WO2013157643A1 - ラジカル架橋性基を有するポリシロキサン組成物 - Google Patents

ラジカル架橋性基を有するポリシロキサン組成物 Download PDF

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WO2013157643A1
WO2013157643A1 PCT/JP2013/061674 JP2013061674W WO2013157643A1 WO 2013157643 A1 WO2013157643 A1 WO 2013157643A1 JP 2013061674 W JP2013061674 W JP 2013061674W WO 2013157643 A1 WO2013157643 A1 WO 2013157643A1
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group
polysiloxane
mass
polysiloxane composition
meth
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PCT/JP2013/061674
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English (en)
French (fr)
Japanese (ja)
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由香 佐々木
徹 勝又
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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 CN201380020944.9A priority Critical patent/CN104245846B/zh
Priority to JP2014511263A priority patent/JP5886420B2/ja
Priority to KR1020147024580A priority patent/KR101566138B1/ko
Publication of WO2013157643A1 publication Critical patent/WO2013157643A1/ja

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • 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
    • 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
    • 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
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

Definitions

  • the present invention relates to the formation of a surface protective film, an interlayer insulating film, an ⁇ -ray shielding film, etc. in a semiconductor device as an insulating material suitably used for a display device, and a semiconductor device equipped with an image sensor, micromachine, or microactuator
  • the present invention relates to a polysiloxane composition having a radically crosslinkable group that is preferably used for, for example, a cured product obtained by curing the polysiloxane composition, or a transparent insulating film.
  • Polyimide resins having excellent heat resistance, electrical properties, and mechanical properties are widely used for insulating materials for electronic parts and surface protection films, interlayer insulation films, and ⁇ -ray shielding films for semiconductor devices.
  • Such a polyimide resin is usually provided in the form of a photosensitive polyimide precursor composition, which is applied to a substrate, soft baked, irradiated with actinic rays (exposure) through a desired patterning mask, and developed. And it has the characteristic that the hardening relief pattern which consists of heat resistant polyimide resin can be formed easily by performing a thermosetting process (for example, refer the following patent documents 1).
  • polyimide having excellent characteristics as described above has absorption derived from the polyimide ring in the vicinity of 500 nm to 400 nm and is not suitable for applications requiring high transparency such as display devices or optical system materials.
  • the lower limit of the curing treatment temperature is 300 ° C. Before and after.
  • Patent Document 2 discloses a photosensitive siloxane-based material that can be cured at a low temperature.
  • the patterned resin When forming a display device or optical material, the patterned resin is exposed to high temperature several times, and after it becomes a final product, it is exposed to temperature shocks due to changes in the surrounding environment, so it has high crack resistance is required.
  • Patent Document 2 when the technique disclosed in Patent Document 2 is used, it has been found that there is room for improvement in crack resistance in the required thick film.
  • area which requires high transparency and low temperature curability like a display apparatus or an optical system material the photosensitive film-forming material which satisfy
  • the problem to be solved by the present invention is a radically crosslinkable group capable of obtaining a cured product having high transparency and excellent crack resistance due to thermal shock, and capable of being cured at low temperature.
  • the present inventors have unexpectedly discovered that the above problems can be solved by using a polysiloxane composition having a specific radical crosslinkable group.
  • the present invention has been completed. That is, the present invention is as follows.
  • the g value is 2.034.
  • a radical crosslinkable group having a peak of ⁇ 1.984 and containing a radical of 0.1 ⁇ 10 ⁇ 6 mol / g to 120 ⁇ 10 ⁇ 6 mol / g with respect to 100 parts by mass of the total solid content in the composition A polysiloxane composition.
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom and / or a monovalent organic group having 1 to 10 carbon atoms, and R 1 and R 2 , or R 4 3 and R 4 may be bonded to each other to form a ring structure.
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom and / or a monovalent organic group having 1 to 10 carbon atoms, and R 1 and R 2 , or R 4 3 and R 4 may be bonded to each other to form a ring structure.
  • a polysiloxane composition further comprising a photoradical initiator.
  • the (C) nitroxy compound has the following general formula: ⁇ Wherein R 5 is bonded through a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an amino group, a carboxylic acid group, a cyano group, a heteroatom-substituted alkyl, or an ether, ester, amide or urethane bond.
  • R 6 represents a divalent or trivalent organic group
  • n 1 and m 1 are integers satisfying 1 ⁇ n 1 + m 1 ⁇ 2
  • n 2 and m 2 are 1 ⁇ n 2 + m 2 ⁇ 2
  • n 3 and m 3 are integers satisfying 1 ⁇ n 3 + m 3 ⁇ 2
  • l is an integer of 2 or 3.
  • polysiloxane according to any one of [1] to [6], wherein the polysiloxane having a radical crosslinkable group (A) is a polysiloxane having a (meth) acryloyl group and / or a styryl group. Composition.
  • the above-mentioned [F] further comprises an alkali-soluble resin having an acid value of 10 to 200 mg KOH / g of 1 to 50 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition.
  • the polysiloxane composition according to any one of [9].
  • the polysiloxane having a radical crosslinkable group (A) has the following general formula: ⁇ In the formula, Ph represents a phenyl group. ⁇
  • the following structure ⁇ Wherein R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom and / or a monovalent organic group having 1 to 10 carbon atoms, and R 1 and R 2 , or R 4 3 and R 4 may be bonded to each other to form a ring structure.
  • a polysiloxane composition further comprising (B) a photoradical initiator.
  • the (C) nitroxy compound has the following general formula: ⁇ Wherein R 5 is bonded through a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an amino group, a carboxylic acid group, a cyano group, a heteroatom-substituted alkyl, or an ether, ester, amide or urethane bond.
  • R 6 represents a divalent or trivalent organic group
  • n 1 and m 1 are integers satisfying 1 ⁇ n 1 + m 1 ⁇ 2
  • n 2 and m 2 are 1 ⁇ n 2 + m 2 ⁇ 2
  • n 3 and m 3 are integers satisfying 1 ⁇ n 3 + m 3 ⁇ 2
  • l is an integer of 2 or 3.
  • composition [20] The above [14] to [14], further comprising (D) a compound having a photopolymerizable double bond in an amount of 5 to 45 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition.
  • the polysiloxane fat composition according to any one of [19].
  • the alkali-soluble resin further comprising (F) an acid value of 10 to 200 mgKOH / g of 1 to 50 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition.
  • the polysiloxane having a radical crosslinkable group (A) has the following general formula: ⁇ In the formula, Ph represents a phenyl group.
  • the polysiloxane composition according to any one of [14] to [22] which has a structure represented by: [24] A cured product obtained by curing the polysiloxane composition according to any one of [14] to [22].
  • a polysiloxane composition having a radical crosslinkable group capable of being cured at low temperature which can obtain a cured product having high transparency and excellent resistance to cracking due to temperature shock.
  • ESR measurement results of electron spin resonance (ESR) measurement of acetone ESR measurement result of 4-hydroxy-TEMPO. The figure explaining the calculation method of g value in ESR.
  • the ESR measurement result of the polysiloxane composition of Example 19 The ESR measurement result of the polysiloxane composition of Example 10.
  • the ESR measurement result of the polysiloxane composition of Example 11 The ESR measurement result of the polysiloxane composition of Example 12.
  • the polysiloxane composition having a radical crosslinkable group includes the following components: (A) polysiloxane having a radical crosslinkable group, and (B) a photoradical initiator, Optionally, other ingredients are included.
  • the polysiloxane having a radical crosslinkable group (A) can be composed of a polysiloxane having a radical crosslinkable group and (C) a nitroxy compound as described below.
  • a cured product obtained by curing a polysiloxane composition having a radical crosslinkable group will be described.
  • the nitroxy compound is allowed to stand for 24 hours in the atmosphere under the condition of shielding light having a wavelength of 24 ° C., atmospheric pressure, and 400 nm or less, and then using an electron spin resonance (ESR) apparatus.
  • ESR electron spin resonance
  • the polysiloxane having a radical crosslinkable group is allowed to stand for 24 hours in the atmosphere under the condition of shielding light having a wavelength of 24 ° C., normal pressure, and 400 nm or less, and then using an electron spin resonance (ESR) apparatus. And a group capable of generating a radical having a peak with a g value of 2.034 to 1.984 when measured.
