydrates may be used, stability and reaction time can be shortened, and reaction time in a heterogeneous state is shortened. From the viewpoint that the reaction can be performed with good reproducibility, it is more preferable to use Ba (OH) 2 .8H 2 O.
  • the amount of the catalyst added is preferably a concentration at which the hydrolysis reaction or transesterification reaction with hydration water contained in the catalyst or the like proceeds appropriately, for example, 0.05 to From the viewpoint of transparency and reaction controllability, it is preferably from 0.1 to 20 mol%, more preferably from 0.1 to 10 mol%, particularly preferably from 0.2 to 10 mol%.
  • the number of charged Si atoms is the total number of Si atoms in the total of the alkoxysilane compound represented by the general formula (1), the silanol compound represented by the general formula (3), and other condensable silane compounds present in the reaction system.
  • the number of moles of the catalyst amount indicates how many moles of the catalyst are added with respect to the number of moles of Si atoms.
  • the silanol compound represented by the general formula (3) is preferably an aromatic group or an alicyclic group in which R 1 and R 2 are bulky substituents from the viewpoint of the stability of the compound. From the viewpoint of light resistance and heat resistance, a compound in which at least one of R 4 and R 5 is an alicyclic group having 3 to 10 carbon atoms which may have a substituent is more preferable. In addition, dicyclohexylsilane diol and dicyclopentylsilane diol are more preferable from the viewpoint of more excellent transparency.
  • the mixing ratio of the alkoxysilane compound represented by the general formula (1) and the silanol compound represented by the general formula (3) is represented by the general formula (1) with respect to 100 mol of the silanol compound represented by the general formula (3).
  • the alkoxysilane compound shown is preferably 10 to 200 mol, preferably 20 to 180 mol, more preferably 30 to 150 mol, further preferably 40 to 120 mol, most preferably from the viewpoint of molecular weight and UV sensitivity of the resulting resin. 60 to 100 moles.
  • the reaction temperature is 20 ° C. to 130 ° C., preferably 30 ° C.
  • the temperature is -100 ° C, more preferably 40-80 ° C
  • the reaction time is 0.1-20 hours, preferably 0.2-10 hours, more preferably 0.3-5 hours.
  • the atmosphere in the reactor may be a nitrogen atmosphere or an air atmosphere. Water may or may not be actively added into the reaction system. Even in the case where water is not actively added, water in the hydrated compound of the catalyst used or water in the silanol may be present in the reaction system.
  • a minimum amount of water may be used, and preferably 0.001 to 0.5 equivalent per 1 equivalent of the alkoxy group bonded to the Si atom. .
  • Fine particles such as silica, zirconia, and titania may be added to the reaction system for the purpose of reducing the linear expansion constant of the cured product and adjusting the refractive index.
  • A is a side derived from an ester bond carboxylic acid
  • B is a side derived from an ester bond alcohol
  • the reduction rate can be obtained by comparing with the NMR of the raw material.
  • H 2 C ⁇ C (Me) — (C ⁇ O) —O— (CH 2 ) 3 —Si (OMe) 3 is used as a raw material, 0.6 ppm in the initial charge, that is, in the NMR spectrum of the raw material In the vicinity, protons of ⁇ Si—C H 2 — appear, and proton peaks of H 2 C ⁇ C ⁇ appear near 5.5 ppm and 6.0 ppm, but their peak area is 2: 2, The ratio is 1.
  • ⁇ Si—C H 2 — which is the alcohol moiety of the ester bond
  • the rate of decrease can be increased by changing the conditions such as increasing the amount of catalyst, extending the time, and increasing the temperature.
  • the alkoxysilane represented by the general formula (1) is an alkoxysilane having a methacrylic acid ester and Ba (OH) 2 .H 2 O is used as a catalyst, the total catalyst concentration is usually used.
  • the peak area derived from the ester bond carboxylic acid does not decrease even when the reaction temperature is 50 ° C. and the reaction time is 2 hours, but the catalyst amount is 0.3 mol%.
  • polyorganosiloxane in which the peak area derived from the ester bond carboxylic acid is reduced by about 30% can be synthesized.
  • the peak area derived from the carboxylic acid of the steal bond can be reduced by the desired amount.
  • the rate at which the ester bond in the alkoxysilane compound represented by the general formula (1) disappears during the polymerization reaction is 5 to 60% with respect to the charged amount of the alkoxysilane compound represented by the general formula (1), preferably It is 7 to 50%, more preferably 10 to 40%, and most preferably 15 to 35%. As described above, these disappearance ratios correspond to the ratios in which the peak area derived from the carboxylic acid of the ester bond of the alkoxysilane compound represented by the general formula (1) decreases.
  • the decrease in the peak area of the carboxylic acid moiety of the ester bond is generated by condensation between the alkoxy moiety of the alkoxysilane compound represented by the general formula (1) and the silanol moiety of the silanol represented by the general formula (3) during the polymerization reaction.
  • reaction formula (6) depends on the production of alcohol (methanol or ethanol), the presence of a small amount of water and a basic catalyst, etc .: (Wherein X is an organic group having 1 to 15 carbon atoms, R 11 is an organic group having 0 to 15 carbon atoms, and the sum of the carbon number of X and R 11 is 1 to 16, R 12 is a methyl group, an ethyl group or hydrogen.) This is probably because the ester bond hydrolysis reaction, transesterification reaction, and the like are progressing.
  • the produced alcohol is represented by the following formula (7) by an alcohol exchange reaction between the alkoxy group of the alkoxysilane compound represented by the general formula (1) and the silanol group of the silanol compound represented by the general formula (3):
  • X is an organic group having 1 to 15 carbon atoms, preferably an organic group having 2 to 10 carbon atoms, more preferably an organic group having 3 to 5 carbon atoms. Most preferably from the viewpoint of sex, it has 3 carbon atoms, and R 12 is a methyl group, an ethyl group or hydrogen.
