WO2018168435A1 - Photosensitive siloxane resin composition, cured film and member for touch panels - Google Patents

Photosensitive siloxane resin composition, cured film and member for touch panels Download PDF

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Publication number
WO2018168435A1
WO2018168435A1 PCT/JP2018/007150 JP2018007150W WO2018168435A1 WO 2018168435 A1 WO2018168435 A1 WO 2018168435A1 JP 2018007150 W JP2018007150 W JP 2018007150W WO 2018168435 A1 WO2018168435 A1 WO 2018168435A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
group
siloxane resin
polysiloxane
photosensitive siloxane
Prior art date
Application number
PCT/JP2018/007150
Other languages
French (fr)
Japanese (ja)
Inventor
小林秀行
諏訪充史
飯塚英祐
Original Assignee
東レ株式会社
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Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to KR1020197022236A priority Critical patent/KR102490287B1/en
Priority to JP2018511507A priority patent/JP6458902B1/en
Priority to CN201880017542.6A priority patent/CN110419000B/en
Publication of WO2018168435A1 publication Critical patent/WO2018168435A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—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
    • G03F7/004—Photosensitive materials
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present invention relates to a photosensitive siloxane resin composition, a cured film using the same, a laminate, a manufacturing method thereof, and a touch panel member.
  • the sensor substrate of the capacitive touch panel has wiring in which ITO (Indium Tin Oxide) and metal (silver, molybdenum, aluminum, etc.) are patterned on glass, and an insulating film, ITO, and metal are placed at the intersection of the wiring.
  • ITO Indium Tin Oxide
  • metal silver, molybdenum, aluminum, etc.
  • a structure having a protective film for protection is common.
  • the touch panel system is an out-cell type in which a touch panel layer is formed between the cover glass and the liquid crystal panel, an OGS (One Glass Solution) type in which the touch panel layer is directly formed on the cover glass, and a touch panel layer is formed on the liquid crystal panel. It is roughly classified into an on-cell type and an in-cell type in which a touch panel layer is formed inside a liquid crystal panel. In recent years, an on-cell type has been actively developed because the manufacturing process can be simplified as compared with the prior art. In the on-cell type, since the touch panel layer is formed directly on the liquid crystal panel, it is necessary to form the wiring, the protective film, and the insulating film at a low temperature lower than the heat resistant temperature of the liquid crystal.
  • the protective film of the touch panel is often formed of high-hardness inorganic SiO 2 , SiN x , a photosensitive transparent material, or the like, and the insulating film is often formed of a photosensitive transparent material.
  • inorganic materials such as SiO 2 and SiN x need to be formed by high-temperature film formation by CVD (Chemical Vapor Deposition), and are difficult to apply to the on-cell type. Therefore, there is a need for a photosensitive transparent material that can be cured at low temperature, has high hardness, is excellent in chemical resistance and substrate adhesion, and can be patterned.
  • a photosensitive transparent material As a photosensitive transparent material, a polymer having a (meth) acryloyl group and an acid group, a trifunctional or higher functional ethylenically unsaturated compound, a photopolymerization initiator, and a phosphate ester structure and an ethylenically unsaturated group
  • a photosensitive resin composition containing a compound for example, see Patent Document 1
  • a negative-type photosensitive resin composition for photospacers that can be developed with alkali for example, see Patent Document 2 has been proposed.
  • Patent Document 1 has a problem of insufficient hardness.
  • the inclusion of the phosphoric acid compound improves the substrate adhesion, but there is a problem that the storage stability is lowered due to the strong acidity of the phosphoric acid compound.
  • Patent Document 2 discloses a salt with a cation such as a quaternary ammonium ion as a salt of an acidic group in a polyfunctional (meth) acrylate monomer.
  • a salt with a cation such as a quaternary ammonium ion as a salt of an acidic group in a polyfunctional (meth) acrylate monomer.
  • the resolution is lowered.
  • problems such as deterioration of pattern processability such as generation of development residues and chemical resistance.
  • the present invention is a photosensitivity that can be cured at low temperature, has excellent storage stability and resolution, can suppress development residue, has high hardness, and has a high chemical resistance and substrate adhesion. It is an object to provide a siloxane resin composition.
  • the present invention is a photosensitive siloxane resin composition containing (A) polysiloxane, (B) a photoradical polymerization initiator, (C) a polyfunctional monomer, and (D) a phosphoric acid derivative amine salt.
  • the photosensitive siloxane resin composition of the present invention can be cured at low temperature, has excellent storage stability and resolution, and can suppress development residue. According to the photosensitive siloxane resin composition of the present invention, a cured film having high hardness and excellent chemical resistance and substrate adhesion can be obtained.
  • the photosensitive siloxane resin composition of the present invention contains (A) polysiloxane, (B) a photo radical polymerization initiator, (C) a polyfunctional monomer, and (D) a phosphoric acid derivative amine salt.
  • A By containing polysiloxane, the thermal polymerization (condensation) of polysiloxane proceeds by heating and the crosslink density is improved, so that a cured film having high hardness can be obtained.
  • polymerization of (C) polyfunctional monomer proceeds by radicals generated from (B) the photoradical polymerization initiator by light irradiation.
  • the exposed portion of the photosensitive siloxane resin composition is insolubilized in the alkaline aqueous solution, and a negative pattern can be formed.
  • low temperature curing becomes possible by combining (A) thermal polymerization reaction of polysiloxane and (C) photo radical polymerization reaction of polyfunctional monomer.
  • C photo radical polymerization reaction of polyfunctional monomer.
  • D a phosphoric acid derivative amine salt
  • (A) Polysiloxane is a hydrolyzed / dehydrated condensate of organosilane, and in the present invention, it preferably has (a1) a radical polymerizable group and (a2) a hydrophilic group.
  • the (a1) radical polymerizable group in the polysiloxane the hardness and chemical resistance can be further improved. Since the contrast of the degree of cure between the exposed area and the unexposed area is easily obtained, the resolution can be further improved and development residues can be further suppressed.
  • a hydrophilic group (a2) in the polysiloxane the developability can be further improved and development residues can be further suppressed.
  • the (a1) radical polymerizable group examples include a vinyl group, an ⁇ -methylvinyl group, an allyl group, a styryl group, and a (meth) acryloyl group. You may have 2 or more types of these. Among these, a styryl group is preferable, and the hardness and chemical resistance of the cured film and the adhesion to the MAM (molybdenum / aluminum / molybdenum) substrate can be further improved.
  • the polysiloxane preferably contains (a1) 20 to 85 mol% of repeating units having a styryl group as a radical polymerizable group in all repeating units.
  • the hardness and chemical resistance of the cured film and the adhesion to the MAM substrate can be further improved. More preferably, it contains 40 mol% or more of repeating units having a styryl group.
  • the resolution can be further improved by containing 85 mol% or less of a repeating unit having a styryl group. It is more preferable to contain 70 mol% or less of repeating units having a styryl group.
  • the content ratio of the organosilane unit having a styryl group is measured by 29 Si-NMR, and the ratio of the integrated value of Si derived from the organosilane unit having a styryl group to the integrated value of the entire Si derived from the organosilane is calculated. Can be obtained.
  • Examples of the (a2) hydrophilic group include a carboxyl group, a carboxylic acid anhydride group, a sulfonic acid group, a phenolic hydroxyl group, and a hydroxyimide group. You may have 2 or more types of these. Among these, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxylic anhydride group is more preferable from the viewpoint of further suppressing development residue and further improving storage stability.
  • the (a) polysiloxane preferably contains 5 to 20 mol% of (a2) repeating units having a carboxylic anhydride group as a hydrophilic group in all repeating units.
  • a development residue can be suppressed more by containing 5 mol% or more of repeating units which have a carboxylic anhydride group.
  • the resolution can be further improved by containing 20 mol% or less of a repeating unit having a carboxylic acid anhydride group.
  • the content ratio of the organosilane unit containing a carboxylic acid anhydride group is determined by measuring 29 Si-NMR, and the Si content derived from the organosilane unit having a carboxylic acid anhydride group with respect to the integrated value of the entire Si derived from the organosilane. It can be obtained by calculating the ratio of the integral value.
  • the polysiloxane having (a1) radical polymerizable group and (a2) hydrophilic group hydrolyzes a plurality of organosilane compounds including, for example, an organosilane compound having a radical polymerizable group and an organosilane compound having a hydrophilic group. And can be obtained by dehydration condensation.
  • An organosilane compound other than an organosilane compound having a radical polymerizable group and an organosilane compound having a hydrophilic group may be hydrolyzed and dehydrated together with them.
  • organosilane compound having a radical polymerizable group examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and vinylmethyldi (methoxyethoxy) silane.
  • Organosilane compounds having a vinyl group Organosilane compounds having an allyl group such as allyltrimethoxysilane, allyltriethoxysilane, allyltri (methoxyethoxy) silane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldi (methoxyethoxy) silane Compound: styryltrimethoxysilane, styryltriethoxysilane, styryltri (methoxyethoxy) silane, styrylmethyldimethoxysilane, styryl Organosilane compounds having a styryl group such as methyldiethoxysilane, styrylmethyldimethoxysilane, styrylmethyldi (methoxyethoxy) silane; ⁇ -acryloylpropyltrimethoxysilane, ⁇ -acryloylpropyltri
  • organosilane compounds having a styryl group are preferable, styryltrimethoxysilane and styryltriethoxysilane are more preferable, and styryltrimethoxysilane is more preferable.
  • an organosilane compound having a hydrophilic group an organosilane compound having a carboxylic acid group and / or a carboxylic acid anhydride group is preferable, and an organosilane compound having a carboxylic acid anhydride group is more preferable.
  • organosilane compound having a carboxylic acid anhydride group examples include organosilane compounds having a structure represented by any one of the following general formulas (3) to (5). Two or more of these may be used.
  • R 6 to R 8 , R 10 to R 12 and R 14 to R 16 are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
  • An alkoxy group having 1 to 6 carbon atoms is preferred.
  • R 9 , R 13 and R 17 are each independently a single bond, a divalent chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, or 3 to 16 carbon atoms.
  • —C 2 H 4 —, —C 3 H 6 —, —C 4 H 8 —, —O—, —C 3 H 6 OCH 2 CH (OH) CH 2 O 2 C—, —CO—, —CO 2 —, —CONH—, a group having the following structure, and the like are preferable.
  • h and k each independently represents an integer of 0 to 3.
  • An integer of 0 to 2 is preferred.
  • organosilane compound having a structure represented by the general formula (3) examples include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilylpropyl succinic anhydride, and 3-triphenoxysilylpropyl succinic acid. An acid anhydride etc. are mentioned.
  • organosilane compound having a structure represented by the general formula (4) examples include 3-trimethoxysilylpropylcyclohexyl dicarboxylic acid anhydride.
  • organosilane compound having a structure represented by the general formula (5) examples include 3-trimethoxysilylsilylpropylphthalic anhydride.
  • organosilane compound other than the organosilane compound having a radical polymerizable group and the organosilane compound having a hydrophilic group examples include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri (methoxyethoxy) silane, methyltripropoxysilane, Methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxys
  • the weight average molecular weight (Mw) of the polysiloxane is preferably 1,000 or more, and more preferably 2,000 or more, from the viewpoint of coating properties.
  • Mw of (A) polysiloxane is preferably 50,000 or less, and more preferably 20,000 or less.
  • Mw of (A) polysiloxane in the present invention refers to a polystyrene conversion value measured by gel per emission chromatography (GPC).
  • the content of (A) polysiloxane can be arbitrarily set depending on the desired film thickness and application, but is 10 to 80% by weight in the photosensitive siloxane resin composition. Is common. Moreover, 10 weight% or more is preferable in solid content of the photosensitive siloxane resin composition, and, as for content of (A) polysiloxane, 30 weight% or more is more preferable. On the other hand, the content of (A) polysiloxane is preferably 70% by weight or less in the solid content of the photosensitive siloxane resin composition.
  • the polysiloxane can be obtained by hydrolyzing the aforementioned organosilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction in the presence of a solvent or without a solvent.
  • Various conditions in the hydrolysis can be set according to the physical properties suitable for the intended application in consideration of the reaction scale, the size and shape of the reaction vessel, and the like. Examples of various conditions include acid concentration, reaction temperature, reaction time, and the like.
  • an acid catalyst such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or its anhydride, or an ion exchange resin can be used.
  • an acidic aqueous solution containing formic acid, acetic acid and / or phosphoric acid is preferable.
  • the amount of the acid catalyst added is 0.05 wt.
  • the addition amount of the acid catalyst is preferably 20 parts by weight or less and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total alkoxysilane compound.
  • the total amount of the alkoxysilane compound means an amount including all of the alkoxysilane compound, its hydrolyzate and its condensate, and the same shall apply hereinafter.
  • the hydrolysis reaction can be performed in a solvent.
  • the solvent can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the photosensitive siloxane resin composition.
  • Examples of the solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, and 3-methyl-3-methoxy.
  • -1-alcohols such as butanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether , Propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol Ethers such as coal diethyl ether, ethylene glycol dibutyl ether, diethyl ether; ketones such as methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone; dimethylformamide, Amides such as dimethylacetamide;
  • diacetone alcohol propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene Glycol mono-t-butyl ether, ⁇ -butyrolactone and the like are preferably used.
  • the hydrolysis can be carried out without a solvent. After completion of the hydrolysis reaction, it is also preferable to adjust the concentration to be appropriate as the photosensitive siloxane resin composition by adding a solvent. It is also possible to distill and remove all or part of the product alcohol etc. by heating and / or under reduced pressure after hydrolysis and then adding a suitable solvent.
  • the amount of the solvent added is preferably 50 parts by weight or more and more preferably 80 parts by weight or more with respect to 100 parts by weight of the total alkoxysilane compound from the viewpoint of suppressing gel formation.
  • the addition amount of the solvent is preferably 500 parts by weight or less and more preferably 200 parts by weight or less with respect to 100 parts by weight of the total alkoxysilane compound from the viewpoint of allowing hydrolysis to proceed more rapidly.
  • water used for the hydrolysis reaction ion-exchanged water is preferable.
  • the amount of water can be arbitrarily set, but is preferably 1.0 to 4.0 mol with respect to 1 mol of all alkoxysilane compounds.
  • Examples of the dehydration condensation method include a method of heating a silanol compound solution obtained by hydrolysis reaction of an organosilane compound as it is.
  • the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower, and the heating time is preferably 1 to 100 hours.
  • reheating or addition of a base catalyst may be performed.
  • an appropriate amount such as the generated alcohol may be distilled and removed under heating and / or reduced pressure, and then a suitable solvent may be added.
  • the polysiloxane solution after hydrolysis and dehydration condensation preferably does not contain the catalyst, and the catalyst can be removed as necessary.
  • the catalyst removal method water washing, treatment with an ion exchange resin, and the like are preferable from the viewpoint of easy operation and removability.
  • Water washing is a method of concentrating an organic layer obtained by diluting a polysiloxane solution with an appropriate hydrophobic solvent and then washing several times with water with an evaporator or the like.
  • the treatment with an ion exchange resin is a method in which a polysiloxane solution is brought into contact with an appropriate ion exchange resin.
  • the photoradical polymerization initiator may be any one that decomposes and / or reacts with light (including ultraviolet rays and electron beams) to generate radicals.
  • the photoradical polymerization initiator may be any one that decomposes and / or reacts with light (including ultraviolet rays and electron beams) to generate radicals.
  • 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl ⁇ -aminoalkylphenone compounds such as -phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
  • 2,4,6-trimethylbenzoylphenyl Phosphine oxide bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxy
  • a benzyl ketal compound 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone ⁇ -hydroxy ketone compounds such as: benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, Benzophenone compounds such as hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; 2,2-diethoxy Acetov
  • acylphosphine oxide compounds and oxime ester compounds are preferred from the viewpoint of further improving exposure sensitivity and hardness of the cured film. Since these compounds are also involved in crosslinking of siloxane as an acid during light irradiation and thermosetting, the hardness can be further improved.
  • the content of the (B) photoradical polymerization initiator in the photosensitive siloxane resin composition of the present invention is preferably 0.01% by weight or more, preferably 1% by weight in the solid content from the viewpoint of effectively promoting radical curing. The above is more preferable.
  • the content of (B) radical photopolymerization initiator is 20% by weight or less in the solid content. Is preferable, and 10 weight% or less is more preferable.
  • a polyfunctional monomer refers to a compound having two or more ethylenically unsaturated double bonds in the molecule. Considering the ease of radical polymerization, the (C) polyfunctional monomer preferably has a (meth) acryl group.
  • the double bond equivalent of the (C) polyfunctional monomer is preferably 80 g / mol or more from the viewpoint of further improving the sensitivity in pattern processing and the hardness of the cured film.
  • the double bond equivalent of the polyfunctional monomer (C) is preferably 400 g / mol or less from the viewpoint of further improving the resolution in pattern processing.
  • the polyfunctional monomer for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylol Methylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclo
  • the content of the (C) polyfunctional monomer in the photosensitive siloxane resin composition of the present invention is preferably 1% by weight or more in the solid content from the viewpoint of effectively promoting radical curing.
  • the content of the polyfunctional monomer (C) is preferably 40% by weight or less in the solid content from the viewpoint of suppressing radical excess reaction and further improving the resolution.
  • Phosphoric acid derivative amine salt in the present invention refers to a salt of (d1) phosphoric acid derivative compound and (d2) amine compound. Part of the photosensitive siloxane resin composition may be dissociated.