  • the polysilosan simple substance has the predetermined peak.
  • a polysiloxane composition having a radical crosslinkable group having a peak of ⁇ 1.984 means that the polysiloxane simple substance having a radical crosslinkable group has the radical generating group, and the polysiloxane simple substance having a radical crosslinkable group is Although it does not have the radical generating group, for example, it includes both in the case of a mixed state of a polysiloxane simple substance, a radical, and a polysiloxane simple substance, a radical and a combination thereof generated when coexisting with a nitroxy compound .
  • the polysiloxane composition having a radical crosslinkable group further has an alkali-soluble group means that the polysiloxane itself has an alkali-soluble group and the composition containing the polysiloxane has an alkali As a result of including a soluble resin, both the case where the polysiloxane composition includes an alkali-soluble group are included.
  • a radical having a peak with a g value of 2.034 to 1.984 when measured using a spin resonance (ESR) apparatus is preferably contained in an amount of 0.1 ⁇ 10 ⁇ 6 mol or more with respect to 1 g of the solid content in the composition. More preferably, it is 0.15 ⁇ 10 ⁇ 6 mol or more.
  • the total solid content in the polysiloxane composition having a radical crosslinkable group can be measured, for example, using a TGA (thermogravimetric apparatus).
  • the amount of radicals can be measured using an ESR (electron spin resonance apparatus).
  • 4-hydroxy TEMPO was prepared as a standard having 1 mole of radical per mole, a calibration curve was created, the amount of radicals in the composition was measured, and the composition was combined with the solid content measured by TGA. It is possible to calculate the radical content contained per gram of solid content.
  • 0.0017 parts by mass of the nitroxy compound corresponds to a radical amount of 0.1 ⁇ 10 ⁇ 6 mol / g
  • the nitroxy compound 0.005 The mass part corresponds to a radical amount of 0.29 ⁇ 10 ⁇ 6 mol / g
  • the nitroxy compound 0.009 part by mass corresponds to a radical amount of 0.523 ⁇ 10 ⁇ 6 mol / g
  • the nitroxy compound 1 part by mass corresponds to a radical amount of 58 ⁇ 10 ⁇ 6 mol / g
  • 2 parts by weight of the nitroxy compound corresponded to a radical amount of 116 ⁇ 10 ⁇ 6 mol / g.
  • the polysiloxane having a radical crosslinkable group has a group that can be crosslinked by radicals in the polysiloxane, and can dramatically improve the hardness of the cured film.
  • the radical crosslinkable group may be a group containing a photopolymerizable unsaturated bond (for example, a double bond). Although it does not restrict
  • the polysiloxane having a radical crosslinkable group may contain two or more of these groups. Further, (A) the polysiloxane having a radical crosslinkable group preferably has at least a (meth) acryloyl group and / or a styryl group from the viewpoint of curability. (A) The molar concentration of the photopolymerizable unsaturated bond group in the polysiloxane having a radical crosslinkable group is preferably 0.01 mmol / g or more from the viewpoint of pattern adhesion, film hardness, and crack resistance. More preferably, it is 0.1 mmol / g or more, and still more preferably 0.5 mmol / g or more.
  • the molar concentration is preferably 10.0 mmol / g or less, more preferably 7.5 mmol / g or less, and still more preferably 5.0 mmol / g or less.
  • the content of the photopolymerizable unsaturated bond group in the polysiloxane having a radical crosslinkable group can be calculated by measuring the iodine value of the obtained polymer.
  • the polysiloxane having a radical crosslinkable group preferably contains an alkali-soluble group in one molecule.
  • the alkali-soluble group is not particularly limited.
  • a carboxyl group, a dicarboxylic acid anhydride group, or a residue of a dicarboxylic acid anhydride group improves the alkali solubility of the polysiloxane and is a residue after development. It is preferable from the viewpoint of suppressing the occurrence of the above.
  • the content of the carboxyl group, dicarboxylic acid anhydride group, or dicarboxylic acid anhydride group residue in the polysiloxane having a radical crosslinkable group is such that (A) the polysiloxane having a radical crosslinkable group is Although it is not particularly limited as long as it has a group, the acid value of the polysiloxane having a radical crosslinkable group (A) is 10 mgKOH / g from the viewpoint of reduction of residues after development and crack resistance of a cured film. The above is preferable, more preferably 15 mgKOH / g or more, and still more preferably 20 mgKOH / g or more.
  • the acid value is preferably 200 mgKOH / g or less, more preferably 190 mgKOH / gmol or less, and still more preferably 180 mgKOH / g or less.
  • the polysiloxane composition having a radical crosslinkable group contains a polysiloxane having two or more types of (A) radical crosslinkable groups, at least one of them has an acid value within the range described above. It is preferable that it contains the residue of a carboxyl group, a dicarboxylic acid anhydride group, or a dicarboxylic acid anhydride group in such a content that it has.
  • the acid value means the number of milligrams of potassium hydroxide necessary to neutralize the carboxyl group in 1 g of a sample.
  • An example of a method for measuring the acid value is as follows: A 3 g sample is accurately weighed and dissolved in 20 ml of ethanol. Stir the resulting solution at room temperature, add another 5 g of purified water and stir for an additional hour at room temperature. Thereafter, several drops of a phenolphthalein methanol solution are added as an indicator, neutralized with a 1/2 N aqueous potassium hydroxide solution, and the acid value is calculated from the amount of the aqueous potassium hydroxide solution used.
  • the polysiloxane having a radical crosslinkable group is represented by the following general formula (I): R 7 R 8 a1 Si (R 9 ) 3-a1 ⁇
  • R 7 represents a monovalent organic group having 2 to 20 carbon atoms including a photopolymerizable unsaturated bond group (for example, a double bond group), and each R 8 independently represents a substituent.
  • R 9 is a hydroxyl group, a linear or branched alkoxy group having 1 to 12 carbon atoms, a phenoxy group, an alkylcarbonyloxy group, chlorine (Cl) or bromine (Br).
  • at least one monovalent group selected from the group consisting of: a hydroxyl group, a methoxy group, an ethoxy group, an n-propoxy group, or an isopropoxy group, and from the viewpoint of reactivity, a hydroxyl group, a methoxy group, or an ethoxy group. Groups are more preferred.
  • R 7 is preferably a monovalent organic group having 2 to 17 carbon atoms having an unsaturated bond (for example, a double bond), specifically, for example, a vinyl group, styryl.
  • R 7 is preferably a monovalent organic group having 2 to 17 carbon atoms having an unsaturated bond (for example, a double bond), specifically, for example, a vinyl group, styryl.
  • a styryl group or a 3- (meth) acryloxypropyl group is preferable.
  • (meth) acryl shows an acryl group and a methacryl group.
  • the polysiloxane having a radical crosslinkable group may contain an alkali-soluble group, at least one silane compound represented by the above general formula (I) and the following general formula Formula (II): R 10 R 11 a2 Si (R 9 ) 3-a2 ⁇
  • R 9 is as defined in the above general formula (I)
  • R 10 represents an alkali-soluble group
  • each R 11 independently represents the number of carbon atoms that may have a substituent.
  • 1 to 20 represents a linear or branched organic group, aryl group, or alkylaryl group
  • a2 is an integer of 0 to 2.
  • R 10 is not particularly limited as long as it has a carboxyl group, a dicarboxylic anhydride group, or a dicarboxylic anhydride group residue. It is preferably selected from the group consisting of monovalent organic groups represented by II-1).
  • Rx is a linear or branched divalent organic group having 1 to 6 carbon atoms
  • Ry and Rz are each independently a methyl group, an ethyl group, a propyl group, or an isopropyl group.
  • Ra is a linear, branched or cyclic divalent group having 2 to 16 carbon atoms.
  • Rs is a linear, branched or cyclic divalent organic group having 1 to 20 carbon atoms
  • Rt is a linear group having 1 to 18 carbon atoms
  • a branched or cyclic divalent organic group, and Ru and Rv are each independently a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, or It is a monovalent organic group represented by the general formula (II-2).
  • Rw is a linear, branched or cyclic divalent organic group having 1 to 16 carbon atoms
  • Rb is a linear or branched chain having 1 to 20 carbon atoms.