  • alkylene alcohol or phenylene alcohol produced by the disappearance of the ester moiety is an alkoxysilane compound represented by the general formula (1), a silanol compound represented by the general formula (3), or at least one of them. It is considered that a polyorganosiloxane (a) crosslinked with one kind of polycondensate is obtained.
  • X may have an aromatic group in the main chain, and is preferably an alkyl group which may be further substituted, or an aromatic group.
  • —X—O— the following general formula (8): (Wherein l is 1-15, m is 0-9, n is 0-9, and n + m ⁇ 9).
  • the carbon number of X is preferably 2 to 10, more preferably 3 to 5, and most preferably 3.
  • the polyorganosiloxane can be confirmed to have the structure represented by the general formula (2) by, for example, 1 H-NMR and 13 C-NMR spectrum measurements.
  • H 2 C ⁇ C (CH 3 ) — (C ⁇ O) —O— (CH 2 ) 3 —Si (OCH 3 ) 3 was used as the alkoxysilane compound represented by the general formula (1).
  • the structure represented by the general formula (2) is a ⁇ Si-O-CH 2 -CH 2 -CH 2 -Si ⁇
  • H 2 C The underlined proton peak in the C (CH 3 ) — (C ⁇ O) —O—C H 2 —CH 2 —CH 2 —Si ⁇ structure appears at 3.9-4.2 ppm
  • ⁇ Si The proton peak in the underlined portion of the —O—C H 2 —CH 2 —CH 2 —Si ⁇ structure appears around 3.4-3.9 ppm.
  • FIG. 7 shows an HH COSY spectrum
  • FIG. 8 shows a CH COSY spectrum.
  • HH COSY a correlation appears between peaks of hydrogen atoms bonded to each of two adjacent carbon atoms
  • CH COSY a correlation appears between peaks of bonded carbon atoms and hydrogen atoms.
  • the peak at 3.4-3.9 ppm and the peak near 1.0 ppm there is a relationship between the peak near 1.0 ppm and the peak near 0.0 ppm. I know that there is. From the CH COSY spectrum shown in FIG.
  • Si atom content by 29 Si NMR spectrum containing the internal standard is, the content of ester structure by 1 H NMR spectrum containing the internal standard, 13 It is possible to identify the structure and calculate the content of ⁇ Si—O—X—Si ⁇ from the C NMR spectrum (NNE mode), HH COSY, and CH COSY spectra.
  • the NMR spectrum was measured using JNM-GSX400.
  • the 1 H NMR spectrum was 400 MHz, and the 13 C NMR spectrum was measured at 100 MHz.
  • the proportion of the polyorganosiloxane that forms bonds of the structure represented by the general formula (2) is 5-60. %, More preferably 7 to 50%, still more preferably 10 to 40%, and most preferably 15 to 35%.
  • a method of increasing the molecular weight while maintaining the equivalent of the crosslinkable functional group of the polyorganosiloxane a method of adding a boron compound or a method of adding a phosphorus compound and a peroxide can also be used.
  • the polyorganosiloxane obtained in the reaction step can be removed with a solvent in which the polyorganosiloxane does not dissolve to remove low molecular weight substances (eg, dimer, trimer, tetramer). Good.
  • a solvent in which the polyorganosiloxane does not dissolve in the washing step include water, alcohol (for example, methanol or ethanol), acetonitrile, and the like.
  • a solvent in which the polyorganosiloxane does not dissolve is added to the polyorganosiloxane obtained in the reaction step, or the polyorganosiloxane obtained in the reaction step is added to a solvent in which the polyorganosiloxane does not dissolve Then, stir. Stirring is continued with the whole being inhomogeneous, and then left to stand. After separating into a polyorganosiloxane layer and a solvent layer, the polyorganosiloxane layer can be collected or removed by removing the solvent layer.
  • the remaining catalyst can be reduced by the washing process.
  • the amount of residual catalyst in the resin composition is preferably 0.1 to 500 ppm.
  • the polyorganosiloxane (a) used in the photosensitive resin composition of the present invention is polymerized by mixing an alkoxysilane compound represented by the general formula (1), a silanol compound represented by the general formula (3) and a catalyst. And the area where the weight average molecular weight in terms of standard polystyrene is 1,050 or more in the gel permeation chromatography (GPC) measurement is 70% or more.
  • the molecular weight evaluation method is as follows. Tosoh HLC-8020, a differential refractometer (RI) as a detector, and a column using G5000HHR, G4000HHR, G3000HHR, G2500HHR manufactured by Tosoh Corporation in series and polystyrene (Tosoh Corporation) TSK standard, 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, A calibration curve was prepared using 500) as standard polystyrene, and measurement was performed using THF as a solvent at a flow rate of 1 mL / min.
  • silanol compound alkoxysilane compound and catalyst, reaction conditions, and the like are the same as described above.
  • High molecular weight is achieved by forming the structure represented by the general formula (2). Therefore, in order to control the molecular weight, the structure represented by the general formula (2), that is, the reactions represented by the reaction formulas (6) and (7) may be controlled.
  • These reactions can be controlled by changing the reaction temperature, reaction time, reaction pressure, amount of catalyst, and type of catalyst.
  • the process for producing polyorganosiloxane (a) is: i) At least one alkoxysilane compound represented by the above general formula (1) and a catalyst are mixed, and the temperature is 20 ° C to 130 ° C, preferably 30 ° C to 100 ° C, more preferably 40 ° C to 80 ° C, The reaction time is 0.1 to 20 hours, preferably 0.2 to 10 hours, more preferably 0.3 to 5 hours, and the polyorganosiloxane ( The step of producing a), and ii) the step of washing the polyorganosiloxane (a) with a solvent in which the polyorganosiloxane does not dissolve are sequentially included.