  • Examples of phosphoric acid derivative compounds include phosphorous acid, phosphorous acid ester, phosphonic acid, phosphonic acid ester, phosphinic acid, phosphinic acid ester, and phosphoric acid ester. Two or more of these may be used. Among these, a phosphoric acid derivative compound having a structure represented by the following general formula (1) is preferable. Since the phosphoric acid derivative compound having a structure represented by the following general formula (1) has a radical polymerizable group and a hydroxyl group, when the photosensitive siloxane resin composition is cured by heat and / or light, phosphoric acid derivative compound The acid derivative amine salt is efficiently incorporated into the (A) polysiloxane, and bleeding out can be suppressed. Moreover, chemical resistance and adhesion with the MAM substrate can be further improved.
  • R 1 represents a monovalent organic group having a radical polymerizable group.
  • the monovalent organic group having a radical polymerizable group for example, at least a part of hydrogen of an alkyl group having 1 to 10 carbon atoms is a vinyl group, an ⁇ -methylvinyl group, an allyl group, a styryl group, (meth) And a group substituted with a radical polymerizable group such as an acryloyl group.
  • the radical polymerizable group is preferably a (meth) acryloyl group, and the alkyl group preferably has 1 to 6 carbon atoms.
  • R 2 represents hydrogen, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having a radical polymerizable group.
  • the monovalent organic group having a radical polymerizable group include those exemplified for R 1 .
  • an alkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms in which at least a part of hydrogen is substituted with a (meth) acryloyl group are preferable.
  • Examples of the phosphoric acid derivative compound having the structure represented by the general formula (1) include 2-methacryloyloxyethyl acid phosphate (trade name P-1M, manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxy. Ethyl acid phosphate (trade name P-1A, manufactured by Kyoeisha Chemical Co., Ltd.), ethylene oxide-modified phosphoric acid dimethacrylate (trade name PM-21, manufactured by Nippon Kayaku Co., Ltd.), phosphoric acid-containing epoxy methacrylate (trade name “ Phosphoric acid (meth) acrylates such as “New Frontier” (registered trademark) S-23A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; vinylphosphonic acid (trade names VPA-90, VPA-100, manufactured by BASF) Examples include vinyl phosphate compounds. Two or more of these may be used.
  • Examples of amine compounds include primary amines, secondary amines, and tertiary amines. Two or more of these may be used. Among these, an amine compound having a structure represented by the following general formula (2) is preferable. Since the amine compound having the structure represented by the following general formula (2) has a hydroxyl group, when the photosensitive siloxane resin composition is cured by heat and / or light, the phosphoric acid derivative amine salt is (A ) Efficiently incorporated into the polysiloxane to suppress bleed out. Moreover, chemical resistance and adhesion with the MAM substrate can be further improved.
  • R 3 represents a monovalent organic group having 1 to 20 carbon atoms and having a hydroxyl group.
  • the monovalent organic group include an alkyl group, an acyl group, and an aryl group, and examples thereof include an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms. preferable.
  • an alkyl group having 1 to 6 carbon atoms in which at least a part of hydrogen is substituted with a hydroxyl group is preferable.
  • R 4 and R 5 each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, or a monovalent organic group having 1 to 20 carbon atoms having a hydroxyl group.
  • the monovalent organic group having 1 to 20 carbon atoms having a hydroxyl group include those exemplified for R 3 .
  • hydrogen, an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms in which at least a part of hydrogen is substituted with a hydroxyl group are preferable.
  • Examples of the amine compound having the structure represented by the general formula (2) include ethanolamine, diethanolamine, triethanolamine, propanolamine, methanolamine, dimethylethanolamine, diethylethanolamine, dibutylethanolamine, and N-methyl.
  • Examples include alkanolamines. Two or more of these may be used.
  • (D) Phosphoric acid derivative amine salt can be obtained by forming a salt by reaction of (d1) phosphoric acid derivative compound and (d2) amine compound.
  • the weight ratio (d2 / d1) of the (d2) amine compound to the (d1) phosphoric acid derivative compound used for salt formation is 0.1 / 9. 9 or more is preferable and 0.3 / 9.7 or more is more preferable.
  • (d2 / d1) is preferably 1/9 or less, and more preferably 0.5 / 9.5 or less.
  • the photosensitive polysiloxane resin composition of the present invention only needs to contain (D) a phosphoric acid derivative amine salt, and the above-mentioned (A) polysiloxane, (B) photo radical polymerization initiator, (C) polyfunctional (D) A phosphoric acid derivative amine salt may be blended together with a monomer or the like, or (d1) a phosphoric acid derivative compound and (d2) an amine compound may be blended with these in the photosensitive polysiloxane composition. (D) A phosphoric acid derivative amine salt may be formed.
  • the photosensitive polysiloxane resin composition of the present invention further contains a thermal radical generator.
  • a thermal radical generator By containing a thermal radical generator, radicals are generated by heating and crosslinking of unsaturated double bonds is promoted, so that the hardness can be further improved.
  • the thermal radical generator include 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamine], 2,2′-azobis [2-methyl-N- (2-propenyl).
  • the content of the (E) thermal radical generator in the photosensitive siloxane resin composition of the present invention is preferably 0.5% by weight or more in the solid content from the viewpoint of more effectively curing.
  • the content of the (E) thermal radical generator is preferably 5% by weight or less in the solid content.
  • the photosensitive siloxane resin composition of the present invention may further contain a curing agent, an ultraviolet absorber, a polymerization inhibitor, a solvent, a surfactant, a dissolution inhibitor, a stabilizer, an antifoaming agent, etc., if necessary. Good.
  • a curing agent in the photosensitive siloxane resin composition of the present invention, curing can be promoted and hardness can be further improved.
  • the curing agent include nitrogen-containing organic substances, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, methylolated melamine derivatives, and methylolated urea derivatives. Two or more of these may be contained.
  • metal chelate compounds, methylolated melamine derivatives, and methylolated urea derivatives are preferably used from the viewpoints of stability of the curing agent and processability of the coating film.
  • the light resistance of the cured film can be improved and the resolution can be further improved.
  • an ultraviolet absorber 2- (2H-benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-tert is used from the viewpoint of suppressing coloring and improving transparency.
  • the resolution can be further improved by including a polymerization inhibitor in the photosensitive siloxane resin composition of the present invention.
  • a polymerization inhibitor examples include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol.
  • polymerization inhibitors include “IRGANOX” (registered trademark) 1010, “IRGANOX” 1035, “IRGANOX” 1076, “IRGANOX” 1098, “IRGANOX” 1135, “IRGANOX” 1330, “IRGANOX” 1726, “ IRGANOX “1425,” IRGANOX “1520,” IRGANOX “245,” IRGANOX “259,” IRGANOX "3114,” IRGANOX “565,” IRGANOX “295 (above, trade name, manufactured by BASF Japan Ltd.) . Two or more of these may be contained.
  • the viscosity suitable for coating can be easily adjusted, and the uniformity of the coating film can be improved. It is preferable to combine a solvent whose boiling point under atmospheric pressure exceeds 150 ° C. and is 250 ° C. or less with a solvent that is 150 ° C. or less. By containing a solvent having a boiling point exceeding 150 ° C. and not more than 250 ° C., the solvent volatilizes appropriately at the time of coating, and drying of the coating proceeds, thereby suppressing coating unevenness and improving film thickness uniformity. Can do. Furthermore, by containing a solvent having a boiling point of 150 ° C.
  • a solvent having a boiling point of 150 ° C. or less under atmospheric pressure is contained by 50% by weight or more of the whole solvent. Is preferred.
  • Examples of the solvent having a boiling point of 150 ° C. or lower under atmospheric pressure include, for example, ethanol, isopropyl alcohol, 1-propyl alcohol, 1-butanol, 2-butanol, isopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol mono Ethyl ether, methoxymethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, acetol, acetylacetone, methyl Isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl lactate Toluene, cyclopentanone, cyclohexane, normal heptane, benzene, methyl
  • Examples of the solvent having a boiling point exceeding 150 ° C. and not higher than 250 ° C. include ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono n-butyl ether, propylene Glycol mono t-butyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, 3-ethoxypropionic acid Ethyl, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, diisobutyl ketone, diacetone alcohol, ethyl lactate, butyl lactate, dimethylformamide, dimethyl ester Ruasetoamido, .gamma.-butyrolactone, .
  • the content of the solvent can be arbitrarily set according to the application method.
  • the content is generally 50% by weight or more and 95% by weight or less in the photosensitive siloxane resin composition.
  • the flowability during coating can be improved.
  • the surfactant include “Megafac” (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (above, trade names, manufactured by Dainippon Ink and Chemicals, Inc.), NBX- 15, Fluorosurfactants such as FTX-218 (trade name, manufactured by Neos Co., Ltd.); “BYK” (registered trademark) -333, “BYK” -301, “BYK” -331, “BYK” -345, “BYK” -307 (trade name, manufactured by Big Chemie Japan Co., Ltd.) and other silicone surfactants; polyalkylene oxide surfactants; poly (meth) acrylate surfactants and the like It is done. Two or more of these may be contained.
  • the solid content concentration of the photosensitive siloxane resin composition of the present invention can be arbitrarily set according to the coating method and the like.
  • the solid content concentration is generally 5% by weight or more and 50% by weight or less.
  • the photosensitive siloxane resin composition of the present invention can be obtained by mixing the aforementioned components (A) to (D) and other components as necessary. More specifically, for example, (B) a radical photopolymerization initiator, (C) a polyfunctional monomer, (D) a phosphate ester amine salt and other additives as required are added to an arbitrary solvent and stirred. (A) Polysiloxane is added, and the mixture is further stirred for 20 minutes to 3 hours, and the resulting solution is filtered.
  • the cured film of the present invention comprises a cured product of the above-described photosensitive polysiloxane resin composition of the present invention.
  • the thickness of the cured film is preferably 0.1 to 15 ⁇ m.
  • the transmittance of light having a wavelength of 400 nm when the thickness of the cured film is 1.5 ⁇ m is preferably 85% or more. The transmittance can be adjusted to a desired range by selecting the exposure amount and the thermosetting temperature in the cured film production method described later.
  • the cured film of the present invention includes a protective film for a touch panel, various hard coating materials, a flattening film for TFT, an overcoat for a color filter, an antireflection film, a passivation film, and other protective films, an optical filter, an insulating film for a touch panel, a TFT It can be suitably used for insulating films for color, photo spacers for color filters, and the like. Among these, since it has high chemical resistance and substrate adhesion, it can be suitably used as an insulating film for touch panels.
  • the cured film of the present invention can be obtained, for example, by applying the above-mentioned photosensitive polysiloxane resin composition of the present invention in a film shape, patterning it if necessary, and then curing it. It is preferable that the photosensitive siloxane resin composition of the present invention is applied on a substrate and pre-baked, and then a negative pattern is formed by exposure and development, followed by heat curing.
  • Examples of the application method for applying the photosensitive siloxane resin composition on the substrate include microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating.
  • Examples of the pre-bake device include a heating device such as a hot plate and an oven.
  • the prebake temperature is preferably 50 to 130 ° C.
  • the prebake time is preferably 30 seconds to 30 minutes.
  • the film thickness after pre-baking is preferably 0.1 to 15 ⁇ m.
  • the exposure may be performed through a desired mask or may be performed without using a mask.
  • Examples of the exposure machine include a stepper, a mirror projection mask aligner (MPA), and a parallel light mask aligner (PLA).
  • Exposure intensity is 10 ⁇ 4000J / m 2 approximately (wavelength 365nm exposure equivalent) are preferred.
  • Examples of the exposure light source include ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like.
  • Developing methods include methods such as shower, dipping and paddle.
  • the immersion time in the developer is preferably 5 seconds to 10 minutes.
  • the developer include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine, tetramethyl
  • alkaline developers such as aqueous solutions containing quaternary ammonium salts such as ammonium hydroxide and choline. After development, it is preferable to rinse with water, followed by drying and baking in the range of 50 to 130 ° C.
  • thermosetting temperature is preferably 80 to 150 ° C.
  • thermosetting time is preferably about 15 minutes to 1 hour.
  • the laminate of the present invention has the above-described cured film of the present invention on a substrate.
  • the base material examples include glass substrates such as soda lime glass and alkali-free glass, transparent base materials made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide, and electrodes or metals on them.
  • glass substrates such as soda lime glass and alkali-free glass
  • transparent base materials made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide, and electrodes or metals on them.
  • Examples include a substrate having wiring.
  • examples of the material for forming the electrode or metal wiring include metal oxides such as indium, tin, zinc, aluminum, and gallium; molybdenum, silver, copper, aluminum, chromium, titanium Metal such as CNT (Carbon Nano Tube).
  • the metal oxide include indium tin oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO), indium gallium zinc oxide (IGZO), and zinc oxide (ZnO).
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • AZO aluminum zinc oxide
  • IGZO indium gallium zinc oxide
  • ZnO zinc oxide
  • a base material having a metal wiring containing molybdenum is preferable.
  • the laminate of the present invention can be obtained, for example, by a production method including the steps of applying the above-described photosensitive polysiloxane resin composition of the present invention on a substrate and heating the coating film at 80 to 150 ° C. in this order. Can do.
  • coating the photosensitive polysiloxane resin composition on a base material the method illustrated as a manufacturing method of a cured film, etc. are mentioned.
  • Examples of the method for heating the coating film at 80 to 150 ° C. include the methods exemplified as the method for producing a cured film. By setting the heating temperature to 80 ° C. or higher, the reaction can proceed sufficiently, and the hardness, chemical resistance, and substrate adhesion can be further improved.
  • the heating temperature to 150 ° C. or lower, it is possible to suppress excessive reaction and accompanying stress and further improve the substrate adhesion. Since the photosensitive siloxane resin composition of the present invention can be cured at a low temperature, it can be sufficiently cured at a temperature of 150 ° C. or lower.
  • the touch panel member of the present invention has the above-mentioned laminated body and a display panel. Furthermore, the cured film in the laminate is preferably an interlayer insulating film.
  • the solid content concentrations of the polysiloxane solutions in Synthesis Examples 1 to 6 and the acrylic resin solution in Synthesis Example 7 were determined by the following method. In an aluminum cup, 1.5 g of the polysiloxane solution or acrylic resin solution was weighed and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid. The weight of the solid content remaining in the heated aluminum cup was weighed, and the solid content concentration of the polysiloxane solution or the acrylic resin solution was determined from the ratio to the weight before the heating.
  • the content ratio of each organosilane unit in the polysiloxane in Synthesis Examples 1 to 6 was determined by the following method.
  • the polysiloxane solution is injected into an NMR sample tube made of “Teflon” (registered trademark) having a diameter of 10 mm, and 29 Si-NMR measurement is performed.
  • the polysiloxane solution is derived from a specific organosilane unit relative to the integral value of the entire Si derived from organosilane.
  • the content ratio of each organosilane unit was calculated from the ratio of the integrated value of Si.
  • the 29 Si-NMR measurement conditions are shown below.
  • Apparatus Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.) Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6669 MHz ( 29 Si nucleus) Spectrum width: 20000Hz Pulse width: 12 ⁇ s (45 ° pulse) Pulse repetition time: 30.0 seconds Solvent: Acetone-d6 Reference substance: Tetramethylsilane Measurement temperature: 23 ° C Sample rotation speed: 0.0 Hz.
  • Nitrogen was allowed to flow at 0.05 liter / min during the temperature rise and heating and stirring. During the reaction, a total of 36.90 g of methanol and water as by-products were distilled out. PGME was added to the obtained polysiloxane solution so that the solid concentration was 40% by weight to obtain a polysiloxane (A-1) solution.
  • the molar ratio of the repeating unit having a styryl group, the repeating unit having an acryloyl group, and the repeating unit having a hydrophilic group in the polysiloxane (A-1) was 65 mol%, 20 mol%, and 15 mol%, respectively.
  • the weight average molecular weight of the polysiloxane (A-1) was 4,000.
  • a polysiloxane solution was obtained by the same procedure as in Synthesis Example 1 except that a phosphoric acid aqueous solution in which 0.317 g of phosphoric acid (0.50% by weight with respect to the charged monomer) was dissolved was added over 30 minutes. PGME was added to the obtained polysiloxane solution so that the solid concentration was 40% by weight to obtain a polysiloxane (A-2) solution.
  • the molar ratio of the repeating unit having an acryloyl group and the repeating unit having a hydrophilic group in the polysiloxane (A-2) was 35 mol% and 15 mol%, respectively.
  • the weight average molecular weight of the polysiloxane (A-2) was 2,500.
  • a polysiloxane solution was obtained by the same procedure as in Synthesis Example 1 except that phosphoric acid in which 0.279 g of phosphoric acid (0.50 wt% with respect to the charged monomer) was dissolved in 74 g was added. PGME was added to the obtained polysiloxane solution so that the solid concentration was 40% by weight to obtain a polysiloxane (A-3) solution.
  • the molar ratio of the repeating unit having a styryl group, the repeating unit having an acryloyl group, and the repeating unit having a hydrophilic group in the polysiloxane (A-3) was 20 mol%, 20 mol%, and 10 mol%, respectively.
  • the weight average molecular weight of the polysiloxane (A-3) was 3,500.
  • a polysiloxane solution was obtained by the same procedure as in Synthesis Example 1 except that phosphoric acid in which .50 wt% was dissolved was added. PGME was added to the obtained polysiloxane solution so that the solid concentration was 40% by weight to obtain a polysiloxane (A-4) solution.
  • the molar ratio of the repeating unit having a styryl group, the repeating unit having an acryloyl group, and the repeating unit having a hydrophilic group in the polysiloxane (A-4) was 80 mol%, 10 mol%, and 10 mol%, respectively.
  • the weight average molecular weight of the polysiloxane (A-4) was 4,000.
  • Synthesis Example 5 Synthesis of polysiloxane (A-5) solution 7.87 g (0.03 mol) of 3-trimethoxysilylpropyl succinic anhydride, 20.43 g (0.15 mol) of methyltrimethoxysilane, phenyltrimethoxy 17.85 g (0.09 mol) of silane, 7.09 g (0.03 mol) of 3-glycidoxypropyltrimethoxysilane, and 49.61 g of PGME were charged, and phosphoric acid was added to 16.74 g of water while stirring at room temperature.