  • Rc is a group represented by the following general formula (II-3) or a hydrogen atom is there.
  • Ra is a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms.
  • R 10 preferred examples of the organic group contained in R 10 include succinic anhydride group (R 10 -1), cyclohexanedicarboxylic anhydride group (R 10 -2), 4-methyl- Cyclohexanedicarboxylic anhydride group (R 10 -3), 5-methyl-cyclohexanedicarboxylic anhydride group (R 10 -4), bicycloheptane dicarboxylic anhydride group (R 10 -5), 7-oxa-bicycloheptane Dicarboxylic anhydride group (R 10 -6), phthalic anhydride group (R 10 -7), succinic acid group or its half ester group (R 10 -8), cyclohexane dicarboxylic acid group or its half ester group (R 10-9), 4-methyl - cyclohexane dicarboxylic acid group or a half ester group (R 10 -10), 5-methyl - cyclohexane Carboxylic acid group
  • Rx is a linear or branched divalent organic group having 1 to 6 carbon atoms.
  • Rx is preferably a hydrocarbon group.
  • the hydrocarbon group include methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, tert-butylene group, n-pentylene group, isopentylene group, neopentylene group, A tert-pentylene group may be mentioned.
  • These groups may contain a double bond and / or a triple bond, and may be used alone or in combination of two or more.
  • a propylene group is the most preferable.
  • a group having an amide bond (R 10 -15) is obtained by reaction of an amino group with a dicarboxylic acid anhydride, a group containing a carboxyl group.
  • Rs is a linear, branched or cyclic divalent organic group having 1 to 20 carbon atoms.
  • the dicarboxylic acid anhydride represented by the general formula (II-1) include succinic anhydride, cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, and 5-methyl-cyclohexane dicarboxylic acid.
  • the group having an isocyanuric skeleton (R 10 -16) is a hydroxyl group generated from an isocyanuric skeleton having a glycidyl group via a ring-opening reaction of glycidyl by a reaction with a carboxyl group or a hydroxyl group. It is a group containing a carboxyl group obtained by reacting with a dicarboxylic acid anhydride.
  • R 10 is a propyl succinic anhydride group (R 10 -1), a propyl succinic acid group, or a half methyl ester group thereof, or a half ethyl ester group thereof (R 10 -8).
  • the polysiloxane having a radical crosslinkable group is at least one silane compound represented by the above general formula (I) and at least one kind represented by the above general formula (II).
  • the silane compound the following general formula (III): R 12 a3 Si (R 9 ) 4-a3 ⁇ Wherein R 9 is as defined in the above general formula (I), and each R 12 is independently a linear or branched chain having 1 to 20 carbon atoms which may have a substituent.
  • a3 is an integer of 0 to 3.
  • silane compound represented by the general formula (I) examples include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and 3- (meth) acrylic.
  • the most preferable compound among the alkoxysilane compounds containing a carboxyl group, a dicarboxylic anhydride group, or a half ester group of a dicarboxylic anhydride group is (3- (Trimethoxysilylpropyl) succinic anhydride, (3-triethoxysilylpropyl) succinic anhydride, (3-trimethoxysilylpropyl) succinic acid, (3-triethoxysilylpropyl) succinic acid, (3-trimethoxy (Silylpropyl) succinic acid half methyl ester, (3-triethoxysilylpropyl) succinic acid half methyl ester, (3-trimethoxysilylpropyl) succinic acid half ethyl ester, and (3-triethoxysilylpropyl) succinic acid It is a half ethyl ester of an acid.
  • examples of the compound having a polymerizable cyclic ether bond group include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxy.
  • Silane 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) triethoxysilane 2- (3,4-epoxycyclohexyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) methyldiethoxysilane, and the like.
  • silane compound represented by the general formula (III) other than the compound having a polymerizable cyclic ether bond group include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxylane, dimethyldiethoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane
  • the polysiloxane having a radical crosslinkable group can be synthesized by any method.
  • the silane compound represented by the general formula (I) and the silane compound represented by the general formula (II) And the silane compound represented by the general formula (III) can be obtained by adding water and a catalyst and then condensing the obtained hydrolyzate in the presence or absence of a solvent. .
  • the hydrolysis reaction is carried out by adding an acidic catalyst and water over 1 minute to 180 minutes to the silane compound in the solvent.
  • the temperature in the process of obtaining a hydrolyzate is preferably 10 ° C. or higher, more preferably 20 ° C. or higher from the viewpoint of hydrolysis reactivity, while 150 ° C.
  • the reaction time in the process of obtaining the hydrolyzed monster is preferably 0.1 hour or more from the viewpoint of hydrolysis reactivity, more preferably 0.5 hour or more, while 10 hours from the viewpoint of protecting the functional group. The following is preferable, and more preferably 5 hours or less.
  • the hydrolysis reaction is preferably performed in the presence of an acidic catalyst.
  • an acidic aqueous solution containing hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid or phosphoric acid is preferable.
  • the preferable content of these acidic catalysts is preferably 0.01 mol% or more from the viewpoint of hydrolysis reactivity with respect to all silane compounds used during the hydrolysis reaction, and 10 mol% or less from the viewpoint of functional group protection. Is preferred.
  • the reaction solution is preferably heated as it is at 50 ° C. or higher and below the boiling point of the solvent used for 1 hour to 100 hours to carry out the condensation reaction.
  • the solvent used for the hydrolysis reaction of the silane compound and the condensation reaction of the hydrolyzate is not particularly limited, and can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition. Further, these reactions may be carried out by combining two or more solvents or without solvent. Specific examples of the solvent include alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, t-butyl alcohol, pentyl alcohol, isopentyl alcohol, diacetone alcohol, ethylene glycol, propylene glycol and the like.
  • Glycols ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and other ethers, methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, Such as methyl isobutyl ketone and cyclopentanone Tons, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, acetates such as methyl lactate, ethyl lactate, butyl lactate, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, etc. be able to.
  • a solvent When a solvent is produced by the hydrolysis reaction, it can be hydrolyzed without a solvent. It is also preferable to adjust the concentration of the resin composition to an appropriate level by adding a solvent after completion of the hydrolysis reaction. Moreover, according to the use of a resin composition, after hydrolysis, an appropriate amount, such as produced
  • the amount of the solvent used for the hydrolysis reaction is preferably 80 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of all silane compounds.
  • the water used for the hydrolysis reaction is preferably ion exchange water. The amount of water can be arbitrarily selected, but is preferably in the range of 1.0 mol to 4.0 mol with respect to 1 mol of the silane compound used in the hydrolysis reaction.
  • Silanol (residual silanol) present in the polysiloxane having a radical crosslinkable group and not involved in the condensation is reduced in shrinkage due to condensation during baking, water generated by condensation, and degassing reduction of alcohol. From the viewpoint, a small amount is preferable, and it is preferable that the amount is almost eliminated.
  • the polysiloxane having a radical crosslinkable group preferably has little or no residual silanol.
  • the cycloalkyl groups may be the same or different from each other, and may be linked to each other via a covalent bond.
  • examples of R 13 include a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a naphthyl group, a methyl group, an ethyl group, a cyclopentyl group, and a cyclohexyl group.
  • silane diol compound represented by the general formula (IV) examples include diphenyl silane diol, di-p-toluyl silane diol, dixyl silane diol, ditrimethyl phenyl silane diol, di-p-styryl silane diol, Examples include dinaphthyl silane diol, dicyclopentyl silane diol, cyclohexyl methyl silane diol, and the like, and diphenyl silane diol, dicyclopentyl silane diol, and cyclohexyl methyl silane diol are particularly preferable from the viewpoint of copolymerization and heat resistance.
  • the temperature of the reaction for performing condensation without positively adding water is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, while from the viewpoint of protecting functional groups. 150 ° C. or lower is preferable, and 130 ° C. or lower is more preferable.
  • the reaction time for performing the condensation without positively adding water is preferably 0.5 hours or more, more preferably 1 hour or more, while from the viewpoint of protecting the functional group. 48 hours or less is preferable, and 30 hours or less is more preferable.
  • a catalyst is used and water is not positively added.
  • the catalyst a basic catalyst or an acidic catalyst can be used.
  • basic catalyst a trivalent or tetravalent metal alkoxide can be used.