  • Water may be added to the reaction system, but the amount of water added is 0.01 to 0.5 equivalents relative to 1 equivalent of the alkoxy group bonded to the Si atom of the alkoxysilane compound present in the reaction system. It is preferably 0.05 to 0.45 equivalent, more preferably 0.1 to 0.4 equivalent from the viewpoint of storage stability and reactivity due to the terminal alkoxy structure.
  • the method for producing polyorganosiloxane (a) is: i) at least one alkoxysilane compound represented by the above general formula (1), At least one silanol compound represented by the general formula (3) and a catalyst are mixed, and the temperature is 20 ° C. to 130 ° C., preferably 30 to 100 ° C., more preferably 40 to 80 ° C., and the reaction time is 0.1 to 20 hours, preferably 0.2 to 10 hours, more preferably 0.3 to 5 hours, and the polyorganosiloxane (a) is removed while removing the alcohol produced by the reaction out of the system.
  • Generating step, ii) Steps of sequentially washing the polyorganosiloxane (a) with a solvent in which the polyorganosiloxane does not dissolve are included.
  • the method for producing polyorganosiloxane (a) is a reaction under a normal pressure when the reaction temperature is equal to or higher than the boiling point of the alcohol to be generated, and under reduced pressure when the reaction temperature is lower than the boiling point, while the generated alcohol is released out of the system. It is characterized by making it. As a result, the amount of alcohol in the reactor is reduced, and the controllability of the reaction is increased (that is, ester cleavage is slowed down and easier to control).
  • the catalyst used for the polymerization is a compound that promotes the dealcoholization condensation reaction between the silanol group of the silanol compound and the alkoxy group of the alkoxysilane compound, and a compound that undergoes an ester hydrolysis reaction or a transesterification reaction during the polymerization.
  • R is an aliphatic group, alicyclic group or aromatic group having 1 to 10 carbon atoms which may have a substituent. It is. More preferably, an alkali metal hydroxide, an alkaline earth metal hydroxide, etc. are mentioned.
  • the catalyst is an alkaline earth metal hydroxide, and specific examples include Ba (OH) 2 , Ca (OH) 2 , and Mg (OH) 2 .
  • Ba (OH) 2 , Ca (OH) 2 , Mg (OH) 2 hydrates may be used, stability and reaction time can be shortened, and reaction time in a heterogeneous state is shortened. From the viewpoint that the reaction can be performed with good reproducibility, it is more preferable to use Ba (OH) 2 .8H 2 O.
  • the amount of the catalyst added is preferably a concentration at which the hydrolysis reaction or transesterification reaction with hydration water contained in the catalyst or the like proceeds appropriately, for example, 0.05 to From the viewpoint of transparency and reaction controllability, it is preferably from 0.1 to 20 mol%, more preferably from 0.1 to 10 mol%, particularly preferably from 0.2 to 10 mol%.
  • the number of charged Si atoms is the total number of Si atoms in the total of the alkoxysilane compound represented by the general formula (1), the silanol compound represented by the general formula (3), and other condensable silane compounds present in the reaction system.
  • the number of moles of the catalyst amount indicates how many moles of the catalyst are added with respect to the number of moles of Si atoms.
  • a solvent in which the obtained polyorganosiloxane is preferably dissolved and the catalyst is not dissolved for example, an alkali metal hydroxide such as Ba (OH) 2 is used .
  • the catalyst can be removed by dissolving only the polyorganosiloxane (a) with cyclohexane and toluene, and filtering.
  • the added solvent is dried after gradually removing the solvent under reduced pressure and heating conditions.
  • the drying temperature is 50 ° C. to 130 ° C., preferably 80 ° C. to 130 ° C.
  • the pressure is 20 hPa or less, preferably 15 hPa or less
  • the drying time is 10 minutes or more, preferably 30 minutes or more. More preferably, it is 1 hour.
  • the number of washings can be repeated several times until the low molecular weight body is removed in a desired amount.
  • a low molecular weight body is added by adding a solvent to a polyorganosiloxane (a), or adding a polyorganosiloxane (a) to a solvent, and stirring. After dissolving in a solvent and stirring for a necessary time, the polymer layer and the solvent layer are separated by allowing to stand. Thereafter, the polyorganosiloxane (a) with reduced low molecular weight can be isolated by removing the solvent layer or recovering the polyorganosiloxane (a) layer.
  • the polyorganosiloxane (a) having a reduced low molecular weight is obtained by drying the isolated polyorganosiloxane (a) after removing the solvent under reduced pressure and heating conditions.
  • Preferred examples of the photopolymerization initiator (b) used in the photosensitive resin composition of the present invention include the following compounds.
  • Benzophenone derivatives for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone
  • Acetophenone derivatives for example, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by Ciba Specialty Chemicals, IRGACURE 651), 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty) Chemicals, IRGACURE 184), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Ciba Specialty Chemicals, IRGAC
  • Oxime compounds for example, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2 -(O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, 1,2-octanedione, 1- [4
  • ⁇ -aminoalkylphenone compounds for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by Ciba Specialty Chemicals, IRGACURE 369), 2-dimethyl Amino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one (Ciba Specialty Chemicals, IRGACURE 379) (9)
  • Phosphine oxide compounds for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by Ciba Specialty Chemicals, IRGACURE 819), bis (2,6-dimethoxybenzoyl) -2,4 , 4-Trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF, Lucirin (registered trademark
  • the benzoin derivative (5) or the phosphine oxide compound (9) is more preferable particularly in terms of photosensitivity and transparency.
  • the addition amount is 0.01 to 30 parts by mass, preferably 0.1 to 5 parts by mass, more preferably 0.2 to 2 parts by mass with respect to 100 parts by mass of the polyorganosiloxane (a). More preferably, it is 0.3 to 1 part by mass. From the viewpoint of obtaining a practical cured pattern, the addition amount of the photopolymerization initiator (b) is 0.01 parts by mass or more, and from the viewpoint of transparency, it is 30 parts by mass or less.