  • a polysiloxane solution was obtained by the same procedure as in Synthesis Example 1 except that phosphoric acid in which 0.266 g (0.50% by weight with respect to the charged monomer) was dissolved was added. PGME was added to the obtained polysiloxane solution so that the solid concentration was 40% by weight to obtain a polysiloxane (A-5) solution.
  • the molar ratio of the repeating unit having a hydrophilic group in the polysiloxane (A-5) was 10 mol%.
  • the weight average molecular weight of the polysiloxane (A-5) was 3,000.
  • Synthesis Example 6 Synthesis of Polysiloxane (A-6) Solution 13.46 g (0.06 mol) of p-styryltrimethoxysilane, 14.06 g (0.06 mol) of ⁇ -acryloylpropyltrimethoxysilane, methyltrimethoxysilane 12.26 g (0.09 mol), tetratrimethoxysilane 13.68 g (0.09 mol), TBC 0.0826 g and PGME 51.56 g were charged, and phosphoric acid was added to 17.82 g of water while stirring at room temperature.
  • a polysiloxane solution was obtained by the same procedure as in Synthesis Example 1 except that phosphoric acid in which 0.267 g (0.50% by weight with respect to the charged monomer) was dissolved was added. PGME was added to the obtained polysiloxane solution so that the solid concentration was 40% by weight to obtain a polysiloxane (A-6) solution.
  • the molar ratio of the repeating unit having a styryl group and the repeating unit having an acryloyl group in the polysiloxane (A-6) was 20 mol% and 20 mol%, respectively.
  • the weight average molecular weight of the polysiloxane (A-6) was 5,000.
  • Synthesis Example 7 Synthesis of Acrylic Resin (a) Solution A 500 ml three-necked flask was charged with 3 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGME. Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature. The mixture was stirred at 5 ° C. for 5 hours.
  • the prepared film is 100 ⁇ m, 50 ⁇ m, 40 ⁇ m, 30 ⁇ m, 20 ⁇ m, 15 ⁇ m, 10 ⁇ m in width. It exposed with the gap of 100 micrometers through the gray scale mask which has a line & space pattern. Thereafter, using an automatic developing device (“AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), the film was shower-developed with 0.045 wt% potassium hydroxide aqueous solution for 60 seconds and then rinsed with water for 30 seconds.
  • AD-2000 automatic developing device
  • the exposure amount for forming a line and space pattern having a width of 100 ⁇ m in a one-to-one width was taken as the optimum exposure amount, and the minimum pattern size after development at the optimum exposure amount was taken as the resolution.
  • the developed pattern was observed visually and with a microscope whose magnification was adjusted to 50 to 100 times, and the development residue was evaluated according to the following criteria according to the degree of undissolved portion of the unexposed area. 5: A residue is not recognized visually, and a residue is also not recognized by the fine pattern below 50 micrometers in microscopic observation.
  • the prepared film was exposed using a parallel light mask aligner (trade name PLA-501F, manufactured by Canon Inc.) using an ultra-high pressure mercury lamp as a light source, and using an oven (trade name IHPS-222, manufactured by ESPEC Corporation). Then, it was cured in air at 120 ° C. for 1 hour to produce a cured film having a thickness of 1.5 ⁇ m.
  • 11 parallel vertical and horizontal lines are drawn at 1 mm intervals so as to reach the substrate of the glass plate with a cutter knife. 100 pieces were produced.
  • Condition 1 50 ° C., 2 minutes Condition 2: 60 ° C., 2 minutes Condition 3: 70 ° C., 2 minutes Condition 4: 80 ° C., 2 minutes
  • Chemical resistance based on conditions judged to have chemical resistance Was evaluated according to the following criteria, and one or more was regarded as acceptable. 4: Conditions 1, 2, 3, 4 all have chemical resistance 3: Conditions 1, 2, and 3 have chemical resistance 2: Conditions 1 and 2 have chemical resistance 1: Conditions 1 have chemical resistance only Yes: No chemical resistance under any conditions.
  • Example 1 Under a yellow light, (B) as radical photopolymerization initiator, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl) Oxime) (“Irgacure” (registered trademark) OXE-02 (trade name), manufactured by BASF Japan Ltd.) 0.080 g and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“Irgacure” ( Registered trademark) -819 (trade name), manufactured by BASF Japan Ltd.) 0.160 g, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (“ Irganox ”(registered trademark) -245 (trade name), BASF Japan Ltd.) PGME 10% by weight solution 0.120 g, tetrakis (acetyl) 3.998 g of
  • Example 2 A photosensitive siloxane resin composition (P-2) was obtained in the same manner as in Example 1 except that 6.167 g of the polysiloxane (A-2) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive siloxane resin composition (P-2).
  • Example 3 A photosensitive siloxane resin composition (P-3) was obtained in the same manner as in Example 1 except that 6.167 g of the polysiloxane (A-3) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-3).
  • Example 4 A photosensitive siloxane resin composition (P-4) was obtained in the same manner as in Example 1 except that 6.167 g of the polysiloxane (A-4) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive siloxane resin composition (P-4).
  • Example 5 A photosensitive siloxane resin composition (P-5) was obtained in the same manner as in Example 1 except that 6.167 g of the polysiloxane (A-5) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-5).
  • Example 6 A photosensitive siloxane resin composition (P-6) was obtained in the same manner as in Example 1 except that 6.167 g of the polysiloxane (A-6) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-6).
  • Example 7 The same procedure as in Example 1 was conducted except that 2-acryloyloxyethyl acid phosphate (P-1A (trade name), manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of the phosphoric acid derivative compound (d1) P-1M. A photosensitive siloxane resin composition (P-7) was obtained. The obtained photosensitive siloxane resin composition (P-7) was used for evaluation in the same manner as in Example 1.
  • P-1A 2-acryloyloxyethyl acid phosphate
  • d1 P-1M phosphoric acid derivative compound
  • Example 8 Amine compound (d2) A photosensitive siloxane resin composition (P-8) was obtained in the same manner as in Example 1 except that triethanolamine was used instead of monoethanolamine. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-8).
  • Example 9 The same procedure as in Example 1 was carried out except that ethyl acid phosphate (JP502 (trade name), manufactured by Johoku Chemical Industry Co., Ltd.) was used instead of the phosphoric acid derivative compound (d1) P-1M. A product (P-9) was obtained. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-9).
  • JP502 trade name
  • Example 10 Amine compound (d2) A photosensitive siloxane resin composition (P-10) was obtained in the same manner as in Example 1 except that triethylamine was used instead of monoethanolamine. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive siloxane resin composition (P-10).
  • a photosensitive siloxane resin composition (P-13) was obtained in the same manner as in Example 1 except that 3.999 g of the solution was used. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-13).
  • a photosensitive siloxane resin composition (P-14) was obtained in the same manner as in Example 1 except that was used. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-14).
  • Example 15 The amount of the polysiloxane (A-1) solution was 5.967 g, (E) 0.080 g of dimethyl 2,2′-azobis (isobutyrate) was added as a thermal radical generator, and the mixed solvent was PGME 1.797 g and PGMEA 3
  • a photosensitive siloxane resin composition (P-15) was obtained in the same manner as in Example 1 except that the amount was 200 g. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-15).
  • Example 16 A photosensitive siloxane resin composition (P-16) was obtained in the same manner as in Example 15 except that the polysiloxane (A-2) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-16).
  • Example 17 A photosensitive siloxane resin composition (P-17) was obtained in the same manner as in Example 15 except that the polysiloxane (A-5) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-17).
  • Example 18 A photosensitive siloxane resin composition (P-18) was obtained in the same manner as in Example 15 except that the polysiloxane (A-6) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-18).
  • Example 19 The amount of the polysiloxane (A-1) solution is 5.967 g, (E) 0.080 g of dimethyl 2,2′-azobis (isobutyrate) is added as a thermal radical generator, and the mixed solvent is PGME 1.797 g and PGMEA3.
  • a photosensitive siloxane resin composition (P-19) was obtained in the same manner as in Example 9 except for 200 g. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-19).
  • Example 20 The amount of the polysiloxane (A-1) solution was 5.967 g, (E) 0.080 g of dimethyl 2,2′-azobis (isobutyrate) was added as a thermal radical generator, and the mixed solvent was PGME 1.797 g and PGMEA 3
  • a photosensitive siloxane resin composition (P-20) was obtained in the same manner as in Example 10 except that the amount was 200 g. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-20).
  • Example 1 except that the amount of the polysiloxane (A-1) solution was 8.166 g, (D) the phosphate ester amine salt was not added, and the mixed solvent was PGME 3.676 g and PGMEA 3.200 g. And a photosensitive siloxane resin composition (P-21) was obtained. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-21).
  • Comparative Example 2 A photosensitive siloxane resin was prepared in the same manner as in Example 1 except that the phosphate ester amine salt was not added and the amount of the phosphoric acid derivative compound (d1) P-1M in 20% by weight of PGME was changed to 3.999 g. A composition (P-22) was obtained. The obtained photosensitive siloxane resin composition (P-22) was used for evaluation in the same manner as in Example 1. Comparative Example 3 A photosensitive siloxane resin composition (P-23) was obtained in the same manner as in Example 1 except that tetraethylammonium, which is a quaternary ammonium cation, was used as the amine compound (d2) instead of monoethanolamine. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive siloxane resin composition (P-23).
  • Comparative Example 4 A photosensitive acrylic resin composition (P-24) was obtained in the same manner as in Example 1 except that 6.167 g of the acrylic resin (a) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive acrylic resin composition (P-24).
  • Tables 2 to 4 show the compositions of Examples 1 to 20 and Comparative Examples 1 to 4, and Table 5 shows the evaluation results.
  • Cured films obtained by curing the photosensitive siloxane resin composition of the present invention include various hard coat films such as touch panel protective films, insulating films for touch sensors, flattened films for TFTs of liquid crystals and organic EL displays, It is suitably used for metal wiring protective films, insulating films, antireflection films, optical filters, color filter overcoats, pillar materials, and the like.

Abstract

The present invention addresses the problem of providing a photosensitive siloxane resin composition which is able to be cured at low temperatures and has excellent storage stability and resolution, while being capable of suppressing development residue, and which enables the achievement of a cured film that exhibits high hardness, while having excellent chemical resistance and excellent adhesion to a substrate. The present invention is a photosensitive siloxane resin composition which contains (A) a polysiloxane, (B) a radical photopolymerization initiator, (C) a polyfunctional monomer and (D) an amine salt of a phosphoric acid derivative.

Description

感光性シロキサン樹脂組成物、硬化膜およびタッチパネル用部材Photosensitive siloxane resin composition, cured film and touch panel member
　本発明は、感光性シロキサン樹脂組成物と、それを用いた硬化膜、積層体とその製造方法およびタッチパネル用部材に関する。 The present invention relates to a photosensitive siloxane resin composition, a cured film using the same, a laminate, a manufacturing method thereof, and a touch panel member.
　現在、スマートフォンやタブレット端末の多くに静電容量式タッチパネルが使用されている。静電容量式タッチパネルのセンサー基板は、ガラス上にＩＴＯ（Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ）や金属（銀、モリブデン、アルミニウムなど）がパターニングされた配線を有し、配線の交差部に絶縁膜、ＩＴＯおよび金属を保護する保護膜を有する構造が一般的である。 Currently, capacitive touch panels are used in many smartphones and tablet terminals. The sensor substrate of the capacitive touch panel has wiring in which ITO (Indium Tin Oxide) and metal (silver, molybdenum, aluminum, etc.) are patterned on glass, and an insulating film, ITO, and metal are placed at the intersection of the wiring. A structure having a protective film for protection is common.
　タッチパネルの方式は、カバーガラスと液晶パネルとの間にタッチパネル層を形成するＯｕｔ－ｃｅｌｌタイプ、カバーガラスにタッチパネル層を直接形成するＯＧＳ（Ｏｎｅ　Ｇｌａｓｓ　Ｓｏｌｕｔｉｏｎ）タイプ、液晶パネル上にタッチパネル層を形成するＯｎ－ｃｅｌｌタイプ、液晶パネルの内部にタッチパネル層を形成するＩｎ－ｃｅｌｌタイプに大別される。近年、従来よりも製造プロセスが簡略化できることから、Ｏｎ－ｃｅｌｌタイプの開発が盛んに行われている。Ｏｎ－ｃｅｌｌタイプにおいては、液晶パネル上に直接タッチパネル層を形成するため、配線や保護膜、絶縁膜を液晶の耐熱温度以下の低温で形成する必要がある。 The touch panel system is an out-cell type in which a touch panel layer is formed between the cover glass and the liquid crystal panel, an OGS (One Glass Solution) type in which the touch panel layer is directly formed on the cover glass, and a touch panel layer is formed on the liquid crystal panel. It is roughly classified into an on-cell type and an in-cell type in which a touch panel layer is formed inside a liquid crystal panel. In recent years, an on-cell type has been actively developed because the manufacturing process can be simplified as compared with the prior art. In the on-cell type, since the touch panel layer is formed directly on the liquid crystal panel, it is necessary to form the wiring, the protective film, and the insulating film at a low temperature lower than the heat resistant temperature of the liquid crystal.
　従来、タッチパネルの保護膜は高硬度な無機系のＳｉＯ２、ＳｉＮｘや感光性透明材料などにより形成される場合が多く、絶縁膜は感光性透明材料により形成される場合が多かった。しかしながら、ＳｉＯ２やＳｉＮｘなどの無機系材料は、ＣＶＤ（Ｃｈｅｍｉａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｉｏｎ）により高温製膜して形成する必要があり、Ｏｎ－ｃｅｌｌタイプへの適用は難しい。そこで、低温硬化が可能で、硬度が高く、耐薬品性、基板密着性に優れ、パターン加工可能な感光性透明材料が求められている。 Conventionally, the protective film of the touch panel is often formed of high-hardness inorganic SiO 2 , SiN x , a photosensitive transparent material, or the like, and the insulating film is often formed of a photosensitive transparent material. However, inorganic materials such as SiO 2 and SiN x need to be formed by high-temperature film formation by CVD (Chemical Vapor Deposition), and are difficult to apply to the on-cell type. Therefore, there is a need for a photosensitive transparent material that can be cured at low temperature, has high hardness, is excellent in chemical resistance and substrate adhesion, and can be patterned.
　感光性透明材料として、（メタ）アクリロイル基と酸基とを有する重合体、３官能以上のエチレン性不飽和化合物、光重合開始剤、及び、リン酸エステル構造とエチレン性不飽和基とを有する化合物とを含む感光性樹脂組成物（例えば、特許文献１参照）や、リン酸基などの特定の酸性基を含有する多官能（メタ）アクリレートモノマー、シロキサン化合物、および光ラジカル重合開始剤を含有するアルカリ現像可能なネガ型のフォトスペーサ用感光性樹脂組成物（例えば、特許文献２参照）が提案されている。 As a photosensitive transparent material, a polymer having a (meth) acryloyl group and an acid group, a trifunctional or higher functional ethylenically unsaturated compound, a photopolymerization initiator, and a phosphate ester structure and an ethylenically unsaturated group A photosensitive resin composition containing a compound (for example, see Patent Document 1), a polyfunctional (meth) acrylate monomer containing a specific acidic group such as a phosphate group, a siloxane compound, and a radical photopolymerization initiator A negative-type photosensitive resin composition for photospacers that can be developed with alkali (for example, see Patent Document 2) has been proposed.
特開２０１６－１５３８３４号公報JP 2016-153834 A 特開２０１１－２０３５７７号公報JP 2011-203577 A
　特許文献１に開示された樹脂組成物は、硬度が不十分である課題があった。また、リン酸化合物を含有することにより、基板密着性が向上する反面、リン酸化合物の強酸性により保存安定性が低下する課題があった。また、特許文献２には、多官能（メタ）アクリレートモノマー中の酸性基の塩として４級アンモニウムイオンなどのカチオンとの塩が開示されているが、かかる塩の高い親水性により、解像度の低下や現像残渣の発生などのパターン加工性の低下および耐薬品性の低下などの課題があった。 The resin composition disclosed in Patent Document 1 has a problem of insufficient hardness. In addition, the inclusion of the phosphoric acid compound improves the substrate adhesion, but there is a problem that the storage stability is lowered due to the strong acidity of the phosphoric acid compound. Further, Patent Document 2 discloses a salt with a cation such as a quaternary ammonium ion as a salt of an acidic group in a polyfunctional (meth) acrylate monomer. However, due to the high hydrophilicity of such a salt, the resolution is lowered. In addition, there are problems such as deterioration of pattern processability such as generation of development residues and chemical resistance.
　そこで、本発明は、低温硬化が可能で、保存安定性および解像度に優れ、現像残渣を抑制することでき、硬度が高く、耐薬品性、基板密着性に優れる硬化膜を得ることのできる感光性シロキサン樹脂組成物を提供することを課題とする。 Therefore, the present invention is a photosensitivity that can be cured at low temperature, has excellent storage stability and resolution, can suppress development residue, has high hardness, and has a high chemical resistance and substrate adhesion. It is an object to provide a siloxane resin composition.
　本発明は、（Ａ）ポリシロキサン、（Ｂ）光ラジカル重合開始剤、（Ｃ）多官能モノマーおよび（Ｄ）リン酸誘導体アミン塩を含有する感光性シロキサン樹脂組成物である。 The present invention is a photosensitive siloxane resin composition containing (A) polysiloxane, (B) a photoradical polymerization initiator, (C) a polyfunctional monomer, and (D) a phosphoric acid derivative amine salt.