  • basic catalysts include trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, tri-iso-propoxyaluminum, tri-n-butoxyaluminum, tri-iso-butoxyaluminum, tri-sec.
  • Alkali metal hydroxides or alkaline earth metal hydroxides such as barium hydroxide, sodium hydroxide, potassium hydroxide, strontium hydroxide, calcium hydroxide, and magnesium hydroxide are used as basic catalysts. May be.
  • NH 4 F ammonium fluoride
  • barium hydroxide, sodium hydroxide, strontium hydroxide, tetra-tert-butoxy titanium, and tetra-iso-propoxy titanium are preferable.
  • the basic catalyst is preferably liquid in the reaction temperature range.
  • the preferable content of these basic catalysts is preferably 0.01 mol% or more from the viewpoint of condensation reactivity with respect to all silane compounds, and is preferably 10 mol% or less from the viewpoint of protection of functional groups.
  • an organic acidic catalyst containing no water can be used. Specifically, as the acidic catalyst, acetic acid, trifluoroacetic acid, acrylic acid, methacrylic acid, citric acid, malic acid, succinic acid, phthalic acid, (3-trimethoxysilylpropyl) succinic acid, or a half ester thereof, And (3-triethoxysilylpropyl) succinic acid or a half ester thereof.
  • the preferable content of these acidic catalysts is preferably 0.01 mol% or more from the viewpoint of condensation reactivity with respect to all silane compounds, and is preferably 10 mol% or less from the viewpoint of protection of functional groups.
  • a polymerization inhibitor may be added during synthesis from the viewpoint of protecting the crosslinkable group.
  • the polysiloxane having a radical crosslinkable group has the following structure: ⁇ In the formula, Ph represents a phenyl group. ⁇ It is also preferable from the viewpoint of heat resistance.
  • the ratio of the silicon atom of the polysiloxane having a radical crosslinkable group having the above structure is preferably 10 mol% to 80 mol%, more preferably 30 mol% to 70 mol%, still more preferably 40 mol% to 60 mol%. %.
  • the content of (A) the polysiloxane having a radical crosslinkable group is not particularly limited and can be arbitrarily selected depending on the desired film thickness or application, but from the viewpoint of heat-resistant transparency.
  • 1 part by mass or more is preferable with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more. From a viewpoint of property, 99 mass parts or less are preferable, More preferably, it is 90 mass parts or less, More preferably, 85 mass parts or less are preferable.
  • (B) Photoradical (polymerization) initiator It is important that the (B) photoradical initiator is added to the polysiloxane composition in order to impart a formability of a photosensitive pattern to the polysiloxane composition.
  • Examples of the (B) photoradical initiator include the following photoradical initiators (1) to (10):
  • 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 BASF, IRGACURE651) ), 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, IRGACURE 184), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF, IRGACURE 907), 2- Hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl ⁇ -2-methylpropan-1-one (manufactured by BASF, IRGACURE127), methyl phenylglyoxylate
  • Thioxanthone derivatives for example, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone
  • Benzyl derivatives for example, benzyl, benzyldimethyl ketal, benzyl- ⁇ -methoxyethyl acetal
  • Benzoin derivatives for example, benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1phenylpropan-1-one (manufactured by BASF, DAROCURE 1173)
  • Oxime compounds for example, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2 -(O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl) Oxime)] (manufactured by BASF, IRGACURE OXE01), ethanone, 1- [9-ethyl-6- (2-methylb
  • ⁇ -hydroxy ketone compounds for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl ⁇ -2-methylpropane
  • ⁇ -aminoalkylphenone compounds for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by BASF, IRGACURE 369), 2-dimethylamino-2- (4-Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one (manufactured by BASF, IRGACURE 379)
  • Phosphine oxide compounds for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, IRGACURE 819), bis (2,6-dimethoxybenzoyl) -2,4,4 -Trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (BASF, Lucirin TPO)
  • Titanocene compound for example, bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium (manufactured by BASF) , IRGACURE 784)
  • the photo radical initiators (1) to (10) may be used alone or in combination of two or more.
  • benzoin derivatives or (9) phosphine oxide compounds are more preferable, particularly from the viewpoint of improving photosensitivity and transparency.
  • the content of the photo radical initiator is preferably 0.01 parts by mass or more, more preferably 0. 0 parts by mass from the viewpoint of obtaining sufficient sensitivity with respect to 100 parts by mass of the total solid content in the polysiloxane composition. From the viewpoint of sufficiently curing the bottom portion of the photosensitive resin layer, it is preferably 15 parts by mass or less, and more preferably 10 parts by mass or less.
  • the nitroxy compound has the following general formula (V): ⁇ Wherein R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and R 1 and R 2 , or R 3 and R 4 4 may be bonded to each other to form a ring structure. ⁇ It is a compound containing the structure represented by this. R 1 , R 2 , R 3 and R 4 are preferably monovalent organic groups having 1 to 10 carbon atoms.
  • the polysiloxane composition of this embodiment is excellent in crack resistance after being cured in a nitrogen atmosphere by containing (C) a nitroxy compound.
  • R 1 , R 2 , R 3 and R 4 may each independently be an alkyl group or an alkyl group substituted with a hetero atom.
  • alkyl group a methyl group, an ethyl group, a propyl group and the like are preferable, and as the hetero atom, a halogen, oxygen, sulfur, nitrogen and the like are preferable.
  • Examples of the (C) nitroxy compound used in the present embodiment include di-tert-butyl nitroxide, di-1,1-dimethylpropyl nitroxide, di-1,2-dimethylpropyl nitroxide, di-2,2-dimethyl.
  • Propyl nitroxide and a compound represented by the following general formula (VI), (VII) or (VIII) are preferred.
  • a compound represented by the following general formula (VI), (VII) or (VIII) is more preferable.
  • R 5 is bonded through a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an amino group, a carboxylic acid group, a cyano group, a heteroatom-substituted alkyl, or an ether, ester, amide or urethane bond.
  • R 6 represents a divalent or trivalent organic group
  • n 1 and m 1 are integers satisfying 1 ⁇ n 1 + m 1 ⁇ 2
  • n 2 and m 2 are 1 ⁇ n 2 + m 2 ⁇ 2 is satisfied
  • n 3 and m 3 are integers satisfying 1 ⁇ n 3 + m 3 ⁇ 2
  • l is an integer of 2 or 3.
  • each R 20 independently represents a linear or branched alkyl group having 1 to 20 carbon atoms, an aromatic group, or an alicyclic group; and R 20 represents another substituent. You may have. ⁇
  • More preferable (C) nitroxy compounds include 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1 from the viewpoint of crack resistance.
  • -Oxyl free radical 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-cyano -2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-methacrylic acid-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acrylic acid-2,2,6 , 6-Tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethyl Piperidine 1-oxyl free radical, 3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4
  • a nitroxy compound may be used independently and may be used in combination of 2 or more types.
  • the nitroxy compound may be contained even in a trace amount in the polysiloxane composition, but from the viewpoint of crack resistance, the content of (C) the nitroxy compound is 100 mass of the total solid content in the polysiloxane composition. Is preferably 0.005 parts by mass or more, more preferably 0.009 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1 part by mass or less from the viewpoint of transparency. .
  • the polysiloxane composition further includes (D) a compound having a photopolymerizable double bond.
  • the compound having a photopolymerizable double bond is a polymerizable monomer containing at least one photopolymerizable double bond group in one molecule.
  • Examples of the compound (D) having a photopolymerizable double bond include polyethylene glycol di (meth) acrylate [number of ethylene glycol units 2 to 20], poly (1,2-propylene glycol) di (meth) acrylate [ 1,2-propylene glycol units 2-20], polytetramethylene glycol di (meth) acrylate [tetramethylene glycol units 2-10], tri-2-hydroxyethyl isocyanurate tri (meth) acrylate, methylenebisacrylamide , Ethylene glycol diglycidyl ether- (meth) acrylic acid adduct, glycerol diglycidyl ether- (meth) acrylic acid adduct, bisphenol A diglycidyl ether- (meth) acrylic acid adduct, N, N′-bis (2 -Methacryloy Of (Ruoxyethyl) urea succinic acid modified pentaerythritol tri (meth) acrylate, phthal
  • the compound having a photopolymerizable double bond may further contain a carboxyl group.