  • the photosensitive resin composition of the present invention preferably contains an ethylenically unsaturated addition polymerizable monomer (c) (hereinafter also referred to as “monomer”).
  • a monomer added to the photosensitive resin composition a compound containing an acryloyl group or a methacryloyl group can be used from the viewpoint of improving crack resistance, heat resistance, and hardness.
  • a monomer for improving crack resistance the following general formula (9): H 2 C ⁇ C (R) — (C ⁇ O) —O— (PO) m ′ — (EO) n ′ — (C ⁇ O) —C (R) ⁇ CH 2 (9) ⁇
  • R is hydrogen or a methyl group
  • PO is a propylene oxide group
  • EO is an ethylene oxide group
  • m ' is a number less than 30
  • n' is a number less than 30.
  • both PO and EO are present, they may be present in random or block, and m ′ + n ′ is a number less than 60.
  • the monomers include polyethylene glycol diacrylate [number of ethylene glycol units 2 to 20], polyethylene glycol dimethacrylate [number of ethylene glycol units 2 to 20], poly (1,2-propylene glycol) diacrylate [1, 2-propylene glycol unit number 2 to 20] and poly (1,2-propylene glycol) dimethacrylate [1,2-propylene glycol unit number 2 to 20].
  • a compound having an alicyclic group is preferable.
  • the following general formula (10) H 2 C ⁇ C (R) — (C ⁇ O) —OY 1 —X′—Y 2 —O— (C ⁇ O) —C (R) ⁇ CH 2 (10) ⁇
  • R is hydrogen or a methyl group
  • Y 1 and Y 2 are organic groups having 1 to 90 carbon atoms including an ethylene oxide group and / or a propylene oxide group
  • Y ′ and X ′ ′ are hydrogen or an organic group containing an alkyl group, an ethylene oxide group or a propylene oxide group, and at least one of Y ′ and X ′ ′ is an acryloyloxy group or a methacryloyloxy group , An acryloyloxymethyl group or a methacryloyloxymethyl group.
  • Examples of the monomers represented by the general formulas (10) and (12) include 1,4-cyclohexane diacrylate, 1,4-cyclohexane dimethacrylate, ethoxylated (hydrogenated bisphenol A) diacrylate [of ethylene glycol unit 2-30], ethoxylated (hydrogenated bisphenol A) dimethacrylate [number of ethylene glycol units 2-30], tricyclodecane dimethanol dimethacrylate, tricyclodecane dimethanol diacrylate, dicyclopentanyl acrylate, di Examples include cyclopentenyloxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentanyl methacrylate, and dicyclopentenyloxyethyl methacrylate.
  • Examples of the monomer represented by the general formula (13) include bisphenol A diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-methacrylic acid adduct, ethoxylated bisphenol A diacrylate [number of ethylene glycol units 2 To 30], and ethoxylated bisphenol A dimethacrylate [number of ethylene glycol units 2 to 30].
  • Examples of the monomer represented by the general formula (15) include pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate [number of ethylene glycol units 2 to 20], Methylolpropane trimethacrylate, tri-2-hydroxyethyl isocyanurate triacrylate, tri-2-hydroxyethyl isocyanurate trimethacrylate, ditrimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate Etc. Moreover, when using the monomers as listed above, they may be used alone or in admixture of two or more as required.
  • a monomer having an alicyclic group from the viewpoint of crack resistance, heat resistance, refractive index, and viscosity (handleability).
  • Specific examples of the monomer having an alicyclic group include tricyclodecane dimethanol dimethacrylate, tricyclodecane dimethanol diacrylate, dicyclopentanyloxy acrylate, dicyclopentanyloxy methacrylate, hydrogenated bisphenol ethylene oxide modified acrylate ( Ethylene oxide unit number 10), hydrogenated bisphenol ethylene oxide modified methacrylate (ethylene oxide unit number 10) and the like.
  • a monomer having an alkyleneoxy group in combination with a monomer having an alicyclic group.
  • the addition amount of the ethylenically unsaturated addition polymerizable monomer (c) is 0.000 per 100 parts by mass of the polyorganosiloxane (a). 1 to 1000 parts by mass, preferably 1 to 500 parts by mass, more preferably 2 to 200 parts by mass, and most preferably 5 to 100 parts by mass from the viewpoint of heat resistance.
  • the photosensitive resin composition according to the present invention includes an ultraviolet absorber and a light stabilizer containing a hindered amine for the purpose of providing a photosensitive resin composition having excellent light resistance of a molded product after curing. At least one compound selected from the group consisting of may be further added. When added, the total amount of the additive is preferably 0.001 to 100 parts by mass with respect to 100 parts by mass of the polyorganosiloxane (a), and 0.01 to 20 in terms of transparency and thermal weight loss. It is more preferable to set it as a mass part.
  • the addition amount in the case of containing a light stabilizer containing an ultraviolet absorber or a hindered amine is preferably 0.2 to 50 parts by mass with respect to 100 parts by mass of the polyorganosiloxane (a), and 1 to 10 parts by mass. Is more preferable. If the addition amount is 0.2 parts by mass or more, it is effective for improving the weather resistance and light resistance of the cured molded product. If the addition amount is 50 parts by mass or less, it is possible to improve light resistance and weather resistance while maintaining high transparency of the photosensitive resin composition and the cured molded product after addition.
  • the photosensitive resin composition according to the present invention includes an adhesion aid such as a silane coupling agent for the purpose of providing a photosensitive resin composition having high adhesion to an inorganic material substrate such as glass or metal. May be further added.
  • an adhesion aid such as a silane coupling agent for the purpose of providing a photosensitive resin composition having high adhesion to an inorganic material substrate such as glass or metal. May be further added.
  • 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-403), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-503), 3-aminopropyl Triethoxysilane (Shin-Etsu Chemical Co., Ltd. KBE-903) is preferred.
  • the addition amount is preferably 1 to 100 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the polyorganosiloxane (a).