　本発明の感光性シロキサン樹脂組成物は、低温硬化が可能で、保存安定性および解像度に優れ、現像残渣を抑制することができる。本発明の感光性シロキサン樹脂組成物によれば、硬度が高く、耐薬品性および基板密着性に優れる硬化膜を得ることができる。 The photosensitive siloxane resin composition of the present invention can be cured at low temperature, has excellent storage stability and resolution, and can suppress development residue. According to the photosensitive siloxane resin composition of the present invention, a cured film having high hardness and excellent chemical resistance and substrate adhesion can be obtained.
　本発明の感光性シロキサン樹脂組成物は（Ａ）ポリシロキサン、（Ｂ）光ラジカル重合開始剤、（Ｃ）多官能モノマーおよび（Ｄ）リン酸誘導体アミン塩を含有する。（Ａ）ポリシロキサンを含有することにより、加熱によりポリシロキサンの熱重合（縮合）が進行し、架橋密度が向上するため、高硬度の硬化膜を得ることができる。また、（Ｂ）光ラジカル重合開始剤および（Ｃ）多官能モノマーを含有することにより、光照射により（Ｂ）光ラジカル重合開始剤から発生したラジカルによって（Ｃ）多官能モノマーの重合が進行し、感光性シロキサン樹脂組成物の露光部がアルカリ水溶液に対して不溶化し、ネガ型のパターンを形成することができる。このように、（Ａ）ポリシロキサンの熱重合反応および（Ｃ）多官能モノマーの光ラジカル重合反応を組み合わせることにより、低温硬化が可能となる。さらに、（Ｄ）リン酸誘導体アミン塩を含有することにより、保存安定性および解像度を向上させ、現像残渣を抑制することでき、耐薬品性および基板密着性を大幅に向上させることができる。 The photosensitive siloxane resin composition of the present invention contains (A) polysiloxane, (B) a photo radical polymerization initiator, (C) a polyfunctional monomer, and (D) a phosphoric acid derivative amine salt. (A) By containing polysiloxane, the thermal polymerization (condensation) of polysiloxane proceeds by heating and the crosslink density is improved, so that a cured film having high hardness can be obtained. Further, by containing (B) a photoradical polymerization initiator and (C) a polyfunctional monomer, polymerization of (C) polyfunctional monomer proceeds by radicals generated from (B) the photoradical polymerization initiator by light irradiation. The exposed portion of the photosensitive siloxane resin composition is insolubilized in the alkaline aqueous solution, and a negative pattern can be formed. Thus, low temperature curing becomes possible by combining (A) thermal polymerization reaction of polysiloxane and (C) photo radical polymerization reaction of polyfunctional monomer. Further, by containing (D) a phosphoric acid derivative amine salt, storage stability and resolution can be improved, development residues can be suppressed, and chemical resistance and substrate adhesion can be greatly improved.
　（Ａ）ポリシロキサン
　（Ａ）ポリシロキサンは、オルガノシランの加水分解・脱水縮合物であり、本発明においては、（ａ１）ラジカル重合性基および（ａ２）親水性基を有することが好ましい。ポリシロキサン中に（ａ１）ラジカル重合性基を有することにより、硬度および耐薬品性をより向上させることができる。露光部と未露光部の硬化度のコントラストがつきやすくなるため、解像度をより向上させ、現像残渣をより抑制することができる。また、ポリシロキサン中に（ａ２）親水性基を有することにより、現像性をより向上させ、現像残渣をより抑制することができる。 (A) Polysiloxane (A) Polysiloxane is a hydrolyzed / dehydrated condensate of organosilane, and in the present invention, it preferably has (a1) a radical polymerizable group and (a2) a hydrophilic group. By having the (a1) radical polymerizable group in the polysiloxane, the hardness and chemical resistance can be further improved. Since the contrast of the degree of cure between the exposed area and the unexposed area is easily obtained, the resolution can be further improved and development residues can be further suppressed. Moreover, by having a hydrophilic group (a2) in the polysiloxane, the developability can be further improved and development residues can be further suppressed.
　（ａ１）ラジカル重合性基としては、例えば、ビニル基、α―メチルビニル基、アリル基、スチリル基、（メタ）アクリロイル基などが挙げられる。これらを２種以上有してもよい。これらの中でも、スチリル基が好ましく、硬化膜の硬度や耐薬品性、ＭＡＭ（モリブデン／アルミニウム／モリブデンの積層膜）基板との密着性をより向上させることができる。（Ａ）ポリシロキサンは、（ａ１）ラジカル重合性基としてスチリル基を有する繰り返し単位を、全繰り返し中２０～８５モル％含有することが好ましい。スチリル基を有する繰り返し単位を２０モル％以上含有することにより、硬化膜の硬度や耐薬品性、ＭＡＭ基板との密着性をより向上させることができる。スチリル基を有する繰り返し単位を４０モル％以上含有することがさらに好ましい。一方、スチリル基を有する繰り返し単位を８５モル％以下含有することにより、解像度をより向上させることができる。スチリル基を有する繰り返し単位を７０モル％以下含有することがさらに好ましい。スチリル基を有するオルガノシラン単位の含有比率は、２９Ｓｉ－ＮＭＲ測定を行い、オルガノシランに由来するＳｉ全体の積分値に対する、スチリル基を有するオルガノシラン単位に由来するＳｉの積分値の割合を算出することにより求めることができる。 Examples of the (a1) radical polymerizable group include a vinyl group, an α-methylvinyl group, an allyl group, a styryl group, and a (meth) acryloyl group. You may have 2 or more types of these. Among these, a styryl group is preferable, and the hardness and chemical resistance of the cured film and the adhesion to the MAM (molybdenum / aluminum / molybdenum) substrate can be further improved. (A) The polysiloxane preferably contains (a1) 20 to 85 mol% of repeating units having a styryl group as a radical polymerizable group in all repeating units. By containing 20 mol% or more of repeating units having a styryl group, the hardness and chemical resistance of the cured film and the adhesion to the MAM substrate can be further improved. More preferably, it contains 40 mol% or more of repeating units having a styryl group. On the other hand, the resolution can be further improved by containing 85 mol% or less of a repeating unit having a styryl group. It is more preferable to contain 70 mol% or less of repeating units having a styryl group. The content ratio of the organosilane unit having a styryl group is measured by 29 Si-NMR, and the ratio of the integrated value of Si derived from the organosilane unit having a styryl group to the integrated value of the entire Si derived from the organosilane is calculated. Can be obtained.
　（ａ２）親水性基としては、例えば、カルボキシル基、カルボン酸無水物基、スルホン酸基、フェノール性水酸基、ヒドロキシイミド基などが挙げられる。これらを２種以上有してもよい。これらの中でも、現像残渣をより抑制し、保存安定性をより向上させる観点から、カルボキシル基、カルボン酸無水物基が好ましく、カルボン酸無水物基がより好ましい。（ａ）ポリシロキサンは、（ａ２）親水性基としてカルボン酸無水物基を有する繰り返し単位を、全繰り返し中５～２０モル％含有することが好ましい。カルボン酸無水物基を有する繰り返し単位を５モル％以上含有することにより、現像残渣をより抑制することができる。一方、カルボン酸無水物基を有する繰り返し単位を２０モル％以下含有することにより、解像度をより向上させることができる。カルボン酸無水物基を含むオルガノシラン単位の含有比率は、２９Ｓｉ－ＮＭＲ測定を行い、オルガノシランに由来するＳｉ全体の積分値に対する、カルボン酸無水物基を有するオルガノシラン単位に由来するＳｉの積分値の割合を算出することにより求めることができる。 Examples of the (a2) hydrophilic group include a carboxyl group, a carboxylic acid anhydride group, a sulfonic acid group, a phenolic hydroxyl group, and a hydroxyimide group. You may have 2 or more types of these. Among these, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxylic anhydride group is more preferable from the viewpoint of further suppressing development residue and further improving storage stability. The (a) polysiloxane preferably contains 5 to 20 mol% of (a2) repeating units having a carboxylic anhydride group as a hydrophilic group in all repeating units. A development residue can be suppressed more by containing 5 mol% or more of repeating units which have a carboxylic anhydride group. On the other hand, the resolution can be further improved by containing 20 mol% or less of a repeating unit having a carboxylic acid anhydride group. The content ratio of the organosilane unit containing a carboxylic acid anhydride group is determined by measuring 29 Si-NMR, and the Si content derived from the organosilane unit having a carboxylic acid anhydride group with respect to the integrated value of the entire Si derived from the organosilane. It can be obtained by calculating the ratio of the integral value.
　（ａ１）ラジカル重合性基および（ａ２）親水性基を有するポリシロキサンは、例えば、ラジカル重合性基を有するオルガノシラン化合物および親水性基を有するオルガノシラン化合物を含む複数のオルガノシラン化合物を加水分解および脱水縮合することによって得ることができる。ラジカル重合性基を有するオルガノシラン化合物および親水性基を有するオルガノシラン化合物以外のオルガノシラン化合物をこれらとともに加水分解および脱水縮合してもよい。 The polysiloxane having (a1) radical polymerizable group and (a2) hydrophilic group hydrolyzes a plurality of organosilane compounds including, for example, an organosilane compound having a radical polymerizable group and an organosilane compound having a hydrophilic group. And can be obtained by dehydration condensation. An organosilane compound other than an organosilane compound having a radical polymerizable group and an organosilane compound having a hydrophilic group may be hydrolyzed and dehydrated together with them.
　ラジカル重合性基を有するオルガノシラン化合物としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリ（メトキシエトキシ）シラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシラン、ビニルメチルジ（メトキシエトキシ）シランなどのビニル基を有するオルガノシラン化合物；アリルトリメトキシシラン、アリルトリエトキシシラン、アリルトリ（メトキシエトキシ）シラン、アリルメチルジメトキシシラン、アリルメチルジエトキシシラン、アリルメチルジ（メトキシエトキシ）シランなどのアリル基を有するオルガノシラン化合物；スチリルトリメトキシシラン、スチリルトリエトキシシラン、スチリルトリ（メトキシエトキシ）シラン、スチリルメチルジメトキシシラン、スチリルメチルジエトキシシラン、スチリルメチルジメトキシシラン、スチリルメチルジ（メトキシエトキシ）シランなどのスチリル基を有するオルガノシラン化合物；γ－アクリロイルプロピルトリメトキシシラン、γ－アクリロイルプロピルトリエトキシシラン、γ－アクリロイルプロピルトリ（メトキシエトキシ）シラン、γ－メタクリロイルプロピルトリメトキシシラン、γ－メタクリロイルプロピルトリエトキシシラン、γ－メタクリロイルプロピルトリ（メトキシエトキシ）シラン、γ－メタクリロイルプロピルメチルジメトキシシラン、γ－メタクリロイルプロピルメチルジエトキシシラン、γ－アクリロイルプロピルメチルジメトキシシラン、γ－アクリロイルプロピルメチルジエトキシシラン、γ－メタクリロイルプロピル（メトキシエトキシ）シランなどの（メタ）アクリロイル基を有するオルガノシラン化合物などが挙げられる。これらを２種以上用いてもよい。これらの中でも、スチリル基を有するオルガノシラン化合物が好ましく、スチリルトリメトキシシラン、スチリルトリエトキシシランがより好ましく、スチリルトリメトキシシランがさらに好ましい。 Examples of the organosilane compound having a radical polymerizable group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and vinylmethyldi (methoxyethoxy) silane. Organosilane compounds having a vinyl group; organosilanes having an allyl group such as allyltrimethoxysilane, allyltriethoxysilane, allyltri (methoxyethoxy) silane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldi (methoxyethoxy) silane Compound: styryltrimethoxysilane, styryltriethoxysilane, styryltri (methoxyethoxy) silane, styrylmethyldimethoxysilane, styryl Organosilane compounds having a styryl group such as methyldiethoxysilane, styrylmethyldimethoxysilane, styrylmethyldi (methoxyethoxy) silane; γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-acryloylpropyltri ( Methoxyethoxy) silane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-methacryloylpropyltri (methoxyethoxy) silane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ -Acryloylpropylmethyldimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-methacryloylpropyl (methoxyethyl) Carboxymethyl) such organosilane compounds having a (meth) acryloyl group such as a silane. Two or more of these may be used. Among these, organosilane compounds having a styryl group are preferable, styryltrimethoxysilane and styryltriethoxysilane are more preferable, and styryltrimethoxysilane is more preferable.
　親水性基を有するオルガノシラン化合物としては、カルボン酸基および／またはカルボン酸無水物基を有するオルガノシラン化合物が好ましく、カルボン酸無水物基を有するオルガノシラン化合物がより好ましい。 As the organosilane compound having a hydrophilic group, an organosilane compound having a carboxylic acid group and / or a carboxylic acid anhydride group is preferable, and an organosilane compound having a carboxylic acid anhydride group is more preferable.
　カルボン酸無水物基を有するオルガノシラン化合物としては、例えば、下記一般式（３）～（５）のいずれかで表される構造を有するオルガノシラン化合物などが挙げられる。これらを２種以上用いてもよい。 Examples of the organosilane compound having a carboxylic acid anhydride group include organosilane compounds having a structure represented by any one of the following general formulas (3) to (5). Two or more of these may be used.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　上記一般式（３）～（５）中、Ｒ６～Ｒ８、Ｒ１０～Ｒ１２およびＲ１４～Ｒ１６はそれぞれ独立に、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、フェニル基、フェノキシ基または炭素数２～６のアルキルカルボニルオキシ基を表す。炭素数１～６のアルコキシ基が好ましい。 In the general formulas (3) to (5), R 6 to R 8 , R 10 to R 12 and R 14 to R 16 are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Group, a phenyl group, a phenoxy group or an alkylcarbonyloxy group having 2 to 6 carbon atoms. An alkoxy group having 1 to 6 carbon atoms is preferred.
　上記一般式（３）～（５）中、Ｒ９、Ｒ１３およびＲ１７はそれぞれ独立に、単結合、炭素数１～１０の２価の鎖状脂肪族炭化水素基、炭素数３～１６の２価の環状脂肪族炭化水素基、カルボニル基、エーテル基、アミド基、芳香族基またはこれらのいずれかを有する２価の基を表す。－Ｃ２Ｈ４－、－Ｃ３Ｈ６－、－Ｃ４Ｈ８－、－Ｏ－、－Ｃ３Ｈ６ＯＣＨ２ＣＨ（ＯＨ）ＣＨ２Ｏ２Ｃ－、－ＣＯ－、－ＣＯ２－、－ＣＯＮＨ－、以下の構造を有する基などが好ましい。 In the general formulas (3) to (5), R 9 , R 13 and R 17 are each independently a single bond, a divalent chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, or 3 to 16 carbon atoms. A divalent cyclic aliphatic hydrocarbon group, a carbonyl group, an ether group, an amide group, an aromatic group, or a divalent group having any one of these. —C 2 H 4 —, —C 3 H 6 —, —C 4 H 8 —, —O—, —C 3 H 6 OCH 2 CH (OH) CH 2 O 2 C—, —CO—, —CO 2 —, —CONH—, a group having the following structure, and the like are preferable.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　上記一般式（３）～（５）中、ｈおよびｋはそれぞれ独立に０～３の整数を表す。０～２の整数が好ましい。 In the above general formulas (3) to (5), h and k each independently represents an integer of 0 to 3. An integer of 0 to 2 is preferred.
　一般式（３）で表される構造を有するオルガノシラン化合物としては、例えば、３－トリメトキシシリルプロピルコハク酸無水物、３－トリエトキシシシリルプロピルコハク酸無水物、３－トリフェノキシシリルプロピルコハク酸無水物などが挙げられる。 Examples of the organosilane compound having a structure represented by the general formula (3) include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilylpropyl succinic anhydride, and 3-triphenoxysilylpropyl succinic acid. An acid anhydride etc. are mentioned.
　一般式（４）で表される構造を有するオルガノシラン化合物としては、例えば、３－トリメトキシシリルプロピルシクロヘキシルジカルボン酸無水物などが挙げられる。 Examples of the organosilane compound having a structure represented by the general formula (4) include 3-trimethoxysilylpropylcyclohexyl dicarboxylic acid anhydride.
　一般式（５）で表される構造を有するオルガノシラン化合物としては、例えば、３－トリメトキシシシリルプロピルフタル酸無水物などが挙げられる。 Examples of the organosilane compound having a structure represented by the general formula (5) include 3-trimethoxysilylsilylpropylphthalic anhydride.