  • the compound (D) having a photopolymerizable double bond further containing a carboxylic acid include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloxy Examples thereof include ethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, and 2,2,2-triacryloyloxymethyl ethyl succinic acid. These may be used alone or in combination of two or more.
  • the content of the compound having a photopolymerizable double bond is from the viewpoint of sufficiently cross-linking each component with respect to 100 parts by mass of the total solid content in the polysiloxane composition and exhibiting adhesion to the substrate. 5 mass parts or more is preferable, More preferably, it is 10 mass parts or more, On the other hand, from a viewpoint of the residue reduction after image development, 45 mass parts or less are preferable, More preferably, it is 40 mass parts or less.
  • ⁇ (E) UV absorber> in order to improve the light resistance of the polysiloxane composition and reduce residues during development, it is preferable to include (E) an ultraviolet absorber in the polysiloxane composition. Further, it is preferable to use (E) an ultraviolet absorber in combination with (C) a nitroxy compound because the resolution of the polysiloxane composition can be greatly improved.
  • an ultraviolet absorber a benzotriazole type compound, a benzophenone type compound, etc. can be mentioned, for example.
  • UV absorbers include, for example, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and ( Reaction product of 2-ethylhexyl) -glycidic acid ester (TINUVIN 405 manufactured by BASF), 2- (2Hbenzotriazol-2-yl) phenol, 2- (2Hbenzotriazol-2-yl) -4,6-t- Pentylphenol, 2- (2Hbenzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2Hbenzotriazol-2-yl) -6-dodecyl-4- Methylphenol, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, 2-hydroxy-4-methoxybenzof Such as non, and the like.
  • the content of the (E) ultraviolet absorber is to prevent curing of the unexposed portion with respect to 100 parts by mass of the total solid content in the polysiloxane composition. From a viewpoint, 0.01 mass part or more is preferable, More preferably, it is 0.1 mass part or more, On the other hand, 10 mass parts or less are preferable from a viewpoint of pattern formation by the radical generation
  • the polysiloxane composition further includes (F) an alkali-soluble resin.
  • (F) an alkali-soluble resin is added to the polysiloxane composition. It is preferable to do.
  • the (F) alkali-soluble resin refers to an alkali-soluble resin having an alkali-soluble group and having an acid value of 10 to 200 mgKOH / g.
  • the acid value of the alkali-soluble resin is preferably close to (A) a polysiloxane having a radical crosslinkable group from the viewpoint of compatibility, and is preferably 10 mgKOH / g or more from the viewpoint of residue reduction during development. Preferably, it is 20 mgKOH / g or more. On the other hand, from the viewpoint of the adhesiveness of the pattern, 200 mgKOH / g or less is preferable, and more preferably 190 mgKOH / g or less.
  • the alkali-soluble resin is not particularly limited as long as it has an alkali-soluble group and has an acid value of 10 to 200 mgKOH / g.
  • a carboxyl group, a dicarboxylic acid anhydride group, or a dicarboxylic acid anhydride is contained in one molecule. It preferably has a group residue. Since the polysiloxane composition has a carboxyl group in the (F) alkali-soluble resin, the polysiloxane composition exhibits alkali solubility while maintaining heat-resistant transparency, and good film properties can be obtained.
  • (F) There is no restriction
  • the amount is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more.
  • 50 parts by mass or less is preferable, and more preferably 45 parts by mass. Part or less, preferably 40 parts by weight or less.
  • the alkali-soluble resin has an alkali-soluble group, and (1) to (5) below: (1) a vinyl polymer composed mainly of a reactant of a polymerizable double bond, (2) an epoxy polymer mainly composed of an addition reaction product of an epoxy group and a hydroxyl group, (3) an aromatic methylene polymer composed mainly of a reaction product of phenol and formaldehyde, (4) At least one selected from the group consisting of urethane polymers composed mainly of reactants of dialcohol and diisocyanate, and (5) ester polymers composed mainly of reactants of dicarboxylic acid and diepoxide.
  • the polymer is preferably.
  • the main component means that the component is contained in an amount of 70 mol% or more in the molecule.
  • Vinyl polymer mainly composed of a reaction product of a polymerizable double bond For example, a carboxyl group-containing vinyl polymer represented by the following general formula (4) or the following general formula (6) may be mentioned.
  • Rd is a linear, branched or cyclic divalent organic group having 0 to 20 carbon atoms
  • Re is represented by the following general formula (5):
  • Rb is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, or a monovalent organic group having a photopolymerizable double bond group
  • Rc is the following general formula (3): (In the formula, Ra is a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms) or hydrogen.
  • Rf is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, and Rh is independently , A methyl group or hydrogen, m is an integer selected from 1 to 500, and n is an integer selected from 10 to 1,000.
  • Rb is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, or a monovalent organic group having a photopolymerizable double bond group; Is a group represented by the general formula (5) or hydrogen, and Rd is a linear, branched or cyclic divalent organic group having 0 to 20 carbon atoms, or a photopolymerizable divalent group.
  • Rf is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, and Rh is a methyl group or hydrogen; M is an integer selected from 1 to 500, and n is an integer selected from 10 to 1,000.
  • Examples of the method for obtaining the carboxyl group-containing vinyl polymer include the following three methods: (I) at least one compound (a) selected from ⁇ , ⁇ -unsaturated carboxylic acids, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylamide and hydrogen on the nitrogen thereof.
  • Examples of the compound (a) used for the preparation of the carboxy-containing vinyl polymer include (meth) acrylic acid, (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and 2- (meth) acrylate. ) Acryloxyethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic acid half ester, etc. Is mentioned. These may be used alone or in combination of two or more.
  • Examples of the compound (b) used for the preparation of the carboxyl group-containing vinyl polymer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meta ) Acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone (meth) Acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylamide, N-meth Roll acrylamide, N-butoxymethyl acrylamide, styrene, ⁇ -methyl
  • the compound (c) used for the preparation of the carboxyl group-containing vinyl polymer is an epoxy (meth) acrylate obtained by reacting an epoxy resin having two epoxy groups with (meth) acrylic acid by a conventional method. If it is a half ester, it will not specifically limit.
  • examples of the compound (c) include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, vinylcyclohexene monooxide, hydroquinone diglycidyl ether.
  • Examples of the compound (d) used for the preparation of the carboxyl group-containing vinyl polymer include succinic anhydride, cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, and 5-methyl-cyclohexane dicarboxylic acid anhydride.
  • Bicycloheptane dicarboxylic anhydride Bicycloheptane dicarboxylic anhydride, 7-oxabicycloheptane dicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, phthalic anhydride, (3-trimethoxy And polybasic acid anhydrides such as (silylpropyl) succinic anhydride and (3-triethoxysilylpropyl) succinic anhydride. These may be used alone or in combination of two or more.
  • the vinyl copolymerization in the preparation of the carboxyl group-containing vinyl polymer can be carried out by a conventional method, and known methods such as solution polymerization, suspension polymerization method and emulsion polymerization method are possible. Polymerization is preferred.
  • the polymerization initiator that can be used in this case those having a 10-hour half-life temperature in the range of 60 ° C. to 120 ° C. are preferable. Examples of such polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyl).
  • Esters such as t-hexylperoxyisopropylmonocarbonate, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexylmonocarbonate, bis-3,5,5-trimethylhexanoyl peroxide, octa Diacyl peroxides such as noyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, dicumyl peroxide, t- Dialkyl peroxides such as chill cumyl peroxide, and the like. These may be used alone or in combination of two or more.
  • the addition reaction between a carboxyl group and a compound having an epoxy group and a (meth) acryl group is preferably performed in a solvent using a polymerization inhibitor and a catalyst.
  • the temperature is preferably 50 to 120 ° C.
  • reaction solvent examples include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether , Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl Teracetate, ethylene glycol monobutyl ether Acetates such as acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propyl
  • reaction catalyst for the preparation of the carboxyl group-containing vinyl polymer examples include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, Examples thereof include phosphorus compounds such as triphenylphosphine, metal salts of organic acids such as lithium, chromium, zirconium, potassium and sodium of naphthenic acid, lauric acid, stearic acid, oleic acid or octoenoic acid. These may be used alone or in combination of two or more.