  • the addition amount is 1 part by mass or more, a cured molded product having excellent adhesion to an inorganic material substrate such as glass or metal can be obtained.
  • a sensitizer for improving photosensitivity can be added to the photosensitive resin composition according to the present invention as desired.
  • sensitizers include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylamino).
  • these compounds can be used alone or as a mixture of two or more.
  • the addition amount in the case of adding a sensitizer is preferably 0.1 to 10 parts by mass with respect to the polyorganosiloxane (a), although it depends on the amount of other additive components. It is more preferable that
  • a polymerization inhibitor can be added to the photosensitive resin composition according to the present invention for the purpose of improving the viscosity during storage or the stability of photosensitivity.
  • examples of such polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid.
  • 2,6-di-tert-butyl-p-methylphenol 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N- Ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt ,Screw 4-hydroxy-3,5-di-tert- butyl) phenyl methane, or the like can be used.
  • the addition amount is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polyorganosiloxane (a). preferable.
  • An antioxidant may be added to the photosensitive resin composition according to the present invention, if desired, for the purpose of improving the thermal stability in the presence of oxygen.
  • antioxidants include hindered phenols, phosphoruss, lactones, vitamin Es, and sulfurs.
  • antioxidants can be used alone or as a mixture of two or more.
  • the addition amount is preferably 0.001 to 30 parts by mass, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyorganosiloxane (a). preferable.
  • a coating film smoothness-imparting agent inorganic fine particles, etc.
  • Various additives can be appropriately blended.
  • the viscosity can be adjusted by adding a solvent.
  • suitable solvents include N, N-dimethylformamide, N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”), N-ethyl-2-pyrrolidone, tetrahydrofuran, N, N-dimethylacetamide (hereinafter referred to as “NMP”).
  • DMAc dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclopentanone, ⁇ -butyrolactone (hereinafter also referred to as "GBL”), ⁇ -acetyl- ⁇ -butyrolactone, tetramethylurea, 1 , 3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, anisole, ethyl acetate, ethyl lactate, butyl lactate, etc.
  • This Al may be used singly or in combination.
  • N-methyl-2-pyrrolidone or ⁇ -butyrolactone and propylene glycol monomethyl ether acetate are particularly preferable.
  • These solvents can be appropriately added to the photosensitive resin composition depending on the coating film thickness and viscosity, but should be used in the range of 0 to 200 parts by mass with respect to 100 parts by mass of the polyorganosiloxane (a). Is preferred.
  • a photosensitive resin composition comprising the photosensitive resin composition of the present invention or the polyorganosiloxane (a) obtained by the above-described method for producing polyorganosiloxane and a photopolymerization initiator (b). Is cured by light to obtain a cured product.
  • the manufacturing method of the molding using the photosensitive resin composition which concerns on this invention is described.
  • the molded product include a microplastic lens or an optical element for a liquid crystal polarizing plate.
  • the micro plastic lens generally indicates a micro plastic lens having a diameter of several millimeters or less.
  • a micro plastic lens having a diameter of several tens of ⁇ m is used to improve light use efficiency.
  • a microlens array in which a large number of lenses are arranged is a microlens having a diameter of about several hundreds ⁇ m in an optical communication connector or a camera module of a mobile phone.
  • the optical element for liquid crystal polarizing plate refers to a structure on a polarizing filter (polarizing plate) which is one of liquid crystal projectors or liquid crystal display members.
  • a liquid crystal panel is provided with a pair of polarizing filters (polarizing plates) on the front and back of a transparent substrate in which liquid crystal is sealed, and allows only polarized light in a certain vibration direction to pass therethrough.
  • a liquid crystal polarizing plate can be produced by stretching a film and orienting the composition.
  • a polarizing filter can also be formed by forming a specific structure on a substrate at a pitch of 0.2 to 0.3 ⁇ m. A material having the following characteristics can be manufactured.
  • the manufacturing method of the molded product of the present invention is: 1) A step of filling a mold for molding a photosensitive resin composition of the present invention or a photosensitive resin composition containing the polyorganosiloxane (a) obtained by the above production method and a photopolymerization initiator (b), 2) pressing the mold opening against the substrate or another mold; 3) A step of exposing the photosensitive resin composition from the mold and / or the substrate side to obtain a photocured product, 4) peeling the mold from the substrate, or peeling the mold on both sides; and 5) heating the photocured material alone or together with the substrate, including.
  • Step of filling photosensitive resin composition into mold for molding Fill photosensitive resin composition into mold for molding from opening of mold for molding, or photosensitive resin composition to substrate or mold The substrate or the mold is pressed so that the substrate / photosensitive resin composition / mold, or the mold / photosensitive resin composition / mold, and the photosensitive resin composition is filled in the mold for molding. .
  • the photosensitive resin composition When applying to the opening of the molding die, the photosensitive resin composition may be dropped into the opening of the molding die using a dropper or a dispenser. In addition, when applying to the substrate side, it is dropped by using a dropper or a dispenser, applied by a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or spray applied by a spray coater, etc.
  • the photosensitive resin composition is applied on a substrate that has been pretreated as necessary to form a film of the photosensitive resin composition.
  • the thickness of the photosensitive resin composition is preferably 0.01 to 10 mm, more preferably 0.05 to 1 mm, and still more preferably 100 to 500 ⁇ m.
  • it may be diluted with a solvent such as NMP, but in this case, a step of removing the solvent used by heating is required. Heating is performed with the thin film forming surface of the photosensitive resin composition of the coated substrate facing up.
  • a known device can be used as long as it can heat an oven, a far-infrared furnace, a hot plate, or the like.
  • the heating conditions are in the range of 50 ° C. to 150 ° C., preferably 100 ° C.
  • a step of heating the entire substrate can be arbitrarily added.
  • a hot plate is preferable.
  • a silane coupling agent may optionally be applied to the substrate for the purpose of imparting adhesion to the substrate.