　ラジカル重合性基を有するオルガノシラン化合物および親水性基を有するオルガノシラン化合物以外のオルガノシラン化合物としては、例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリ（メトキシエトキシ）シラン、メチルトリプロポキシシラン、メチルトリイソプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ヘキシルトリメトキシシラン、オクタデシルトリメトキシシラン、オクタデシルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、３－クロロプロピルトリメトキシシラン、３－（Ｎ，Ｎ－グリシジル）アミノプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、Ｎ－β－（アミノエチル）－γ－アミノプロピルトリメトキシシラン、β－シアノエチルトリエトキシシラン、グリシドキシメチルトリメトキシシラン、グリシドキシメチルトリエトキシシラン、α－グリシドキシエチルトリメトキシシラン、α－グリシドキシエチルトリエトキシシラン、β－グリシドキシプロピルトリメトキシシラン、β－グリシドキシプロピルトリエトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、γ－グリシドキシプロピルトリプロポキシシラン、γ－グリシドキシプロピルトリイソプロポキシシラン、γ－グリシドキシプロピルトリブトキシシラン、γ－グリシドキシプロピルトリ（メトキシエトキシ）シラン、α－グリシドキシブチルトリメトキシシラン、α－グリシドキシブチルトリエトキシシラン、β－グリシドキシブチルトリメトキシシラン、β－グリシドキシブチルトリエトキシシラン、γ－グリシドキシブチルトリメトキシシラン、γ－グリシドキシブチルトリエトキシシラン、σ－グリシドキシブチルトリメトキシシラン、σ－グリシドキシブチルトリエトキシシラン、（３，４－エポキシシクロヘキシル）メチルトリメトキシシラン、（３，４－エポキシシクロヘキシル）メチルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリプロポキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリブトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリフェノキシシラン、３－（３，４－エポキシシクロヘキシル）プロピルトリメトキシシラン、３－（３，４－エポキシシクロヘキシル）プロピルトリエトキシシラン、４－（３，４－エポキシシクロヘキシル）ブチルトリメトキシシラン、４－（３，４－エポキシシクロヘキシル）ブチルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、γ－グリシドキシプロピルメチルジメチルジメトキシシラン、γ－アミノプロピルメチルジメトキシシラン、γ－アミノプロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、グリシドキシメチルジメトキシシラン、グリシドキシメチルメチルジエトキシシラン、α－グリシドキシエチルメチルジメトキシシラン、α－グリシドキシエチルメチルジエトキシシラン、β－グリシドキシエチルメチルジメトキシシラン、β－グリシドキシエチルメチルジエトキシシラン、α－グリシドキシプロピルメチルジメトキシシラン、α－グリシドキシプロピルメチルジエトキシシラン、β－グリシドキシプロピルメチルジメトキシシラン、β－グリシドキシプロピルメチルジエトキシシラン、γ－グリシドキシプロピルメチルジメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、γ－グリシドキシプロピルメチルジプロポキシシラン、β－グリシドキシプロピルメチルジブトキシシラン、γ－グリシドキシプロピルメチルジ（メトキシエトキシ）シラン、γ－グリシドキシプロピルエチルジメトキシシラン、γ－グリシドキシプロピルエチルジエトキシシラン、３－クロロプロピルメチルジメトキシシラン、３－クロロプロピルメチルジエトキシシラン、シクロヘキシルメチルジメトキシシラン、オクタデシルメチルジメトキシシラン、テトラメトキシシラン、テトラエトキシシランなどが挙げられる。これらを２種以上用いてもよい。 Examples of the organosilane compound other than the organosilane compound having a radical polymerizable group and the organosilane compound having a hydrophilic group include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri (methoxyethoxy) silane, methyltripropoxysilane, Methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-glycidyl) aminopro Rutrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyl Triethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriisopropoxysilane , γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyltri (methoxyethoxy) silane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltri Methoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, σ-glycidoxybutyltrimethoxysilane, σ-glycidoxybutyltri Ethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrib Xysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, 3- ( 3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4-epoxy (Cyclohexyl) butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (2- Aminoethyl) -3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β -Glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane , Β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxy Propylmethyldibutoxysilane, γ-glycidoxypropylmethyldi (methoxyethoxy) silane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, Examples include 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, and tetraethoxysilane. Two or more of these may be used.
　（Ａ）ポリシロキサンの重量平均分子量（Ｍｗ）は、塗布特性の観点から、１，０００以上が好ましく、２，０００以上がより好ましい。一方、現像性の観点から、（Ａ）ポリシロキサンのＭｗは、５０，０００以下が好ましく、２０，０００以下がより好ましい。ここで、本発明における（Ａ）ポリシロキサンのＭｗとは、ゲルパーエミッションクロマトグラフィー（ＧＰＣ）で測定されるポリスチレン換算値を言う。 (A) The weight average molecular weight (Mw) of the polysiloxane is preferably 1,000 or more, and more preferably 2,000 or more, from the viewpoint of coating properties. On the other hand, from the viewpoint of developability, Mw of (A) polysiloxane is preferably 50,000 or less, and more preferably 20,000 or less. Here, Mw of (A) polysiloxane in the present invention refers to a polystyrene conversion value measured by gel per emission chromatography (GPC).
　本発明の感光性シロキサン樹脂組成物において、（Ａ）ポリシロキサンの含有量は、所望の膜厚や用途により任意に設定することができるが、感光性シロキサン樹脂組成物中、１０～８０重量％が一般的である。また、（Ａ）ポリシロキサンの含有量は、感光性シロキサン樹脂組成物の固形分中、１０重量％以上が好ましく、３０重量％以上がより好ましい。一方、（Ａ）ポリシロキサンの含有量は、感光性シロキサン樹脂組成物の固形分中、７０重量％以下が好ましい。 In the photosensitive siloxane resin composition of the present invention, the content of (A) polysiloxane can be arbitrarily set depending on the desired film thickness and application, but is 10 to 80% by weight in the photosensitive siloxane resin composition. Is common. Moreover, 10 weight% or more is preferable in solid content of the photosensitive siloxane resin composition, and, as for content of (A) polysiloxane, 30 weight% or more is more preferable. On the other hand, the content of (A) polysiloxane is preferably 70% by weight or less in the solid content of the photosensitive siloxane resin composition.
　（Ａ）ポリシロキサンは、前述のオルガノシラン化合物を加水分解した後、該加水分解物を溶媒の存在下または無溶媒で脱水縮合反応させることによって得ることができる。 (A) The polysiloxane can be obtained by hydrolyzing the aforementioned organosilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction in the presence of a solvent or without a solvent.
　加水分解における各種条件は、反応スケール、反応容器の大きさ、形状などを考慮して、目的とする用途に適した物性に合わせて設定することができる。各種条件としては、例えば、酸濃度、反応温度、反応時間などが挙げられる。 Various conditions in the hydrolysis can be set according to the physical properties suitable for the intended application in consideration of the reaction scale, the size and shape of the reaction vessel, and the like. Examples of various conditions include acid concentration, reaction temperature, reaction time, and the like.
　加水分解反応には、塩酸、酢酸、蟻酸、硝酸、蓚酸、塩酸、硫酸、リン酸、ポリリン酸、多価カルボン酸やその無水物、イオン交換樹脂などの酸触媒を用いることができる。これらの中でも、蟻酸、酢酸および／またはリン酸を含む酸性水溶液が好ましい。 In the hydrolysis reaction, an acid catalyst such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or its anhydride, or an ion exchange resin can be used. Among these, an acidic aqueous solution containing formic acid, acetic acid and / or phosphoric acid is preferable.
　加水分解反応に酸触媒を用いる場合、酸触媒の添加量は、加水分解をより速やかに進行させる観点から、加水分解反応に使用される全アルコキシシラン化合物１００重量部に対して、０．０５重量部以上が好ましく、０．１重量部以上がより好ましい。一方、加水分解反応の進行を適度に調整する観点から、酸触媒の添加量は、全アルコキシシラン化合物１００重量部に対して、２０重量部以下が好ましく、１０重量部以下がより好ましい。ここで、全アルコキシシラン化合物量とは、アルコキシシラン化合物、その加水分解物およびその縮合物の全てを含む量のことを言い、以下同じとする。 When an acid catalyst is used for the hydrolysis reaction, the amount of the acid catalyst added is 0.05 wt. With respect to 100 parts by weight of the total alkoxysilane compound used for the hydrolysis reaction, from the viewpoint of allowing the hydrolysis to proceed more rapidly. Part or more is preferable, and 0.1 part by weight or more is more preferable. On the other hand, from the viewpoint of appropriately adjusting the progress of the hydrolysis reaction, the addition amount of the acid catalyst is preferably 20 parts by weight or less and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total alkoxysilane compound. Here, the total amount of the alkoxysilane compound means an amount including all of the alkoxysilane compound, its hydrolyzate and its condensate, and the same shall apply hereinafter.
　加水分解反応は、溶媒中で行うことができる。感光性シロキサン樹脂組成物の安定性、濡れ性、揮発性などを考慮して、溶媒を適宜選択することができる。溶媒としては、例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、ｔ－ブタノール、ペンタノール、４－メチル－２－ペンタノール、３－メチル－２－ブタノール、３－メチル－３－メトキシ－１－ブタノール、ジアセトンアルコールなどのアルコール類；エチレングリコール、プロピレングリコールなどのグリコール類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノ－ｔ－ブチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル、ジエチルエーテルなどのエーテル類；メチルエチルケトン、アセチルアセトン、メチルプロピルケトン、メチルブチルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロペンタノン、２－ヘプタノンなどのケトン類；ジメチルホルムアミド、ジメチルアセトアミドなどのアミド類；エチルアセテート、プロピルアセテート、ブチルアセテート、イソブチルアセテート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、３－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート、乳酸メチル、乳酸エチル、乳酸ブチルなどのアセテート類；トルエン、キシレン、ヘキサン、シクロヘキサンなどの芳香族または脂肪族炭化水素；γ－ブチロラクトン、Ｎ－メチル－２－ピロリドン、ジメチルスルホキシドなどが挙げられる。これらを２種以上用いてもよい。 The hydrolysis reaction can be performed in a solvent. The solvent can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the photosensitive siloxane resin composition. Examples of the solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, and 3-methyl-3-methoxy. -1-alcohols such as butanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether , Propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol Ethers such as coal diethyl ether, ethylene glycol dibutyl ether, diethyl ether; ketones such as methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone; dimethylformamide, Amides such as dimethylacetamide; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate , Acetates such as ethyl lactate and butyl lactate; toluene, xylene, hexane, cyclohexane Aromatic or aliphatic hydrocarbons, such as Sun; .gamma.-butyrolactone, N- methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may be used.
　これらの中でも、硬化膜の透過率およびクラック耐性等の観点から、ジアセトンアルコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノ－ｔ－ブチルエーテル、γ－ブチロラクトン等が好ましく用いられる。 Among these, from the viewpoint of the transmittance and crack resistance of the cured film, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene Glycol mono-t-butyl ether, γ-butyrolactone and the like are preferably used.
　加水分解反応によって溶媒が生成する場合には、無溶媒で加水分解を行うことも可能である。加水分解反応終了後に、さらに溶媒を添加することにより、感光性シロキサン樹脂組成物として適切な濃度に調整することも好ましい。また、加水分解後に加熱および／または減圧下により生成アルコール等の全量あるいは一部を留出、除去し、その後好適な溶媒を添加することも可能である。 When a solvent is generated by a hydrolysis reaction, the hydrolysis can be carried out without a solvent. After completion of the hydrolysis reaction, it is also preferable to adjust the concentration to be appropriate as the photosensitive siloxane resin composition by adding a solvent. It is also possible to distill and remove all or part of the product alcohol etc. by heating and / or under reduced pressure after hydrolysis and then adding a suitable solvent.
　加水分解反応に溶媒を使用する場合、溶媒の添加量は、ゲルの生成を抑制する観点から、全アルコキシシラン化合物１００重量部に対して、５０重量部以上が好ましく、８０重量部以上がより好ましい。一方、溶媒の添加量は、加水分解をより速やかに進行させる観点から、全アルコキシシラン化合物１００重量部に対して、５００重量部以下が好ましく、２００重量部以下がより好ましい。 When a solvent is used for the hydrolysis reaction, the amount of the solvent added is preferably 50 parts by weight or more and more preferably 80 parts by weight or more with respect to 100 parts by weight of the total alkoxysilane compound from the viewpoint of suppressing gel formation. . On the other hand, the addition amount of the solvent is preferably 500 parts by weight or less and more preferably 200 parts by weight or less with respect to 100 parts by weight of the total alkoxysilane compound from the viewpoint of allowing hydrolysis to proceed more rapidly.
　また、加水分解反応に用いる水としては、イオン交換水が好ましい。水の量は任意に設定することができるが、全アルコキシシラン化合物１モルに対して、１．０～４．０モルが好ましい。 Moreover, as the water used for the hydrolysis reaction, ion-exchanged water is preferable. The amount of water can be arbitrarily set, but is preferably 1.0 to 4.0 mol with respect to 1 mol of all alkoxysilane compounds.
　脱水縮合反応の方法としては、例えば、オルガノシラン化合物の加水分解反応により得られたシラノール化合物溶液をそのまま加熱する方法などが挙げられる。加熱温度は、５０℃以上、溶媒の沸点以下が好ましく、加熱時間は、１～１００時間が好ましい。また、ポリシロキサンの重合度を高めるために、再加熱または塩基触媒の添加を行ってもよい。また、目的に応じて、加水分解後に、生成アルコールなどの適量を加熱および／または減圧下にて留出、除去し、その後好適な溶媒を添加してもよい。 Examples of the dehydration condensation method include a method of heating a silanol compound solution obtained by hydrolysis reaction of an organosilane compound as it is. The heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower, and the heating time is preferably 1 to 100 hours. In order to increase the degree of polymerization of the polysiloxane, reheating or addition of a base catalyst may be performed. Further, depending on the purpose, after hydrolysis, an appropriate amount such as the generated alcohol may be distilled and removed under heating and / or reduced pressure, and then a suitable solvent may be added.
　感光性ポリシロキサン樹脂組成物の保存安定性の観点から、加水分解、脱水縮合後のポリシロキサン溶液には前記触媒が含まれないことが好ましく、必要に応じて触媒の除去を行うことができる。触媒除去方法としては、操作の簡便さと除去性の観点から、水洗浄、イオン交換樹脂による処理などが好ましい。水洗浄とは、ポリシロキサン溶液を適当な疎水性溶媒で希釈した後、水で数回洗浄して得られた有機層をエバポレーター等で濃縮する方法である。イオン交換樹脂による処理とは、ポリシロキサン溶液を適当なイオン交換樹脂に接触させる方法である。 From the viewpoint of the storage stability of the photosensitive polysiloxane resin composition, the polysiloxane solution after hydrolysis and dehydration condensation preferably does not contain the catalyst, and the catalyst can be removed as necessary. As the catalyst removal method, water washing, treatment with an ion exchange resin, and the like are preferable from the viewpoint of easy operation and removability. Water washing is a method of concentrating an organic layer obtained by diluting a polysiloxane solution with an appropriate hydrophobic solvent and then washing several times with water with an evaporator or the like. The treatment with an ion exchange resin is a method in which a polysiloxane solution is brought into contact with an appropriate ion exchange resin.
　（Ｂ）光ラジカル重合開始剤
　（Ｂ）光ラジカル重合開始剤は、光（紫外線、電子線を含む）により分解および／または反応し、ラジカルを発生させるものであればどのようなものでもよく、例えば、２－メチル－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、２－ジメチルアミノ－２－（４－メチルベンジル）－１－（４－モルフォリン－４－イル－フェニル）－ブタン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１などのα－アミノアルキルフェノン化合物；２，４，６－トリメチルベンゾイルフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル)－フェニルフォスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－（２，４，４－トリメチルペンチル）－フォスフィンオキサイドなどのアシルホスフィンオキサイド化合物；１－フェニル－１，２－プロパンジオン－２－（Ｏ－エトキシカルボニル）オキシム、１，２－オクタンジオン,１－［４－（フェニルチオ）－２－（Ｏ－ベンゾイルオキシム）］、１－フェニル－１，２－ブタジオン－２－（Ｏ－メトキシカルボニル）オキシム、１，３－ジフェニルプロパントリオン－２－（Ｏ－エトキシカルボニル）オキシム、エタノン,１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム)などのオキシムエステル化合物；ベンジルジメチルケタールなどのベンジルケタール化合物；２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、４－（２－ヒドロキシエトキシ）フェニル－（２－ヒドロキシ－２－プロピル）ケトン、１－ヒドロキシシクロヘキシル－フェニルケトンなどのα－ヒドロキシケトン化合物；ベンゾフェノン、４，４－ビス（ジメチルアミノ）ベンゾフェノン、４，４－ビス（ジエチルアミノ）ベンゾフェノン、Ｏ－ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、４，４－ジクロロベンゾフェノン、ヒドロキシベンゾフェノン、４－ベンゾイル－４’－メチル－ジフェニルサルファイド、アルキル化ベンゾフェノン、３，３’，４，４’－テトラ（ｔ－ブチルパーオキシカルボニル）ベンゾフェノンなどのベンゾフェノン化合物；２，２－ジエトキシアセトフェノン、２，３－ジエトキシアセトフェノン、４－ｔ－ブチルジクロロアセトフェノン、ベンザルアセトフェノン、４－アジドベンザルアセトフェノンなどのアセトフェノン化合物；２－フェニル－２－オキシ酢酸メチルなどの芳香族ケトエステル化合物；４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸（２－エチル）ヘキシル、４－ジエチルアミノ安息香酸エチル、２－ベンゾイル安息香酸メチルなどの安息香酸エステル化合物などが挙げられる。これらを２種以上含有してもよい。 (B) Photoradical polymerization initiator (B) The photoradical polymerization initiator may be any one that decomposes and / or reacts with light (including ultraviolet rays and electron beams) to generate radicals. For example, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl Α-aminoalkylphenone compounds such as -phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2,4,6-trimethylbenzoylphenyl Phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2 , 4,4-trimethylpentyl) -phosphine oxide compounds; 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [ 4- (phenylthio) -2- (O-benzoyloxime)], 1-phenyl-1,2-butadion-2- (O-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (O-ethoxy) Oxime ester compounds such as carbonyl) oxime, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); benzyldimethyl ketal, etc. A benzyl ketal compound; 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone Α-hydroxy ketone compounds such as: benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, Benzophenone compounds such as hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; 2,2-diethoxy Acetov Acetophenone compounds such as enone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, 4-azidobenzalacetophenone; aromatic ketoester compounds such as methyl 2-phenyl-2-oxyacetate; 4 And benzoic acid ester compounds such as ethyl dimethylaminobenzoate, (2-ethyl) hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, methyl 2-benzoylbenzoate, and the like. Two or more of these may be contained.
　これらの中でも、露光感度および硬化膜の硬度をより向上させる観点から、アシルホスフィンオキサイド化合物、オキシムエステル化合物が好ましい。これらの化合物は、光照射および熱硬化の際に酸としてシロキサンの架橋にも関与することから、硬度をより向上させることができる。 Among these, acylphosphine oxide compounds and oxime ester compounds are preferred from the viewpoint of further improving exposure sensitivity and hardness of the cured film. Since these compounds are also involved in crosslinking of siloxane as an acid during light irradiation and thermosetting, the hardness can be further improved.