  • Examples of the polymerization inhibitor in the preparation of the carboxyl group-containing vinyl polymer include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and phenothiazine. These may be used alone or in combination of two or more. Further, although the dicarboxylic anhydride can be partially added to the hydroxyl group of the reaction product, the reaction temperature is preferably 50 to 120 ° C.
  • a novolak type phenol polymer represented by the following general formula (9) may be mentioned.
  • Rb is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, or a monovalent organic group having a photopolymerizable double bond group
  • Rc is
  • Rj is a methyl group, a hydroxyl group or hydrogen
  • Rk is the above general formula (5) or the following general formula (8):
  • m is an integer selected from 0 to 100
  • n is an integer selected from 4 to 1,000.
  • the novolak type phenol polymer used in the present embodiment is obtained by reacting an epihalohydrin with a condensation reaction product of phenol and formaldehyde. Furthermore, an epoxy group of the reaction product may be subjected to an addition reaction between a carboxyl group or a (meth) acrylate compound having a hydroxyl group, and the hydroxyl group of the reaction product may be reacted with a dicarboxylic acid anhydride.
  • the phenol used for the preparation of the novolak type phenol polymer include phenol, cresol, xylenol, trimethylphenol and the like. These may be used alone or in combination of two or more.
  • Examples of the epihalohydrin used in the novolac type phenol polymer include epichlorohydrin and epibromohydrin. These may be used alone or in combination of two or more.
  • Examples of the compound having a carboxyl group and a (meth) acrylate group in one molecule used for the preparation of the novolak type phenol polymer include (meth) acrylic acid, (meth) acrylic acid, carboxyethyl (meth) acrylate, Carboxypentyl (meth) acrylate, 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, fumaric acid, cinnamic acid, croton Examples include acids, itaconic acid, and maleic acid half esters. These may be used alone or in combination of two or more.
  • Examples of the hydroxyl group and (meth) acrylate compound used in the preparation of the novolak type phenol polymer in one molecule include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerol methacrylate acrylate, Examples include pentaerythritol tri (meth) acrylate and caprolactone adducts of these monomers.
  • epoxy (meth) acrylate compounds in which an epoxy group is (meth) acrylate-modified include epoxy (meth) acrylates of phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, and bisphenol.
  • Epoxy (meth) acrylates of bisphenol type epoxy compounds such as hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2- (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound, etc.
  • Epoxy (meth) acrylates of aliphatic diglycidyl ether compounds such as epoxy (meth) acrylates of alicyclic diglycidyl ether compounds, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether, etc. ) Acrylate and the like.
  • Dicarboxylic acid anhydrides used for the preparation of novolak type phenol polymers include succinic anhydride, cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, 5-methyl-cyclohexane dicarboxylic acid anhydride, bicycloheptane dicarboxylic acid.
  • Acid anhydride 7-oxabicycloheptanedicarboxylic acid anhydride, tetrahydrophthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, adipic acid anhydride, phthalic anhydride, (3-trimethoxysilylpropyl) succinate
  • polybasic acid anhydrides such as acid anhydride and (3-triethoxysilylpropyl) succinic acid anhydride. These may be used alone or in combination of two or more.
  • an acid catalyst When performing the condensation reaction of phenol and formaldehyde in the preparation of the novolak type phenol polymer, it is preferable to use an acid catalyst, and various acid catalysts can be used, such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, Acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride and the like are preferable, and p-toluenesulfonic acid, sulfuric acid and hydrochloric acid are particularly preferable.
  • the condensation reaction of phenol and formaldehyde can be performed in the absence of a solvent or in the presence of an organic solvent.
  • organic solvent include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone and the like.
  • the amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the raw materials charged.
  • the reaction temperature is usually 40 ° C. to 180 ° C., and the reaction time is usually 1 hour to 10 hours. These solvents may be used alone or in combination of two or more.
  • water washing treatment is performed until the pH value of the water washing liquid of the reaction mixture becomes 3 to 7, preferably 5 to 7.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide
  • ammonia sodium dihydrogen phosphate, diethylenetriamine
  • You may process using various basic substances, such as organic amines, such as ethylenetetramine, aniline, and phenylenediamine, as a neutralizing agent.
  • organic amines such as ethylenetetramine, aniline, and phenylenediamine
  • An alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like is added to the dissolved mixture of the phenol-formaldehyde condensate obtained in the above reaction and epihalohydrin such as epichlorohydrin, epibromohydrin or the like.
  • An epoxy resin can be obtained by reacting at ⁇ 120 ° C. for 1 to 10 hours. After the reaction product of these epoxidation reactions is washed with water or without washing, epihalohydrin or other added solvent is removed under reduced pressure by heating at 110 ° C. to 250 ° C. and a pressure of 10 mmHg or less.
  • the obtained epoxy resin is again dissolved in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved.
  • Further reaction can be performed by adding an aqueous solution to ensure ring closure.
  • the reaction temperature is usually 50 ° C. to 120 ° C., and the reaction time is usually 0.5 hours to 2 hours.
  • the produced salt is removed by filtration, washing with water, and the solvent of toluene, methyl isobutyl ketone and the like is distilled off under heating and reduced pressure to obtain the epoxy compound of the present invention.
  • the addition reaction between the epoxy group and the compound having a carboxyl group or a hydroxyl group and a (meth) acryl group in the preparation of the novolak type phenol polymer is preferably carried out in a solvent using a polymerization inhibitor and a catalyst,
  • the reaction temperature is preferably 50 to 120 ° C.
  • the reaction solvent, the reaction catalyst, and the polymerization inhibitor are each described in (1)
  • Preparation of a vinyl polymer mainly composed of a reactant of a polymerizable unsaturated double bond can be used.
  • dicarboxylic anhydride can be partially added to the hydroxyl group of the reaction product, but the reaction temperature is preferably 50 ° C. to 120 ° C.
  • the alkali-soluble resin is mainly composed of a vinyl polymer composed mainly of a polymerizable unsaturated double bond reactant and an addition product of an epoxy group and a hydroxyl group from the viewpoint of heat resistance of the reactant composed mainly of the polymer.
  • a seed polymer is preferred.
  • Ratio of acid value (A) (mgKOH / g) of polysiloxane having radical crosslinkable group and acid value (F) (mgKOH / g) of alkali-soluble resin that is, acid value (A) / acid value (F) Is preferably 0.1 or more, more preferably 0.2 or more, from the viewpoint of compatibility by polarity between (A) a polysiloxane having a radical crosslinkable group and (F) an alkali-soluble resin. More preferably, it is 0.3 or more. On the other hand, this ratio is preferably 5.0 or less, more preferably 4.0 or less, and further preferably 3.0 or less.
  • a silane coupling agent can be added to the polysiloxane composition in order to improve the adhesion between the cured film after exposure and development of the polysiloxane composition and the substrate.
  • a silane coupling agent can be added to the polysiloxane composition in order to improve the adhesion between the cured film after exposure and development of the polysiloxane composition and the substrate.
  • the content of the silane coupling agent in the case of adding the silane coupling agent to the polysiloxane composition is such that the adhesiveness with the substrate is expressed with respect to 100 parts by mass of the total solid content in the polysiloxane composition.
  • 0.1 mass part or more is preferable, More preferably, it is 0.5 mass part or more.
  • 20 mass parts or less are preferable, More preferably, 15 mass parts or less It is.