  • a silane coupling agent dilute the silane coupling agent with an organic solvent such as NMP and apply it using a spin coater, bar coater, blade coater, curtain coater, screen printer, etc.
  • the solvent used is removed by heating. Heating is performed by using a known one such as an oven, a far-infrared furnace, or a hot plate.
  • chemical species of the silane coupling agent 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.
  • a copper substrate such as a glass substrate, a quartz substrate, a silicon substrate, or a copper clad laminate can be used.
  • a glass substrate or a quartz substrate is preferable.
  • the step of pressing the opening of the mold for molding against the substrate or another mold The opening of the mold for molding, for example, the mold of the micro plastic lens or the optical element for the liquid crystal polarizing plate is replaced with the substrate or the other mold. Press against the thin film forming surface. At this time, pressurization may be performed as necessary.
  • the molding material include rubber, glass, resin such as polydimethylsiloxane, and metal such as Ni, and transparent resin is particularly preferable.
  • the opening of the mold against the substrate when pressing the opening of the mold against the substrate, it is preferable to add a step of applying a silane coupling agent on the substrate before the step.
  • the step of pressing the substrate against the substrate it is preferable to press the opening of the mold against the surface of the substrate coated with the silane coupling agent.
  • Step of exposing the photosensitive resin composition from the mold and / or substrate side to obtain a photocured product In a state where the photosensitive resin composition is sandwiched between the substrate and the mold for molding, Among these, ultraviolet rays are irradiated from the side of the material through which the exposure light is transmitted. If desired, ultraviolet rays may be irradiated from both sides of the laminate in a state in which the photosensitive resin composition is sandwiched between the substrate and the mold for molding or between the molds. From the viewpoint of pattern resolution and handleability as a photocurable resin, i-line is preferred as the wavelength of the exposure light source.
  • Step of heating the photocured material alone or with the substrate By heating at a temperature of 150 ° C. to 270 ° C. for 5 seconds to 5 hours, the remaining reactive groups are bonded to obtain a molded product having excellent heat resistance, for example, a microplastic lens or an optical element for a liquid crystal polarizing plate.
  • Heating can be performed using a hot plate, an oven, or a temperature rising oven that can set a temperature program.
  • the atmospheric gas at the time of heating can be air, but it is preferable to use an inert gas such as nitrogen or argon.
  • this heating process is a process which can be arbitrarily added in order to raise the hardness of a molded article, for example, the optical element for a micro plastic lens or a liquid-crystal polarizing plate.
  • the molded product of the present invention can be obtained by performing the steps described above.
  • the method for producing a cured relief pattern is: 1) A photosensitive resin composition comprising the photosensitive resin composition of the present invention or the polyorganosiloxane (a) obtained by the method for producing a polyorganosiloxane of the present invention and a photopolymerization initiator (b) is applied.
  • a step of obtaining a coating film 2) A step of irradiating the coating film with an actinic ray to photocure the exposed portion, 3) including a step of removing an uncured portion of the film using a developer; and 4) a step of heating the cured portion together with the substrate.
  • the photosensitive resin composition of this invention is apply
  • a spin coater, a die coater, a spray coater, dipping, printing, a blade coater, roll coating, or the like can be used as the coating apparatus or coating method.
  • the coated substrate is soft baked at 80 to 200 ° C. for 10 seconds to 1 hour.
  • Actinic rays are irradiated through a desired photomask using an exposure projection apparatus such as a contact aligner, mirror projection, or stepper.
  • an exposure projection apparatus such as a contact aligner, mirror projection, or stepper.
  • X-rays, electron beams, ultraviolet rays, visible rays and the like can be used as the actinic rays, but in the present invention, those having a wavelength of 200 to 500 nm are preferably used.
  • the light source wavelength is particularly preferably UV-i rays (365 nm), and a stepper is particularly preferable as the exposure projection apparatus.
  • step 2) for the purpose of improving photosensitivity, etc., if necessary, in any combination of temperature and time (preferably temperature 40 ° C. to 200 ° C., time 10 seconds to 30 minutes), Post-exposure baking (PEB) or pre-development baking may be performed.
  • PEB Post-exposure baking
  • Step of removing uncured portion of film using developer The step can be performed by a method such as an immersion method, a paddle method, or a rotary spray method.
  • a developing solution the good solvent of the photosensitive resin composition which concerns on this invention can be used individually or in mixture of a good solvent and a poor solvent suitably.
  • Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, ⁇ -acetyl-gammabutyrolactone, cyclopenta Non-cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone and the like.
  • the poor solvent include methanol, ethanol, isopropanol, water, and the like.
  • the film is washed with a rinse solution and the developer is removed to obtain a coating film with a relief pattern.
  • a rinse solution As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, or the like can be used alone or in an appropriate mixture, or these can be used in a stepwise combination.
  • Step of heating the cured portion together with the substrate ((final) heating step, PEB treatment)
  • the relief pattern obtained as described above is converted into a cured relief pattern at 150 to 260 ° C.
  • This heat curing can be performed using a hot plate, an inert oven, a temperature rising oven that can set a temperature program, and the like.
  • atmosphere gas at the time of heat curing air (air) may be used, and inert gas such as nitrogen and argon may be used as necessary.
  • the cured relief pattern obtained by the above manufacturing method is used to form a micro structure such as a surface protective film, an interlayer insulating film, an ⁇ -ray shielding film, and a micro lens array of a semiconductor device formed on a substrate such as a silicon wafer and its package.
  • An optical element such as a CMOS image sensor can be used by any one selected from the group consisting of supports (partitions) between materials, and by applying other processes in a known semiconductor device manufacturing method.
  • Various semiconductor devices can be manufactured.
  • the electronic component or semiconductor device which has a coating film which consists of resin obtained by hardening the photosensitive resin composition can be obtained.