　本発明の感光性シロキサン樹脂組成物中における（Ｂ）光ラジカル重合開始剤の含有量は、ラジカル硬化を効果的に進める観点から、固形分中、０．０１重量％以上が好ましく、１重量％以上がより好ましい。一方、残留した（Ｂ）光ラジカル重合開始剤の溶出等を抑制し、耐薬品性をより向上させる観点から、（Ｂ）光ラジカル重合開始剤の含有量は、固形分中、２０重量％以下が好ましく、１０重量％以下がより好ましい。 The content of the (B) photoradical polymerization initiator in the photosensitive siloxane resin composition of the present invention is preferably 0.01% by weight or more, preferably 1% by weight in the solid content from the viewpoint of effectively promoting radical curing. The above is more preferable. On the other hand, from the viewpoint of suppressing elution and the like of the remaining (B) radical photopolymerization initiator and further improving chemical resistance, the content of (B) radical photopolymerization initiator is 20% by weight or less in the solid content. Is preferable, and 10 weight% or less is more preferable.
　（Ｃ）多官能モノマー
　（Ｃ）多官能モノマーとは、分子中に２つ以上のエチレン性不飽和二重結合を有する化合物をいう。ラジカル重合性のしやすさを考えると、（Ｃ）多官能モノマーは、（メタ）アクリル基を有することが好ましい。また、（Ｃ）多官能モノマーの二重結合当量は、パターン加工における感度および硬化膜の硬度をより向上させる観点から、８０ｇ／ｍｏｌ以上が好ましい。一方、（Ｃ）多官能モノマーの二重結合当量は、パターン加工における解像度をより向上させる観点から、４００ｇ／ｍｏｌ以下が好ましい。 (C) Polyfunctional monomer (C) A polyfunctional monomer refers to a compound having two or more ethylenically unsaturated double bonds in the molecule. Considering the ease of radical polymerization, the (C) polyfunctional monomer preferably has a (meth) acryl group. In addition, the double bond equivalent of the (C) polyfunctional monomer is preferably 80 g / mol or more from the viewpoint of further improving the sensitivity in pattern processing and the hardness of the cured film. On the other hand, the double bond equivalent of the polyfunctional monomer (C) is preferably 400 g / mol or less from the viewpoint of further improving the resolution in pattern processing.
　（Ｃ）多官能モノマーとしては、例えば、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、トリメチロールプロパンジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパンジメタクリレート、トリメチロールプロパントリメタクリレート、１，３－ブタンジオールジアクリレート、１，３－ブタンジオールジメタクリレート、ネオペンチルグリコールジアクリレート、１，４－ブタンジオールジアクリレート、１，４－ブタンジオールジメタクリレート、１，６－ヘキサンジオールジアクリレート、１，９－ノナンジオールジメタクリレート、１，１０－デカンジオールジメタクリレート、ジメチロール－トリシクロデカンジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、トリペンタエリスリトールヘプタアクリレート、トリペンタエリスリトールオクタアクリレート、テトラペンタエリスリトールノナアクリレート、テトラペンタエリスリトールデカアクリレート、ペンタペンタエリスリトールウンデカアクリレート、ペンタペンタエリスリトールドデカアクリレート、トリペンタエリスリトールヘプタメタクリレート、トリペンタエリスリトールオクタメタクリレート、テトラペンタエリスリトールノナメタクリレート、テトラペンタエリスリトールデカメタクリレート、ペンタペンタエリスリトールウンデカメタクリレート、ペンタペンタエリスリトールドデカメタクリレート、ジメチロール－トリシクロデカンジアクリレートなどが挙げられる。これらを２種以上含有してもよい。これらの中でも、現像時の残渣をより抑制する観点から、ペンタエリスリトールアクリレートが好ましい。 (C) As the polyfunctional monomer, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylol Methylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol penta Acrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecaacrylate, pentapentaerythritol dodecaacrylate, tripentaerythritol Hepta methacrylate, tripentaerythritol octa methacrylate, tetra pentaerythritol nona methacrylate, tetra pentaerythritol deca methacrylate, pentaerythritol pentaerythritol undecalactone methacrylate, pentaerythritol pentaerythritol dodeca methacrylate, dimethylol - such as tricyclodecane acrylate. Two or more of these may be contained. Among these, pentaerythritol acrylate is preferable from the viewpoint of further suppressing residues during development.
　本発明の感光性シロキサン樹脂組成物中における（Ｃ）多官能モノマーの含有量は、ラジカル硬化を効果的に進める観点から、固形分中、１重量％以上が好ましい。一方、ラジカルの過剰反応を抑制し解像度をより向上させる観点から、（Ｃ）多官能モノマーの含有量は、固形分中、４０重量％以下が好ましい。 The content of the (C) polyfunctional monomer in the photosensitive siloxane resin composition of the present invention is preferably 1% by weight or more in the solid content from the viewpoint of effectively promoting radical curing. On the other hand, the content of the polyfunctional monomer (C) is preferably 40% by weight or less in the solid content from the viewpoint of suppressing radical excess reaction and further improving the resolution.
　（Ｄ）リン酸誘導体アミン塩
　本発明における（Ｄ）リン酸誘導体アミン塩とは、（ｄ１）リン酸誘導体化合物と（ｄ２）アミン化合物の塩を言う。感光性シロキサン樹脂組成物中において、その一部が解離していてもよい。 (D) Phosphoric acid derivative amine salt (D) Phosphoric acid derivative amine salt in the present invention refers to a salt of (d1) phosphoric acid derivative compound and (d2) amine compound. Part of the photosensitive siloxane resin composition may be dissociated.
　（ｄ１）リン酸誘導体化合物としては、例えば、亜リン酸、亜リン酸エステル、ホスホン酸、ホスホン酸エステル、ホスフィン酸、ホスフィン酸エステル、リン酸エステルなどが挙げられる。これらを２種以上用いてもよい。これらの中でも、下記一般式（１）で表される構造を有するリン酸誘導体化合物が好ましい。下記一般式（１）で表される構造を有するリン酸誘導体化合物は、ラジカル重合性基とヒドロキシル基を有することから、感光性シロキサン樹脂組成物を熱および／または光により硬化させる際に、リン酸誘導体アミン塩が（Ａ）ポリシロキサン中に効率的に取り込まれ、ブリードアウトを抑制することができる。また、耐薬品性およびＭＡＭ基板との密着性をより向上させることができる。 (D1) Examples of phosphoric acid derivative compounds include phosphorous acid, phosphorous acid ester, phosphonic acid, phosphonic acid ester, phosphinic acid, phosphinic acid ester, and phosphoric acid ester. Two or more of these may be used. Among these, a phosphoric acid derivative compound having a structure represented by the following general formula (1) is preferable. Since the phosphoric acid derivative compound having a structure represented by the following general formula (1) has a radical polymerizable group and a hydroxyl group, when the photosensitive siloxane resin composition is cured by heat and / or light, phosphoric acid derivative compound The acid derivative amine salt is efficiently incorporated into the (A) polysiloxane, and bleeding out can be suppressed. Moreover, chemical resistance and adhesion with the MAM substrate can be further improved.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　上記一般式（１）中、Ｒ１はラジカル重合性基を有する１価の有機基を示す。ラジカル重合性基を有する１価の有機基としては、例えば、炭素数１～１０のアルキル基の水素の少なくとも一部が、ビニル基、α－メチルビニル基、アリル基、スチリル基、（メタ）アクリロイル基などのラジカル重合性基により置換された基などが挙げられる。前記ラジカル重合性基としては（メタ）アクリロイル基が好ましく、前記アルキル基の炭素数は１～６が好ましい。 In the general formula (1), R 1 represents a monovalent organic group having a radical polymerizable group. As the monovalent organic group having a radical polymerizable group, for example, at least a part of hydrogen of an alkyl group having 1 to 10 carbon atoms is a vinyl group, an α-methylvinyl group, an allyl group, a styryl group, (meth) And a group substituted with a radical polymerizable group such as an acryloyl group. The radical polymerizable group is preferably a (meth) acryloyl group, and the alkyl group preferably has 1 to 6 carbon atoms.
　前記一般式（１）中、Ｒ２は水素、炭素数１～２０のアルキル基またはラジカル重合性基を有する１価の有機基を示す。ラジカル重合性基を有する１価の有機基としては、Ｒ１において例示したものが挙げられる。中でも、炭素数１～６のアルキル基、水素の少なくとも一部が（メタ）アクリロイル基により置換された炭素数１～６のアルキル基が好ましい。 In the general formula (1), R 2 represents hydrogen, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having a radical polymerizable group. Examples of the monovalent organic group having a radical polymerizable group include those exemplified for R 1 . Of these, an alkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms in which at least a part of hydrogen is substituted with a (meth) acryloyl group are preferable.
　前記一般式（１）で表される構造を有するリン酸誘導体化合物としては、例えば、２－メタクリロイロキシエチルアシッドホスフェート（商品名Ｐ－１Ｍ、共栄社化学（株）製）、２－アクリロイロキシエチルアシッドホスフェート（商品名Ｐ－１Ａ、共栄社化学（株）製）、エチレンオキサイド変性リン酸ジメタクリレート（商品名ＰＭ－２１、日本化薬（株）製）、リン酸含有エポキシメタクリレート（商品名“ニューフロンティア”（登録商標）Ｓ－２３Ａ、第一工業製薬（株）製）などのリン酸（メタ）アクリレート類；ビニルホスホン酸（商品名ＶＰＡ－９０、ＶＰＡ－１００、ＢＡＳＦ社製）などのリン酸ビニル化合物などが挙げられる。これらを２種以上用いてもよい。 Examples of the phosphoric acid derivative compound having the structure represented by the general formula (1) include 2-methacryloyloxyethyl acid phosphate (trade name P-1M, manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxy. Ethyl acid phosphate (trade name P-1A, manufactured by Kyoeisha Chemical Co., Ltd.), ethylene oxide-modified phosphoric acid dimethacrylate (trade name PM-21, manufactured by Nippon Kayaku Co., Ltd.), phosphoric acid-containing epoxy methacrylate (trade name “ Phosphoric acid (meth) acrylates such as “New Frontier” (registered trademark) S-23A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; vinylphosphonic acid (trade names VPA-90, VPA-100, manufactured by BASF) Examples include vinyl phosphate compounds. Two or more of these may be used.
　（ｄ２）アミン化合物としては、例えば、第１級アミン、第２級アミン、第３級アミンなどが挙げられる。これらを２種以上用いてもよい。これらの中でも、下記一般式（２）で表される構造を有するアミン化合物が好ましい。下記一般式（２）で表される構造を有するアミン化合物は、ヒドロキシル基を有することから、感光性シロキサン樹脂組成物を熱および／または光により硬化させる際に、リン酸誘導体アミン塩が（Ａ）ポリシロキサン中に効率的に取り込まれ、ブリードアウトを抑制することができる。また、耐薬品性およびＭＡＭ基板との密着性をより向上させることができる。 (D2) Examples of amine compounds include primary amines, secondary amines, and tertiary amines. Two or more of these may be used. Among these, an amine compound having a structure represented by the following general formula (2) is preferable. Since the amine compound having the structure represented by the following general formula (2) has a hydroxyl group, when the photosensitive siloxane resin composition is cured by heat and / or light, the phosphoric acid derivative amine salt is (A ) Efficiently incorporated into the polysiloxane to suppress bleed out. Moreover, chemical resistance and adhesion with the MAM substrate can be further improved.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　上記一般式（２）中、Ｒ３はヒドロキシル基を有する炭素数１～２０の１価の有機基を示す。１価の有機基としては、例えば、アルキル基、アシル基、アリール基などが挙げられ、炭素数１～１０のアルキル基、炭素数２～６のアシル基、炭素数６～１５のアリール基が好ましい。これらの中でも、水素の少なくとも一部がヒドロキシル基で置換された炭素数１～６のアルキル基が好ましい。 In the general formula (2), R 3 represents a monovalent organic group having 1 to 20 carbon atoms and having a hydroxyl group. Examples of the monovalent organic group include an alkyl group, an acyl group, and an aryl group, and examples thereof include an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms. preferable. Among these, an alkyl group having 1 to 6 carbon atoms in which at least a part of hydrogen is substituted with a hydroxyl group is preferable.
　前記一般式（２）中、Ｒ４およびＲ５はそれぞれ独立に水素、炭素数１～１０のアルキル基またはヒドロキシル基を有する炭素数１～２０の１価の有機基を示す。ヒドロキシル基を有する炭素数１～２０の１価の有機基としては、Ｒ３において例示したものが挙げられる。これらの中でも、水素、炭素数１～６のアルキル基、水素の少なくとも一部がヒドロキシル基で置換された炭素数１～６のアルキル基が好ましい。 In the general formula (2), R 4 and R 5 each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, or a monovalent organic group having 1 to 20 carbon atoms having a hydroxyl group. Examples of the monovalent organic group having 1 to 20 carbon atoms having a hydroxyl group include those exemplified for R 3 . Among these, hydrogen, an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms in which at least a part of hydrogen is substituted with a hydroxyl group are preferable.
　前記一般式（２）で表される構造を有するアミン化合物としては、例えば、エタノールアミン、ジエタノールアミン、トリエタノールアミン、プロパノールアミン、メタノールアミン、ジメチルエタノールアミン、ジエチルエタノールアミン、ジブチルエタノールアミン、Ｎ－メチルエタノールアミン、Ｎ－メチルジエタノールアミン、Ｎ－エチルエタノールアミン、Ｎ－エチルジエタノールアミン、Ｎ－ｎ－ブチルエタノールアミン、Ｎ－ｎ－ブチルジエタノールアミン、Ｎ－ｔ－ブチルエタノールアミン、Ｎ－ｔ－ブチルジエタノールアミンなどのアルカノールアミンが挙げられる。これらを２種以上用いてもよい。 Examples of the amine compound having the structure represented by the general formula (2) include ethanolamine, diethanolamine, triethanolamine, propanolamine, methanolamine, dimethylethanolamine, diethylethanolamine, dibutylethanolamine, and N-methyl. Ethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-ethyldiethanolamine, Nn-butylethanolamine, Nn-butyldiethanolamine, Nt-butylethanolamine, Nt-butyldiethanolamine, etc. Examples include alkanolamines. Two or more of these may be used.
　（Ｄ）リン酸誘導体アミン塩は、（ｄ１）リン酸誘導体化合物と（ｄ２）アミン化合物との反応により塩を形成させることにより得ることができる。塩形成に用いる（ｄ１）リン酸誘導体化合物に対する（ｄ２）アミン化合物の重量比（ｄ２／ｄ１）は、感光性シロキサン樹脂組成物の保存安定性をより向上させる観点から、０．１／９．９以上が好ましく、０．３／９．７以上がより好ましい。一方、感光性シロキサン樹脂組成物の保存安定性をより向上させる観点から、（ｄ２／ｄ１）は、１／９以下が好ましく、０．５／９．５以下がより好ましい。 (D) Phosphoric acid derivative amine salt can be obtained by forming a salt by reaction of (d1) phosphoric acid derivative compound and (d2) amine compound. From the viewpoint of further improving the storage stability of the photosensitive siloxane resin composition, the weight ratio (d2 / d1) of the (d2) amine compound to the (d1) phosphoric acid derivative compound used for salt formation is 0.1 / 9. 9 or more is preferable and 0.3 / 9.7 or more is more preferable. On the other hand, from the viewpoint of further improving the storage stability of the photosensitive siloxane resin composition, (d2 / d1) is preferably 1/9 or less, and more preferably 0.5 / 9.5 or less.
　本発明の感光性ポリシロキサン樹脂組成物は、（Ｄ）リン酸誘導体アミン塩を含有していればよく、前述の（Ａ）ポリシロキサン、（Ｂ）光ラジカル重合開始剤、（Ｃ）多官能モノマーなどとともに（Ｄ）リン酸誘導体アミン塩を配合したものであってもよいし、これらに（ｄ１）リン酸誘導体化合物と（ｄ２）アミン化合物を配合して、感光性ポリシロキサン組成物中において（Ｄ）リン酸誘導体アミン塩を形成したものであってもよい。感光性ポリシロキサン樹脂組成物の保存安定性をより向上させる観点から、前述の（Ａ）ポリシロキサン、（Ｂ）光ラジカル重合開始剤、（Ｃ）多官能モノマーなどとともに（Ｄ）リン酸誘導体アミン塩を配合したものが好ましい。 The photosensitive polysiloxane resin composition of the present invention only needs to contain (D) a phosphoric acid derivative amine salt, and the above-mentioned (A) polysiloxane, (B) photo radical polymerization initiator, (C) polyfunctional (D) A phosphoric acid derivative amine salt may be blended together with a monomer or the like, or (d1) a phosphoric acid derivative compound and (d2) an amine compound may be blended with these in the photosensitive polysiloxane composition. (D) A phosphoric acid derivative amine salt may be formed. From the viewpoint of further improving the storage stability of the photosensitive polysiloxane resin composition, (D) phosphoric acid derivative amine together with (A) polysiloxane, (B) photo radical polymerization initiator, (C) polyfunctional monomer, etc. Those containing a salt are preferred.