  • Suitable solvents include the following solvents (1) to (6): (1) Aliphatic alcohols: methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, 1-pentanol, isoamyl alcohol, s-amyl alcohol, t- Amyl alcohol, 2-methyl-1-butanol, 1-hexanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, isohexyl alcohol, methyl-1-pentanol, s-hexanol, 1-heptanol , Isoheptyl alcohol, 2,3-dimethyl-1-pentanol, 1-octan
  • Aromatic alcohol benzyl alcohol, (2-hydroxyphenyl) methanol, (methoxyphenyl) methanol, (3,4-dihydroxyphenyl) methanol, 4- (hydroxymethyl) benzene-1,2-diol, (4 -Hydroxy-3-methoxyphenyl) methanol, (3,4-dimethoxyphenyl) methanol, (4-isopropylphenyl) methanol, 2-phenylethanol, 1-phenylethanol, 2-phenyl-1-propanol, p-tolyl alcohol 2- (4-hydroxy-3-methoxyphenyl) ethane-1-ol, 2- (3,4-dimethoxyphenyl) ethane-1-ol, 3-phenylpropan-1-ol, 2-phenylpropane-2 -All, cinnamyl alcohol, 3- (4-H Loxy-3-methoxyphenyl) prop-2-en-1-ol, 3- (4-hydroxy-3,5-
  • Glycol or derivatives thereof for example, ethylene glycol, ethylene glycol monoalkyl (1 to 8 carbon atoms) ether, ethylene glycol monovinyl ether, ethylene glycol monophenyl ether, dioxane, diethylene glycol monoalkyl (1 to 6 carbon atoms) ) Ether, diethylene glycol monovinyl ether, diethylene glycol monophenyl ether, triethylene glycol monoalkyl (1 to 3 carbon atoms) ether, triethylene glycol monovinyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether, propylene glycol, Propylene glycol monoalkyl (1 to 4 carbon atoms) ether, propylene glycol monophenyl Ether, dipropylene glycol monoalkyl (1-3 carbon atoms) ether, ethylene glycol monoacetate, propylene glycol monoacrylate, propylene glycol monoacetate
  • Ketone compounds acetone, methyl ethyl ketone, 3-butyn-2-one, methyl-n-propyl ketone, methyl isopropyl ketone, 3-pentyn-2-one, methyl isopropenyl ketone, methyl n-butyl ketone, methyl isobutyl Ketone, mesityl oxide, 4-hydroxy-4-methyl-2-pentanone, methyl-n-amyl ketone, methyl isoamyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisopropyl ketone, 2-octanone, 3- Octanone, 5-methyl-3-heptanone, 5-nonanone, diisobutylketone, trimethylnonanone, 2,4-pentanedione, 2,5-hexanedione, cyclopentanone, cyclohexanone, methylcycl
  • propylene glycol monomethyl ether acetate, ethyl lactate, gamma butyrolactone, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether and the like are preferable from the viewpoint of heating the coating film and evaporating the solvent.
  • These solvents can be appropriately added to the polysiloxane composition depending on the coating film thickness and viscosity, but are 50 to 1,000 parts by mass with respect to 100 parts by mass of all solid components in the polysiloxane composition. It is preferable to use in the range.
  • a surfactant may be contained in the polysiloxane composition in order to ensure applicability of the polysiloxane composition and film smoothness after drying.
  • the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, or polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether.
  • Polyoxyethylene arylalkyl ethers, or polyoxyethylene dialkyl esters such as polyoxyethylene ethylene dilaurate and polyoxyethylene distearate, MegaFac F171, 172, 173 (Dainippon Ink), Florard FC430, 431 (Sumitomo) 3M), Asahi Guard AG710, Surflon S-382, SC-101,102,103,104,105 (Asahi Glass) Active agents, such as DBE-712, DBE821 (manufactured by DAICEL-CYTEC Co., Ltd.) silicone surfactants, and the like.
  • the content of these surfactants is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass, from the viewpoint of coating suitability and residue reduction with respect to 100 parts by mass of the total solid content in the polysiloxane composition. From the viewpoint of pattern adhesion after development, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
  • the polysiloxane composition may contain a polymerization inhibitor (for example, a radical polymerization inhibitor).
  • a polymerization inhibitor for example, a radical polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2, 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N -Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium
  • the content of the polymerization inhibitor causes the polymerization inhibiting effect of the photopolymerizable double bond to be expressed with respect to 100 parts by mass of the total solid content in the polysiloxane composition.
  • 0.001 mass part or more is preferable, More preferably, 0.01 mass part or more is preferable,
  • 5 mass parts or less are preferable from a viewpoint of pattern formation by the radical generation
  • an antioxidant can be added to the polysiloxane composition in order to improve the thermal stability of the polysiloxane composition in the presence of oxygen.
  • antioxidants include hindered phenols, phosphoruss, lactones, vitamin Es, and sulfurs.
  • the antioxidant is not limited, but is triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Corporation).
  • IRGANOX 245) 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) (IRGANOX 259 manufactured by BASF), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (IRGANOX565 manufactured by BASF), pentaerythrityl tetrakis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate) (IRGANOX1010 manufactured by BASF), 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (IRGANOX1035 manufactured by BASF), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IR
  • the antioxidant is not limited, but is 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy. ] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (SUMILIZER GA-80, manufactured by Sumitomo Chemical Co., Ltd.), 2,2′-methylenebis (6-t-butyl) -4-methylphenol) (SUMILIZER MDP-S, manufactured by Sumitomo Chemical Co., Ltd.), 4,4′-butylidenebis (6-t-butyl-3-methylphenol) (SUMILIZER BBM-S, manufactured by Sumitomo Chemical Co., Ltd.), 4, 4 ′ -Thiobis (6-tert-butyl-3-methylphenol) (SUMIZER WX-R manufactured by Sumitomo Chemical Co., Ltd.), pentaerythrityl-te
  • antioxidants can be used alone or as a mixture of two or more.
  • the content of the antioxidant in the case of adding an antioxidant to the polysiloxane composition is such that the heat stability effect in the presence of oxygen is expressed with respect to 100 parts by mass of the total solid content in the polysiloxane composition. From 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and still more preferably 0.1 parts by mass or more.
  • the amount is preferably at most 10 parts by mass, more preferably at most 10 parts by mass, even more preferably at most 5 parts by mass.
  • the polysiloxane composition may contain additives such as a plasticizer as necessary.
  • additives include phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri- Examples thereof include n-propyl, tri-n-butyl acetylcitrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.
  • the content of the plasticizer when adding the plasticizer to the polysiloxane composition is 0.1 parts by mass or more from the viewpoint of increasing the flexibility of the film with respect to 100 parts by mass of the total solid content in the polysiloxane composition. Is more preferably 0.5 parts by mass or more, still more preferably 0.7 parts by mass or more. On the other hand, from the viewpoint of the glass transition temperature, 10 parts by mass or less is preferable, and more preferably 8 parts by mass or less. More preferably, it is 5 parts by mass or less.
  • the acid value of the polysiloxane composition used in the present embodiment is preferably 0.1 mgKOH / g or more, more preferably 1 mgKOH / g or more, further from the viewpoint of reduction of residues after development and crack resistance of the cured film. Preferably, it is 5 mgKOH / g or more. On the other hand, from the viewpoint of pattern adhesion, it is preferably 200 mgKOH / g or less, more preferably 170 mgKOH / gmol or less, and further preferably 150 mgKOH / g or less.
  • the transmittance of light at a wavelength of 400 nm after baking at 220 ° C. for 3 hours in the atmosphere of the cured product having a thickness of 10 ⁇ m It is preferable that it is 70% or more. It is also preferable to obtain a transparent insulating film by curing the polysiloxane composition used in the present invention.
  • the radical content in the cured product is preferably contained in an amount of 0.1 ⁇ 10 ⁇ 6 mol or more, more preferably 0.15 ⁇ 10 ⁇ 6 mol or more with respect to 1 g of the cured product.
  • preferably 120 ⁇ 10 -6 mol or less from the viewpoint of pattern formation more preferably 60 ⁇ 10 - is 6 mol or less.
  • the method for measuring the radical content in the cured product is the same as that described above for the polysiloxane composition.
  • a method for forming a cured relief pattern includes a first step of applying a polysiloxane composition on a substrate, a second step of irradiating actinic rays, a third step of removing uncured portions with a developer, A fourth step of heat curing is included.
  • the polysiloxane composition is applied on various desired substrates such as a silicon wafer, a ceramic substrate, and an aluminum substrate.
  • a spin coater As the coating apparatus or coating method, a spin coater, a die coater, a spray coater, dipping, printing, a blade coater, roll coating, or the like can be used.
  • the coated substrate is soft baked at 80 ° C. to 200 ° C. for 1 to 15 minutes, and then irradiated with actinic rays through a desired photomask using 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. In the present invention, those having a wavelength of 200 nm to 500 nm are preferably used.