  • Photosensitive resin composition 1.37 mol (275 g) of dicyclopentylsilanediol as a silanol compound and (CH 3 O) 3 —Si— (CH 2 ) 3 as an alkoxysilane compound in a 2 L separable flask.
  • the pressure is reduced to 500 hPa in an oil bath, the temperature is gradually raised from room temperature to 50 ° C., and the reaction solution becomes transparent from the start of the reaction (ie, dicyclopentylsilanediol) The pressure was reduced to 250 hPa.
  • the reaction was continued for another 2 hours after confirming that methanol generated by continuing stirring as it was was cooled and liquefied by the Liebig condenser and started to be removed from the system. Then, the degree of vacuum was gradually lowered so that bumping did not occur at the same temperature as that at the time of depressurization, and the reaction was continued for 2 hours while further removing methanol at 8 to 15 hPa.
  • a polyorganosiloxane was synthesized in the same manner as in Example 1 except that acetonitrile was used. The resulting polyorganosiloxane had a weight average molecular weight of 1,582.
  • Example 3 Photosensitive resin composition The same procedure as in Example 2 was repeated except that the reaction time in Example 2 was changed to 60 minutes.
  • the resulting polyorganosiloxane had a weight average molecular weight of 1,495.
  • 21% of the number of Si atoms was contained in the structure represented by the general formula (2), and X was — (CH 2 ) 3 — ( 13 C— From NMR).
  • X was — (CH 2 ) 3 — ( 13 C— From NMR).
  • 1 H-NMR the peak derived from the carboxylic acid at the ester site was reduced by 22%.
  • Example 4 Photosensitive resin composition The same procedure as in Example 2 was repeated except that the reaction time in Example 2 was changed to 45 minutes.
  • the resulting polyorganosiloxane had a weight average molecular weight of 1,380.
  • 12% of the number of Si atoms was contained in the structure represented by the general formula (2), and X was — (CH 2 ) 3 —.
  • 1 H-NMR the peak derived from the carboxylic acid at the ester site was reduced by 13%.
  • Example 5 Photosensitive resin composition The same procedure as in Example 2 was repeated except that the reaction time in Example 2 was changed to 30 minutes.
  • the obtained polyorganosiloxane had a weight average molecular weight of 1,260.
  • 9% of the number of Si atoms was contained in the structure represented by the general formula (2), and X was — (CH 2 ) 3 — ( 13 C— From NMR).
  • X was — (CH 2 ) 3 — ( 13 C— From NMR).
  • 1 H-NMR the peak derived from the carboxylic acid at the ester site was reduced by 9%.
  • Example 6 Photosensitive resin composition After cooling the photosensitive resin of Example 1 to room temperature, together with a radical photopolymerization initiator, 5% by mass of A-600 (manufactured by Shin-Nakamura Chemical Co., Ltd.), A-DCP A photosensitive resin composition was obtained by carrying out the same treatment as in Example 1 except that 45% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added.
  • Example 7 Photosensitive resin composition After cooling the photosensitive resin of Example 2 to room temperature, together with a radical photopolymerization initiator, 10% by mass of A-600 (manufactured by Shin-Nakamura Chemical Co., Ltd.), A- A photosensitive resin composition was obtained in the same manner except that 5% by mass of DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added.
  • the reaction was continued for another 2 hours after confirming that methanol generated by continuing stirring as it was was cooled and liquefied by the Liebig condenser and started to be removed from the system. Thereafter, the reaction temperature is gradually raised to 80 ° C., and after further reaction for 2 hours, the degree of vacuum is gradually lowered so that bumping does not occur, and the reaction is continued for 2 hours while further removing methanol at 8 to 15 hPa. I let you. Finally, the pressure was returned to normal pressure, and methanol removal was completed. The obtained cloudy viscous liquid was dissolved in cyclohexane, filtered, and after removing the solvent with an evaporator, vacuum suction was performed at 80 ° C. for 30 minutes.
  • the resulting polyorganosiloxane had a weight average molecular weight of 5,256.
  • 14% of the number of Si atoms was contained in the structure represented by the general formula (2), and X was — (CH 2 ) 3 — ( 13 C— From NMR). In 1 H-NMR, the peak derived from the carboxylic acid at the ester site was reduced by 16%.
  • the reaction was continued for another 2 hours after confirming that methanol generated by continuing stirring as it was was cooled and liquefied by the Liebig condenser and started to be removed from the system. Then, the degree of vacuum was gradually lowered so that bumping did not occur at the same temperature as that at the time of depressurization, and the reaction was continued for 2 hours while further removing methanol at 8 to 15 hPa. Finally, the pressure was returned to normal pressure, and methanol removal was completed. The obtained cloudy viscous liquid was dissolved in cyclohexane, filtered, and after removing the solvent with an evaporator, vacuum suction was performed at 80 ° C. for 30 minutes.
  • the resulting polyorganosiloxane had a weight average molecular weight of 1,002.
  • 1% or less of the number of Si atoms was contained in the structure represented by the general formula (2), and X was — (CH 2 ) 3 — ( 13 C -From NMR).
  • 1 H-NMR the reduction rate of the peak derived from the carboxylic acid at the ester site was 1% or less.
  • 2 parts by mass of a photo radical polymerization initiator Lucirin (registered trademark) TPO manufactured by BASF
  • Example 9 Photosensitive resin composition
  • the reaction temperature was changed to 95 ° C, the reaction pressure to normal pressure, the reaction time to 30 minutes, the drying temperature to 130 ° C, and the drying temperature to 30 minutes, respectively.
  • the same operation as in Example 1 was performed.
  • the resulting polyorganosiloxane had a weight average molecular weight of 7,830.
  • 48% of the number of Si atoms was contained in the structure represented by the general formula (2), and X was — (CH 2 ) 3 —.
  • the peak derived from the carboxylic acid at the ester site was reduced by 54%, and the area having a molecular weight of 1,050 or more in the GPC chart was 89% (FIGS. 5 and 6).