　（Ｅ）熱ラジカル発生剤
　本発明の感光性ポリシロキサン樹脂組成物は、さらに熱ラジカル発生剤を含有することが好ましい。熱ラジカル発生剤を含有することにより、加熱によりラジカルが発生し、不飽和二重結合の架橋が促進されることから、硬度をより向上させることができる。熱ラジカル発生剤としては、例えば、２，２’－アゾビス［２－メチル－Ｎ－（２－ヒドロキシエチル）プロピオンアミン］、２，２’－アゾビス［２－メチル－Ｎ－（２－プロペニル）－２－メチルプロピオンアミン］、２，２’－アゾビス（Ｎ－ブチル－２－メチルプロピオンアミン）、ジメチル２，２’－アゾビス（イソブチレート）、４，４’－アゾビス（４－シアノ吉草酸）、２，２’－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］２塩酸塩、２，２’－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］、２，２’－アゾビス（２－メチルプロピオンアミジン）２塩酸塩、２，２’－アゾビス［Ｎ－（２－カルボキシエチル）２－メチルプロピオンアミジン］ｎ水和物などが挙げられる。これらを２種以上含有してもよい。これらの中でも、硬化膜の硬度をより向上させる観点から、ジメチル２，２’－アゾビス（イソブチレート）が好ましい。 (E) Thermal radical generator It is preferable that the photosensitive polysiloxane resin composition of the present invention further contains a thermal radical generator. By containing a thermal radical generator, radicals are generated by heating and crosslinking of unsaturated double bonds is promoted, so that the hardness can be further improved. Examples of the thermal radical generator include 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamine], 2,2′-azobis [2-methyl-N- (2-propenyl). -2-methylpropionamine], 2,2'-azobis (N-butyl-2-methylpropionamine), dimethyl 2,2'-azobis (isobutyrate), 4,4'-azobis (4-cyanovaleric acid) 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2 ′ -Azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) 2-methylpropionamidine] n hydrate, and the like. Two or more of these may be contained. Among these, dimethyl 2,2′-azobis (isobutyrate) is preferable from the viewpoint of further improving the hardness of the cured film.
　本発明の感光性シロキサン樹脂組成物中における（Ｅ）熱ラジカル発生剤の含有量は、硬化をより効果的に進める観点から、固形分中、０．５重量％以上が好ましい。一方、着色を抑制して透明性を向上させる観点から、（Ｅ）熱ラジカル発生剤の含有量は、固形分中、５重量％以下が好ましい。 The content of the (E) thermal radical generator in the photosensitive siloxane resin composition of the present invention is preferably 0.5% by weight or more in the solid content from the viewpoint of more effectively curing. On the other hand, from the viewpoint of suppressing coloring and improving transparency, the content of the (E) thermal radical generator is preferably 5% by weight or less in the solid content.
　本発明の感光性シロキサン樹脂組成物は、必要に応じて、硬化剤、紫外線吸収剤、重合禁止剤、溶媒、界面活性剤、溶解抑止剤、安定剤、消泡剤などをさらに含有してもよい。 The photosensitive siloxane resin composition of the present invention may further contain a curing agent, an ultraviolet absorber, a polymerization inhibitor, a solvent, a surfactant, a dissolution inhibitor, a stabilizer, an antifoaming agent, etc., if necessary. Good.
　本発明の感光性シロキサン樹脂組成物に硬化剤を含有することにより、硬化を促進することができ、硬度をより向上させることができる。硬化剤としては、例えば、窒素含有有機物、シリコーン樹脂硬化剤、各種金属アルコレート、各種金属キレート化合物、イソシアネート化合物およびその重合体、メチロール化メラミン誘導体、メチロール化尿素誘導体などが挙げられる。これらを２種以上含有してもよい。これらの中でも、硬化剤の安定性、塗布膜の加工性などの観点から、金属キレート化合物、メチロール化メラミン誘導体、メチロール化尿素誘導体が好ましく用いられる。 By containing a curing agent in the photosensitive siloxane resin composition of the present invention, curing can be promoted and hardness can be further improved. Examples of the curing agent include nitrogen-containing organic substances, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, methylolated melamine derivatives, and methylolated urea derivatives. Two or more of these may be contained. Among these, metal chelate compounds, methylolated melamine derivatives, and methylolated urea derivatives are preferably used from the viewpoints of stability of the curing agent and processability of the coating film.
　本発明の感光性シロキサン樹脂組成物に紫外線吸収剤を含有することにより、硬化膜の耐光性を向上させ、解像度をより向上させることができる。紫外線吸収剤としては、着色を抑制して透明性を向上させる観点から、２－（２Ｈベンゾトリアゾール－２－イル）フェノール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ｔｅｒｔ－ペンチルフェノール、２－（２Ｈベンゾトリアゾール－２－イル）－４－（１，１，３，３－テトラメチルブチル）フェノール、２（２Ｈ－ベンゾトリアゾール－２－イル）－６－ドデシル－４－メチルフェノール、２－（２’－ヒドロキシ－５’－メタクリロキシエチルフェニル）－２Ｈ－ベンゾトリアゾールなどのベンゾトリアゾール系化合物；２－ヒドロキシ－４－メトキシベンゾフェノンなどのベンゾフェノン系化合物；２－（４，６－ジフェニル－１，３，５トリアジン－２－イル）－５－［（ヘキシル）オキシ］－フェノールなどのトリアジン系化合物が好ましく用いられる。 By containing the ultraviolet absorber in the photosensitive siloxane resin composition of the present invention, the light resistance of the cured film can be improved and the resolution can be further improved. As an ultraviolet absorber, 2- (2H-benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-tert is used from the viewpoint of suppressing coloring and improving transparency. -Pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4 Benzotriazole compounds such as methylphenol and 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole; benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone; 2- (4 , 6-Diphenyl-1,3,5triazin-2-yl) -5-[(hexyl) oxy] -phenol, etc. Triazine compounds are preferably used.
　本発明の感光性シロキサン樹脂組成物に重合禁止剤を含有することにより、解像度をより向上させることができる。重合禁止剤としては、例えば、ジ－ｔ－ブチルヒドロキシトルエン、ブチルヒドロキシアニソール、ハイドロキノン、４－メトキシフェノール、１，４－ベンゾキノン、ｔ－ブチルカテコールが挙げられる。また、市販の重合禁止剤としては、“ＩＲＧＡＮＯＸ”（登録商標）１０１０、“ＩＲＧＡＮＯＸ”１０３５、“ＩＲＧＡＮＯＸ”１０７６、“ＩＲＧＡＮＯＸ”１０９８、“ＩＲＧＡＮＯＸ”１１３５、“ＩＲＧＡＮＯＸ”１３３０、“ＩＲＧＡＮＯＸ”１７２６、“ＩＲＧＡＮＯＸ”１４２５、“ＩＲＧＡＮＯＸ”１５２０、“ＩＲＧＡＮＯＸ”２４５、“ＩＲＧＡＮＯＸ”２５９、“ＩＲＧＡＮＯＸ”３１１４、“ＩＲＧＡＮＯＸ”５６５、“ＩＲＧＡＮＯＸ”２９５（以上、商品名、ＢＡＳＦジャパン（株）製）などが挙げられる。これらを２種以上含有してもよい。 The resolution can be further improved by including a polymerization inhibitor in the photosensitive siloxane resin composition of the present invention. Examples of the polymerization inhibitor include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol. Commercially available polymerization inhibitors include “IRGANOX” (registered trademark) 1010, “IRGANOX” 1035, “IRGANOX” 1076, “IRGANOX” 1098, “IRGANOX” 1135, “IRGANOX” 1330, “IRGANOX” 1726, “ IRGANOX "1425," IRGANOX "1520," IRGANOX "245," IRGANOX "259," IRGANOX "3114," IRGANOX "565," IRGANOX "295 (above, trade name, manufactured by BASF Japan Ltd.) . Two or more of these may be contained.
　本発明の感光性シロキサン樹脂組成物に溶媒を含有することにより、塗布に適した粘度に容易に調整し、塗布膜の均一性を向上させることができる。大気圧下の沸点が１５０℃を超えて２５０℃以下の溶媒と、１５０℃以下の溶媒を組み合わせることが好ましい。沸点が１５０℃を超えて２５０℃以下の溶媒を含有することにより、塗布時に適度に溶媒が揮発して塗膜の乾燥が進行するため、塗布ムラを抑制し、膜厚均一性を向上させることができる。さらに、大気圧下の沸点が１５０℃以下の溶媒を含有することにより、後述する本発明の硬化膜中への溶媒の残存を抑制することができる。硬化膜中への溶媒の残存を抑制し、耐薬品性および密着性を長期間より向上させる観点から、大気圧下の沸点が１５０℃以下の溶媒を、溶媒全体の５０重量％以上含有することが好ましい。 By containing a solvent in the photosensitive siloxane resin composition of the present invention, the viscosity suitable for coating can be easily adjusted, and the uniformity of the coating film can be improved. It is preferable to combine a solvent whose boiling point under atmospheric pressure exceeds 150 ° C. and is 250 ° C. or less with a solvent that is 150 ° C. or less. By containing a solvent having a boiling point exceeding 150 ° C. and not more than 250 ° C., the solvent volatilizes appropriately at the time of coating, and drying of the coating proceeds, thereby suppressing coating unevenness and improving film thickness uniformity. Can do. Furthermore, by containing a solvent having a boiling point of 150 ° C. or lower under atmospheric pressure, the remaining of the solvent in the cured film of the present invention described later can be suppressed. From the viewpoint of suppressing the remaining of the solvent in the cured film and improving the chemical resistance and adhesiveness over a long period of time, a solvent having a boiling point of 150 ° C. or less under atmospheric pressure is contained by 50% by weight or more of the whole solvent. Is preferred.
　大気圧下の沸点が１５０℃以下の溶媒としては、例えば、エタノール、イソプロピルアルコール、１－プロピルアルコール、１－ブタノール、２－ブタノール、イソペンチルアルコール、エチレングリコールモノメチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールモノエチルエーテル、酢酸メトキシメチル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノプロピルエーテル、エチレングリコールモノメチルエーテルアセテート、１－メトキシプロピル－２－アセテート、アセトール、アセチルアセトン、メチルイソブチルケトン、メチルエチルケトン、メチルプロピルケトン、乳酸メチル、トルエン、シクロペンタノン、シクロヘキサン、ノルマルヘプタン、ベンゼン、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソブチル、酢酸ブチル、酢酸イソペンチル、酢酸ペンチル、３－ヒドロキシ－３－メチル－２－ブタノン、４－ヒドロキシ－３－メチル－２－ブタノン、５－ヒドロキシ－２－ペンタノンが挙げられる。これらを２種以上用いてもよい。 Examples of the solvent having a boiling point of 150 ° C. or lower under atmospheric pressure include, for example, ethanol, isopropyl alcohol, 1-propyl alcohol, 1-butanol, 2-butanol, isopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol mono Ethyl ether, methoxymethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, acetol, acetylacetone, methyl Isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl lactate Toluene, cyclopentanone, cyclohexane, normal heptane, benzene, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy- Examples thereof include 3-methyl-2-butanone and 5-hydroxy-2-pentanone. Two or more of these may be used.
　大気圧下の沸点が１５０℃を超えて２５０℃以下の溶媒としては、例えば、エチレングリコールジエチルエーテル、エチレングリコールモノ－ｎ－ブチルエーテル、エチレングリコールモノ－ｔｅｒｔ－ブチルエーテル、プロピレングリコールモノｎ－ブチルエーテル、プロピレングリコールモノｔ－ブチルエーテル、酢酸２－エトキシエチル、３－メトキシ－１－ブタノール、３－メトキシ－３－メチルブタノール、３－メトキシ－３－メチルブチルアセテート、３－メトキシブチルアセテート、３－エトキシプロピオン酸エチル、プロピレングリコールモノメチルエーテルプロピオネート、ジプロピレングリコールメチルエーテル、ジイソブチルケトン、ジアセトンアルコール、乳酸エチル、乳酸ブチル、ジメチルホルムアミド、ジメチルアセトアミド、γ－ブチロラクトン、γ－バレロラクトン、δ－バレロラクトン、炭酸プロピレン、Ｎ－メチルピロリドン、シクロヘキサノン、シクロヘプタノン、ジエチレングリコールモノブチルエーテル、エチレングリコールジブチルエーテルが挙げられる。これらを２種以上用いてもよい。 Examples of the solvent having a boiling point exceeding 150 ° C. and not higher than 250 ° C. include ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono n-butyl ether, propylene Glycol mono t-butyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, 3-ethoxypropionic acid Ethyl, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, diisobutyl ketone, diacetone alcohol, ethyl lactate, butyl lactate, dimethylformamide, dimethyl ester Ruasetoamido, .gamma.-butyrolactone, .gamma.-valerolactone, .delta.-valerolactone, propylene carbonate, N- methylpyrrolidone, cyclohexanone, cycloheptanone, diethylene glycol monobutyl ether, ethylene glycol dibutyl ether. Two or more of these may be used.
　溶媒の含有量は、塗布方法などに応じて任意に設定することができる。例えば、スピンコーティングにより膜形成を行う場合には、感光性シロキサン樹脂組成物中、５０重量％以上、９５重量％以下とすることが一般的である。 The content of the solvent can be arbitrarily set according to the application method. For example, when film formation is performed by spin coating, the content is generally 50% by weight or more and 95% by weight or less in the photosensitive siloxane resin composition.
　本発明の感光性シロキサン樹脂組成物に界面活性剤を含有することにより、塗布時のフロー性を向上させることができる。界面活性剤としては、例えば、“メガファック”（登録商標）Ｆ１４２Ｄ、Ｆ１７２、Ｆ１７３、Ｆ１８３、Ｆ４４５、Ｆ４７０、Ｆ４７５、Ｆ４７７（以上、商品名、大日本インキ化学工業（株）製）、ＮＢＸ－１５、ＦＴＸ－２１８（以上、商品名、（株）ネオス製）などのフッ素系界面活性剤；“ＢＹＫ”（登録商標）－３３３、“ＢＹＫ”－３０１、“ＢＹＫ”－３３１、“ＢＹＫ”－３４５、“ＢＹＫ”－３０７（以上、商品名、ビックケミー・ジャパン（株）製）などのシリコーン系界面活性剤；ポリアルキレンオキシド系界面活性剤；ポリ（メタ）アクリレート系界面活性剤などが挙げられる。これらを２種以上含有してもよい。 By containing a surfactant in the photosensitive siloxane resin composition of the present invention, the flowability during coating can be improved. Examples of the surfactant include “Megafac” (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (above, trade names, manufactured by Dainippon Ink and Chemicals, Inc.), NBX- 15, Fluorosurfactants such as FTX-218 (trade name, manufactured by Neos Co., Ltd.); “BYK” (registered trademark) -333, “BYK” -301, “BYK” -331, “BYK” -345, “BYK” -307 (trade name, manufactured by Big Chemie Japan Co., Ltd.) and other silicone surfactants; polyalkylene oxide surfactants; poly (meth) acrylate surfactants and the like It is done. Two or more of these may be contained.
　本発明の感光性シロキサン樹脂組成物の固形分濃度は、塗布方法などに応じて任意に設定することができる。例えば、後述のようにスピンコーティングにより膜形成を行う場合には、固形分濃度を、５重量％以上、５０重量％以下とすることが一般的である。 The solid content concentration of the photosensitive siloxane resin composition of the present invention can be arbitrarily set according to the coating method and the like. For example, when a film is formed by spin coating as will be described later, the solid content concentration is generally 5% by weight or more and 50% by weight or less.
　次に、本発明の感光性シロキサン樹脂組成物の製造方法について説明する。前述の（Ａ）～（Ｄ）成分および必要に応じてその他成分を混合することにより、本発明の感光性シロキサン樹脂組成物を得ることができる。より具体的には、例えば、（Ｂ）光ラジカル重合開始剤、（Ｃ）多官能モノマー、（Ｄ）リン酸エステルアミン塩および必要に応じてその他の添加剤を任意の溶媒に加え、撹拌して溶解させた後、（Ａ）ポリシロキサンを加え、さらに２０分間～３時間撹拌し、得られた溶液を濾過する方法などが挙げられる。 Next, a method for producing the photosensitive siloxane resin composition of the present invention will be described. The photosensitive siloxane resin composition of the present invention can be obtained by mixing the aforementioned components (A) to (D) and other components as necessary. More specifically, for example, (B) a radical photopolymerization initiator, (C) a polyfunctional monomer, (D) a phosphate ester amine salt and other additives as required are added to an arbitrary solvent and stirred. (A) Polysiloxane is added, and the mixture is further stirred for 20 minutes to 3 hours, and the resulting solution is filtered.
　次に、本発明の硬化膜について説明する。本発明の硬化膜は、前述の本発明の感光性ポリシロキサン樹脂組成物の硬化物からなる。硬化膜の膜厚は、０．１～１５μｍが好ましい。また、硬化膜の膜厚１．５μｍにおける波長４００ｎｍの光の透過率は、８５％以上が好ましい。なお、透過率は、後述する硬化膜の製造方法において、露光量や熱硬化温度を選択することにより、所望の範囲に調整することができる。 Next, the cured film of the present invention will be described. The cured film of the present invention comprises a cured product of the above-described photosensitive polysiloxane resin composition of the present invention. The thickness of the cured film is preferably 0.1 to 15 μm. Further, the transmittance of light having a wavelength of 400 nm when the thickness of the cured film is 1.5 μm is preferably 85% or more. The transmittance can be adjusted to a desired range by selecting the exposure amount and the thermosetting temperature in the cured film production method described later.
　本発明の硬化膜は、タッチパネル用保護膜、各種ハードコート材、ＴＦＴ用平坦化膜、カラーフィルター用オーバーコート、反射防止フィルム、パッシベーション膜などの各種保護膜、光学フィルター、タッチパネル用絶縁膜、ＴＦＴ用絶縁膜、カラーフィルター用フォトスペーサーなどに好適に用いることができる。これらの中でも、高い耐薬品性、基板密着性を有することから、タッチパネル用絶縁膜として好適に用いることができる。 The cured film of the present invention includes a protective film for a touch panel, various hard coating materials, a flattening film for TFT, an overcoat for a color filter, an antireflection film, a passivation film, and other protective films, an optical filter, an insulating film for a touch panel, a TFT It can be suitably used for insulating films for color, photo spacers for color filters, and the like. Among these, since it has high chemical resistance and substrate adhesion, it can be suitably used as an insulating film for touch panels.