  • the light source wavelength is particularly preferably UV-i rays (365 nm), and a stepper is particularly preferred as the exposure projection apparatus. Thereafter, for the purpose of improving the photosensitivity, etc., any combination of temperature and time is used as necessary (preferably, the temperature is 40 ° C. to 200 ° C., and the time is 10 seconds to 360 seconds).
  • Post-exposure baking (PEB) or pre-development baking may be performed.
  • a developer an organic solvent or an alkaline developer is preferable.
  • the good solvent of the composition of the present invention can be used alone, or a good solvent and a poor solvent can be appropriately mixed.
  • suitable alkali developers include ammonium hydroxides such as alkali metal or alkaline earth metal carbonate aqueous solutions, alkali metal hydroxide aqueous solutions, tetraethylammonium hydroxide, tetrapropylammonium hydroxide aqueous solutions, and the like.
  • amines such as diethylamine, triethylamine, diethanolamine, and triethanolamine.
  • carbonates such as sodium carbonate, potassium carbonate and lithium carbonate, ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and amines such as diethylamine and diethanolamine are contained in an amount of 0.05 to 10% by mass.
  • Development is preferably performed at a temperature of 20 ° C. to 35 ° C. using a weakly alkaline aqueous solution.
  • organic solvent developers include glycols such as ethylene glycol and propylene glycol.
  • glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol.
  • An example is monoethyl ether.
  • Other organic solvent developers include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, ⁇ -acetyl- Examples thereof include gamma butyrolactone, cyclopentanone, and cyclohexanone.
  • the film is washed with a rinse solution, and the developer solution 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, and the like can be used alone, or appropriately mixed, or used in a stepwise combination.
  • the relief pattern thus obtained is converted into a cured relief pattern at a curing temperature of 150 ° C. to 250 ° C., which is much lower than the conventional polyimide precursor composition.
  • 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. Air may be used as the atmospheric gas for heat curing, and an inert gas such as nitrogen or argon may be used as necessary.
  • the above-described cured relief pattern is applied to, for example, a silicon wafer, glass, a film, a surface protection film of a semiconductor device formed on a base material such as a base material on which one or more kinds of metals are sputtered, an interlayer insulating film, an ⁇ -ray shielding. It is used as one selected from the group consisting of a film and a support (partition) between a microstructure such as a microlens array and its packaging material, and a known semiconductor device manufacturing method is applied to other processes. As a result, various display devices and semiconductor devices including optical elements such as a touch panel and a CMOS image sensor can be manufactured. Moreover, an electronic component or a semiconductor device having a coating film made of a resin obtained by curing the polysiloxane composition can be obtained.
  • ⁇ Calculation method of g value> Among the six peaks of Mn 2+, the third peak counted from the low magnetic field side is used as the standard peak.
  • the absorption magnetic field of the standard peak is H s
  • the g s value is 2.034
  • the absorption magnetic field of the measurement sample is H 0 .
  • Examples 1 to 14, Examples 16 to 27, and Comparative Examples 1 to 5 Following exposure, an alkali developer (developer made by AZ Electronic Materials Co., Ltd., 2.38% tetramethylammonium hydroxide aqueous solution) was used for development under conditions of 23 ° C. and 30 seconds ⁇ 2 times, and rinsed with pure water. The unexposed part of the coating film was removed. Subsequently, the substrate patterned as described above was baked and cured at 220 ° C. for 30 minutes in an oven purged with nitrogen. (About Example 15) Following exposure, PGMEA (propylene glycol monomethyl ether acetate) was used and developed under the conditions of 23 ° C.
  • PGMEA propylene glycol monomethyl ether acetate
  • resolution range is wider than 420mJ / cm 2 ⁇ : the resolution range is wider than 300mJ / cm 2 ⁇ : wider than the resolution range is 120mJ / cm 2 ⁇ : resolution range is 120mJ / cm 2 or less
  • the polysiloxane composition was applied to an aluminum-sputtered silicon substrate so that the film thickness after baking was 15 ⁇ m, and baked on a hot plate at 95 ° C. for 4 minutes.
  • the substrate having the coating film was exposed to 400 mJ / cm 2 using an i-line stepper through a reticle with a test pattern. Exposure was performed in air and the focus was set to -15.
  • Examples 1 to 14, Examples 16 to 27, and Comparative Examples 1 to 5 Following exposure, an alkali developer (developer made by AZ Electronic Materials Co., Ltd., 2.38% tetramethylammonium hydroxide aqueous solution) was used for development under conditions of 23 ° C. and 30 seconds ⁇ 2 times, and rinsed with pure water. The unexposed part of the coating film was removed. Subsequently, the substrate patterned as described above was baked and cured at 220 ° C. for 30 minutes in an oven purged with nitrogen. (About Example 15) Following exposure, PGMEA was used and developed under the conditions of 23 ° C. and 30 seconds ⁇ 2 times to remove the unexposed portion of the coating film.
  • an alkali developer developer made by AZ Electronic Materials Co., Ltd., 2.38% tetramethylammonium hydroxide aqueous solution
  • the substrate patterned as described above was baked and cured at 220 ° C. for 30 minutes in an oven purged with nitrogen.
  • the patterned substrates obtained in Examples 1 to 27 and Comparative Examples 1 to 5 were further baked at 300 ° C. for 30 minutes in an oven purged with nitrogen, and subsequently -40 ° C. at 15 ° C. using a thermal shock tester. Minute, 120 ° C. and 15 minutes once were repeated 100 times, then visually and observed with an optical microscope, and evaluated according to the following criteria.
  • ⁇ : No cracks confirmed in 5 substrates ⁇ : 1-5 cracks occurred in 5 substrates
  • the substrate developed above was baked at 220 ° C. for 6 hours in an atmosphere using an oven.
  • a spectrophotometer UV-1600PC manufactured by Shimadzu Corporation
  • a glass substrate without a coating film was placed on the reference portion, and the light transmittance at 800 nm to 300 nm was measured to confirm the light transmittance at 400 nm.
  • Example 2 to 27 and Comparative Examples 1 to 5 For Examples 2 to 27 and Comparative Examples 1 to 5, the same as in Example 1 except that the components described in Table 1, Table 2, and Table 3 below were used in the ratios described in the same table. A siloxane composition or a resin composition was obtained.
  • ⁇ (C) component> c-1 The following formula: 4-Hydroxy-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) c-2: The following formula: TEMPO having a structure represented by (manufactured by Tokyo Chemical Industry Co., Ltd.) c-3: The following formula: 4-oxo-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) having the structure represented by c-4: The following formula: 3-Carboxy-proxyl-free radical having a structure represented by (Tokyo Chemical Industry Co., Ltd.)
  • Examples 1 to 27 The crack resistance of Examples 1 to 27 was evaluated using a Mo-sputtered silicon wafer. As a result, in Examples 1 to 20 and Examples 24 to 27, the pattern was not peeled off and no cracks were generated. However, in Examples 21 to 23, the pattern peeled off. Comparative Example 5 could not be evaluated because exposure and development did not leave a film.
  • the polysiloxane composition having an alkali-soluble group of the present invention is used as an insulating material for a display device, for forming a surface protective film, an interlayer insulating film, an ⁇ -ray shielding film, etc. in a semiconductor device, and for an image sensor, a micromachine, or a microactuator. It can be suitably used for a semiconductor device or the like on which is mounted.

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WO2015118992A1 (ja) * 2014-02-07 2015-08-13 モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 付加硬化型シリコーン組成物
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WO2015152154A1 (ja) * 2014-03-31 2015-10-08 日産化学工業株式会社 反応性含フッ素シリコーン化合物を含む重合性組成物
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EP3705534A1 (en) * 2015-07-09 2020-09-09 Tokyo Ohka Kogyo Co., Ltd. Silicon-containing resin composition
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JP6916619B2 (ja) * 2016-12-28 2021-08-11 東京応化工業株式会社 ポリシラン化合物、組成物、硬化物及び基板の製造方法、並びにアニオン重合選択的促進剤
KR101975149B1 (ko) * 2017-09-14 2019-05-03 스미또모 가가꾸 가부시키가이샤 비수 전해액 이차 전지용 세퍼레이터
CN116478406A (zh) * 2023-04-04 2023-07-25 浙江精一新材料科技有限公司 一种用于光阀的聚硅氧烷及光阀

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