  • Example 10 Photosensitive resin composition After cooling the photosensitive resin of Example 1 to room temperature, dicyclopentanyloxyacrylate (FA-513AS, manufactured by Hitachi Chemical Co., Ltd.) was added together with a radical photopolymerization initiator. A photosensitive resin composition was obtained by carrying out the same treatment as in Example 1 except that the addition by mass% was performed.
  • dicyclopentanyloxyacrylate FA-513AS, manufactured by Hitachi Chemical Co., Ltd.
  • Photosensitive Resin Composition A photosensitive resin composition was obtained in the same manner as in Example 1 using polyorganosiloxane synthesized according to the method described in Synthesis Example 1 of Patent Document 3.
  • Example 11 Photosensitive resin composition
  • 0.28 parts by mass of antioxidant IRGANOX245 manufactured by BASF
  • antioxidant GSY-P101 manufactured by Osaki Kogyo Co., Ltd.
  • a photosensitive resin composition was obtained in the same manner as in Example 7 except that 0.11 part by mass was added.
  • Each of the resin compositions obtained in Examples 7 and 11 was sandwiched between glass substrates, and one glass substrate was peeled off from the cured film obtained by performing exposure at 3000 mJ / cm 2 at a thickness of 500 ⁇ m to prepare a sample. .
  • a wavelength of 400 nm when the obtained sample was subjected to heat treatment at 150 ° C.
  • Example 3 shows the transmittance at 400 nm when the heat treatment sample was further subjected to heat treatment (B) at 260 ° C. for 10 seconds ⁇ 3 times in nitrogen.
  • the transmittance of the cured film was measured using a UV-visible spectrophotometer V-550 manufactured by JASCO Corporation with an untreated glass substrate as a reference. It can be seen that the photosensitive resin composition of Example 10 to which the antioxidant is added has improved thermal stability in the presence of oxygen.
  • a heat-resistant photosensitive transparent resin useful for manufacturing a solid-state imaging device or an electronic component integrated product that requires a solder reflow process at 260 ° C. can be obtained.
  • the optical element for liquid crystal polarizing plates for projectors can be obtained.

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Abstract

La présente invention concerne : une composition de résine transparente photosensible possédant une excellente résistance aux chocs thermiques, dans la production de produits avec des parties électroniques intégrées ou d'éléments d'imagerie à semi-conducteurs, qui nécessite un procédé de soudage par refusion ; et une lentille microplastique ou un produit moulé d'élément optique pour plaques de polarisation à cristaux liquides qui utilise ladite composition de résine transparente photosensible. Cette composition de résine photosensible contient : 100 parties en masse d'un polyorganosiloxane (a) possédant un groupe fonctionnel polymérisable, préparé selon un procédé consistant à mélanger un composé alkoxysilane représenté par la formule générale (1), R1 aR2 bSi(OR3)4-a-b (avec R1, R2, R3, a, et b étant tels que définis dans la description) avec un catalyseur, et à polymériser ledit composé alkoxysilane. Ledit polyorganosiloxane (a) comprend une structure représentée par la formule générale suivante (2), ≡Si-O-X-Si≡ (X étant tel que défini dans la description), et la structure de ladite formule générale (2) contient entre 5 et 60 % des atomes de Si compris dans ledit polyorganosiloxane (a), et entre 0,01 et 30 parties en masse d'un initiateur de photopolymérisation (b).
PCT/JP2011/073704 2010-10-14 2011-10-14 Composition de résine photosensible et son procédé de production WO2012050201A1 (fr)

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SG2013027719A SG189383A1 (en) 2010-10-14 2011-10-14 Photosensitive resin composition and method for producing same
JP2012538732A JPWO2012050201A1 (ja) 2010-10-14 2011-10-14 感光性樹脂組成物及びその製造方法
KR1020137009392A KR20130066684A (ko) 2010-10-14 2011-10-14 감광성 수지 조성물 및 그의 제조 방법
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WO2013031985A1 (fr) * 2011-08-31 2013-03-07 旭化成イーマテリアルズ株式会社 Composition de résine de silicone photosensible alcalino-soluble
JP2014057016A (ja) * 2012-09-14 2014-03-27 Tokuyama Corp 光硬化性ナノインプリント用組成物およびパターンの形成方法
JP2023521261A (ja) * 2021-03-16 2023-05-24 モメンティブ・パフォーマンス・マテリアルズ・コリア・カンパニー・リミテッド シリコーン系組成物及びその硬化物

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TWI801443B (zh) * 2017-10-27 2023-05-11 美商陶氏有機矽公司 可固化聚有機矽氧烷組成物、藉由固化該等組成物獲得之固化體、及包含其之電子裝置
JP2019104836A (ja) * 2017-12-13 2019-06-27 信越化学工業株式会社 オルガノポリシロキサン化合物およびそれを含む活性エネルギー線硬化性組成物
TWI698636B (zh) * 2018-12-18 2020-07-11 英業達股份有限公司 印刷機刮刀自動檢測設備

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WO2013031985A1 (fr) * 2011-08-31 2013-03-07 旭化成イーマテリアルズ株式会社 Composition de résine de silicone photosensible alcalino-soluble
JP2014222367A (ja) * 2011-08-31 2014-11-27 旭化成イーマテリアルズ株式会社 感光性アルカリ可溶シリコーン樹脂組成物
JP2014057016A (ja) * 2012-09-14 2014-03-27 Tokuyama Corp 光硬化性ナノインプリント用組成物およびパターンの形成方法
JP2023521261A (ja) * 2021-03-16 2023-05-24 モメンティブ・パフォーマンス・マテリアルズ・コリア・カンパニー・リミテッド シリコーン系組成物及びその硬化物
JP7408807B2 (ja) 2021-03-16 2024-01-05 モメンティブ・パフォーマンス・マテリアルズ・コリア・カンパニー・リミテッド シリコーン系組成物及びその硬化物

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