　本発明の硬化膜は、例えば、前述の本発明の感光性ポリシロキサン樹脂組成物を膜状に塗布し、必要に応じてパターン加工した後、硬化させることにより得ることができる。本発明の感光性シロキサン樹脂組成物を基材上に塗布し、プリベークした後、露光・現像によりネガ型のパターンを形成し、熱硬化させることが好ましい。 The cured film of the present invention can be obtained, for example, by applying the above-mentioned photosensitive polysiloxane resin composition of the present invention in a film shape, patterning it if necessary, and then curing it. It is preferable that the photosensitive siloxane resin composition of the present invention is applied on a substrate and pre-baked, and then a negative pattern is formed by exposure and development, followed by heat curing.
　基材上に感光性シロキサン樹脂組成物を塗布する塗布方法としては、例えば、マイクログラビアコーティング、スピンコーティング、ディップコーティング、カーテンフローコーティング、ロールコーティング、スプレーコーティング、スリットコーティングなどの方法が挙げられる。プリベーク装置としては、ホットプレート、オーブンなどの加熱装置が挙げられる。プリベーク温度は５０～１３０℃が好ましく、プリベーク時間は３０秒間～３０分間が好ましい。プリベーク後の膜厚は、０．１～１５μｍが好ましい。 Examples of the application method for applying the photosensitive siloxane resin composition on the substrate include microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating. Examples of the pre-bake device include a heating device such as a hot plate and an oven. The prebake temperature is preferably 50 to 130 ° C., and the prebake time is preferably 30 seconds to 30 minutes. The film thickness after pre-baking is preferably 0.1 to 15 μm.
　露光は、所望のマスクを介して行ってもよいし、マスクを介さずに行ってもよい。露光機としては、例えば、ステッパー、ミラープロジェクションマスクアライナー（ＭＰＡ）、パラレルライトマスクアライナー（ＰＬＡ）などが挙げられる。露光強度は１０～４０００Ｊ／ｍ２程度（波長３６５ｎｍ露光量換算）が好ましい。露光光源としては、ｉ線、ｇ線、ｈ線等の紫外線や、ＫｒＦ（波長２４８ｎｍ）レーザー、ＡｒＦ（波長１９３ｎｍ）レーザー等が挙げられる。 The exposure may be performed through a desired mask or may be performed without using a mask. Examples of the exposure machine include a stepper, a mirror projection mask aligner (MPA), and a parallel light mask aligner (PLA). Exposure intensity is 10 ~ 4000J / m 2 approximately (wavelength 365nm exposure equivalent) are preferred. Examples of the exposure light source include ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like.
　現像方法としては、シャワー、ディッピング、パドルなどの方法が挙げられる。現像液に浸漬する時間は５秒間～１０分間が好ましい。現像液としては、例えば、アルカリ金属の水酸化物、炭酸塩、リン酸塩、ケイ酸塩、ホウ酸塩などの無機アルカリ、２－ジエチルアミノエタノール、モノエタノールアミン、ジエタノールアミン等のアミン類、テトラメチルアンモニウムヒドロキサイド、コリン等の４級アンモニウム塩を含む水溶液等のアルカリ現像液が挙げられる。現像後、水でリンスすることが好ましく、続いて５０～１３０℃の範囲で乾燥ベークを行うこともできる。 Developing methods include methods such as shower, dipping and paddle. The immersion time in the developer is preferably 5 seconds to 10 minutes. Examples of the developer include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine, tetramethyl Examples include alkaline developers such as aqueous solutions containing quaternary ammonium salts such as ammonium hydroxide and choline. After development, it is preferable to rinse with water, followed by drying and baking in the range of 50 to 130 ° C.
　熱硬化に用いる加熱装置としては、ホットプレート、オーブンなどが挙げられる。熱硬化温度は８０～１５０℃が好ましく、熱硬化時間は１５分間～１時間程度が好ましい。 Examples of the heating device used for thermosetting include a hot plate and an oven. The thermosetting temperature is preferably 80 to 150 ° C., and the thermosetting time is preferably about 15 minutes to 1 hour.
　次に、本発明の積層体について説明する。本発明の積層体は、基材上に前述の本発明の硬化膜を有する。 Next, the laminate of the present invention will be described. The laminate of the present invention has the above-described cured film of the present invention on a substrate.
　基材としては、例えば、ソーダライムガラス、無アルカリガラス等のガラス基板、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエーテルスルホン、ポリカーボネート、ポリイミド等のプラスチックからなる透明基材や、それらの上に電極または金属配線を有する基材などが挙げられる。 Examples of the base material include glass substrates such as soda lime glass and alkali-free glass, transparent base materials made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide, and electrodes or metals on them. Examples include a substrate having wiring.
　電極または金属配線を有する基材において、電極または金属配線を形成する材料としては、例えば、インジウム、スズ、亜鉛、アルミニウム、ガリウムなどの金属の酸化物；モリブデン、銀、銅、アルミニウム、クロム、チタンなどの金属；ＣＮＴ（Ｃａｒｂｏｎ　Ｎａｎｏ　Ｔｕｂｅ）などが挙げられる。金属の酸化物としては、例えば、酸化インジウムスズ（ＩＴＯ）、酸化インジウム亜鉛（ＩＺＯ）、酸化アルミニウム亜鉛（ＡＺＯ）、酸化インジウムガリウム亜鉛（ＩＧＺＯ）、酸化亜鉛（ＺｎＯ）が挙げられる。これらの中でも、モリブデンを含有する金属配線を有する基材が好ましい。 In a base material having an electrode or metal wiring, examples of the material for forming the electrode or metal wiring include metal oxides such as indium, tin, zinc, aluminum, and gallium; molybdenum, silver, copper, aluminum, chromium, titanium Metal such as CNT (Carbon Nano Tube). Examples of the metal oxide include indium tin oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO), indium gallium zinc oxide (IGZO), and zinc oxide (ZnO). Among these, a base material having a metal wiring containing molybdenum is preferable.
　本発明の積層体は、例えば、前述の本発明の感光性ポリシロキサン樹脂組成物を基材上に塗布する工程および塗布膜を８０～１５０℃で加熱する工程をこの順に含む製造方法により得ることができる。なお、感光性ポリシロキサン樹脂組成物を基材上に塗布する方法としては、硬化膜の製造方法として例示した方法などが挙げられる。また、塗布膜を８０～１５０℃で加熱する方法としては、硬化膜の製造方法として例示した方法などが挙げられる。加熱温度を８０℃以上とすることにより、反応を十分に進行させ、硬度、耐薬品性、基板密着性をより向上させることができる。一方、加熱温度を１５０℃以下とすることにより、過剰な反応とそれに伴う応力を抑制し、基板密着性をより向上させることができる。本発明の感光性シロキサン樹脂組成物は低温硬化可能であるため、１５０℃以下の温度で十分に硬化させることができる。 The laminate of the present invention can be obtained, for example, by a production method including the steps of applying the above-described photosensitive polysiloxane resin composition of the present invention on a substrate and heating the coating film at 80 to 150 ° C. in this order. Can do. In addition, as a method of apply | coating the photosensitive polysiloxane resin composition on a base material, the method illustrated as a manufacturing method of a cured film, etc. are mentioned. Examples of the method for heating the coating film at 80 to 150 ° C. include the methods exemplified as the method for producing a cured film. By setting the heating temperature to 80 ° C. or higher, the reaction can proceed sufficiently, and the hardness, chemical resistance, and substrate adhesion can be further improved. On the other hand, by setting the heating temperature to 150 ° C. or lower, it is possible to suppress excessive reaction and accompanying stress and further improve the substrate adhesion. Since the photosensitive siloxane resin composition of the present invention can be cured at a low temperature, it can be sufficiently cured at a temperature of 150 ° C. or lower.
　次に、本発明のタッチパネル用部材について説明する。本発明のタッチパネル用部材は、前述の積層体と表示パネルを有することが好ましい。さらに、前記積層体中の硬化膜が層間絶縁膜であることが好ましい。 Next, the touch panel member of the present invention will be described. It is preferable that the member for touch panels of this invention has the above-mentioned laminated body and a display panel. Furthermore, the cured film in the laminate is preferably an interlayer insulating film.
　以下、実施例を挙げて、本発明をさらに具体的に説明するが、本発明はこれら実施例に限定されない。合成例および実施例に用いた化合物のうち、略語を使用しているものについて、その内容を以下に示す。
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＰＧＭＥ:プロピレングリコールモノメチルエーテル
ＴＢＣ：４－ｔｅｒｔ－ブチルピロカテコール
Ｐ－１Ｍ：２－メタクリロイロキシエチルアシッドホスフェート（共栄社化学（株）製）。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. Of the compounds used in the synthesis examples and examples, those using abbreviations are shown below.
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether TBC: 4-tert-butylpyrocatechol P-1M: 2-methacryloyloxyethyl acid phosphate (manufactured by Kyoeisha Chemical Co., Ltd.).
　合成例１～６におけるポリシロキサン溶液および合成例７におけるアクリル樹脂溶液の固形分濃度は、以下の方法により求めた。アルミカップにポリシロキサン溶液またはアクリル樹脂溶液を１．５ｇ秤取し、ホットプレートを用いて２５０℃で３０分間加熱して液分を蒸発させた。加熱後のアルミカップに残った固形分の重量を秤量して、加熱前の重量に対する割合からポリシロキサン溶液またはアクリル樹脂溶液の固形分濃度を求めた。 The solid content concentrations of the polysiloxane solutions in Synthesis Examples 1 to 6 and the acrylic resin solution in Synthesis Example 7 were determined by the following method. In an aluminum cup, 1.5 g of the polysiloxane solution or acrylic resin solution was weighed and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid. The weight of the solid content remaining in the heated aluminum cup was weighed, and the solid content concentration of the polysiloxane solution or the acrylic resin solution was determined from the ratio to the weight before the heating.
　合成例１～６におけるポリシロキサンおよび合成例７におけるアクリル樹脂の重量平均分子量は、以下の方法により求めた。ＧＰＣ分析装置（ＨＬＣ－８２２０；東ソー（株）製）を用い、流動層としてテトラヒドロフランを用いて、「ＪＩＳ　Ｋ７２５２－３（制定年月日＝２００８／０３／２０）」に基づきＧＰＣ分析を行い、ポリスチレン換算の重量平均分子量を測定した。 The weight average molecular weights of the polysiloxanes in Synthesis Examples 1 to 6 and the acrylic resin in Synthesis Example 7 were determined by the following method. Using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation) and using tetrahydrofuran as a fluidized bed, GPC analysis was performed based on “JIS K7252-3 (established date = 2008/03/20)” The weight average molecular weight in terms of polystyrene was measured.
　合成例１～６におけるポリシロキサン中の各オルガノシラン単位の含有比率は、以下の方法により求めた。ポリシロキサン溶液を直径１０ｍｍの“テフロン”（登録商標）製ＮＭＲサンプル管に注入して２９Ｓｉ－ＮＭＲ測定を行い、オルガノシランに由来するＳｉ全体の積分値に対する、特定のオルガノシラン単位に由来するＳｉの積分値の割合から、各オルガノシラン単位の含有比率を算出した。２９Ｓｉ－ＮＭＲ測定条件を以下に示す。
装置：核磁気共鳴装置（ＪＮＭ－ＧＸ２７０；日本電子（株）製）
測定法：ゲーテッドデカップリング法
測定核周波数：５３．６６９３ＭＨｚ（２９Ｓｉ核）
スペクトル幅：２００００Ｈｚ
パルス幅：１２μｓ（４５°パルス）
パルス繰り返し時間：３０．０秒
溶媒：アセトン－ｄ６
基準物質：テトラメチルシラン
測定温度：２３℃
試料回転数：０．０Ｈｚ。 The content ratio of each organosilane unit in the polysiloxane in Synthesis Examples 1 to 6 was determined by the following method. The polysiloxane solution is injected into an NMR sample tube made of “Teflon” (registered trademark) having a diameter of 10 mm, and 29 Si-NMR measurement is performed. The polysiloxane solution is derived from a specific organosilane unit relative to the integral value of the entire Si derived from organosilane. The content ratio of each organosilane unit was calculated from the ratio of the integrated value of Si. The 29 Si-NMR measurement conditions are shown below.
Apparatus: Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.)
Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6669 MHz ( 29 Si nucleus)
Spectrum width: 20000Hz
Pulse width: 12μs (45 ° pulse)
Pulse repetition time: 30.0 seconds Solvent: Acetone-d6
Reference substance: Tetramethylsilane Measurement temperature: 23 ° C
Sample rotation speed: 0.0 Hz.
　合成例１　ポリシロキサン（Ａ－１）溶液
　５００ｍｌの三口フラスコに、ｐ－スチリルトリメトキシシランを４３．７４ｇ（０．１９５ｍｏｌ）、γ－アクリロイルプロピルトリメトキシシランを１４．０６ｇ（０．０６ｍｏｌ）、３－トリメトキシシリルプロピルコハク酸無水物を１１．８０ｇ（０．０４５ｍｏｌ）、ＴＢＣを０．１７３ｇ、ＰＧＭＥを７４．５８ｇ仕込み、室温で撹拌しながら、水１７．０１ｇにリン酸０．３４８ｇ（仕込みモノマーに対して０．５０重量％）を溶かしたリン酸水溶液を３０分間かけて添加した。その後、三口フラスコを７０℃のオイルバスに浸けて９０分間撹拌した後、オイルバスを３０分間かけて１１５℃まで昇温した。昇温開始１時間後に三口フラスコの内温（溶液温度）が１００℃に到達し、そこから２時間加熱撹拌し（内温は１００～１１０℃）、ポリシロキサン溶液を得た。なお、昇温および加熱撹拌中、窒素を０．０５リットル／分流した。反応中に、副生成物であるメタノールおよび水が合計３６．９０ｇ留出した。得られたポリシロキサン溶液に、固形分濃度が４０重量％となるようにＰＧＭＥを追加し、ポリシロキサン（Ａ－１）溶液を得た。ポリシロキサン（Ａ－１）のスチリル基を有する繰り返し単位、アクリロイル基を有する繰り返し単位、親水性基を有する繰り返し単位のモル比は、それぞれ６５ｍｏｌ％、２０ｍｏｌ％、１５ｍｏｌ％であった。ポリシロキサン（Ａ－１）の重量平均分子量は、４，０００であった。 Synthesis Example 1 Polysiloxane (A-1) Solution In a 500 ml three-necked flask, 43.74 g (0.195 mol) of p-styryltrimethoxysilane, 14.06 g (0.06 mol) of γ-acryloylpropyltrimethoxysilane, 11.80 g (0.045 mol) of 3-trimethoxysilylpropyl succinic anhydride, 0.173 g of TBC, and 74.58 g of PGME were charged. While stirring at room temperature, 0.348 g of phosphoric acid was added to 17.01 g of water ( An aqueous phosphoric acid solution in which 0.50% by weight of the charged monomer) was dissolved was added over 30 minutes. Thereafter, the three-necked flask was immersed in a 70 ° C. oil bath and stirred for 90 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature (solution temperature) of the three-neck flask reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution. Nitrogen was allowed to flow at 0.05 liter / min during the temperature rise and heating and stirring. During the reaction, a total of 36.90 g of methanol and water as by-products were distilled out. PGME was added to the obtained polysiloxane solution so that the solid concentration was 40% by weight to obtain a polysiloxane (A-1) solution. The molar ratio of the repeating unit having a styryl group, the repeating unit having an acryloyl group, and the repeating unit having a hydrophilic group in the polysiloxane (A-1) was 65 mol%, 20 mol%, and 15 mol%, respectively. The weight average molecular weight of the polysiloxane (A-1) was 4,000.
　合成例２　ポリシロキサン（Ａ－２）溶液
　γ－アクリロイルプロピルトリメトキシシランを２４．６０ｇ（０．１０５ｍｏｌ）、フェニルトリメトキシシランを８．９２ｇ（０．０４５ｍｏｌ）、３－トリメトキシシリルプロピルコハク酸無水物を１１．８０ｇ（０．０４５ｍｏｌ）、メチルトリメトキシシランを１４．３０ｇ（０．１０５ｍｏｌ）、ＴＢＣを０．０７３８ｇ、ＰＧＭＥを５９．６１ｇ仕込み、室温で撹拌しながら、水１７．０１ｇにリン酸０．３１７ｇ（仕込みモノマーに対して０．５０重量％）を溶かしたリン酸水溶液を３０分間かけて添加したこと以外は合成例１と同様の手順により、ポリシロキサン溶液を得た。得られたポリシロキサン溶液に、固形分濃度が４０重量％となるようにＰＧＭＥを追加し、ポリシロキサン（Ａ－２）溶液を得た。ポリシロキサン（Ａ－２）のアクリロイル基を有する繰り返し単位、親水性基を有する繰り返し単位のモル比は、それぞれ３５ｍｏｌ％、１５ｍｏｌ％であった。ポリシロキサン（Ａ－２）の重量平均分子量は、２，５００であった。 Synthesis Example 2 Polysiloxane (A-2) solution 24.60 g (0.105 mol) of γ-acryloylpropyltrimethoxysilane, 8.92 g (0.045 mol) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic acid 11.80 g (0.045 mol) of anhydride, 14.30 g (0.105 mol) of methyltrimethoxysilane, 0.0738 g of TBC, and 59.61 g of PGME were charged into 17.01 g of water while stirring at room temperature. A polysiloxane solution was obtained by the same procedure as in Synthesis Example 1 except that a phosphoric acid aqueous solution in which 0.317 g of phosphoric acid (0.50% by weight with respect to the charged monomer) was dissolved was added over 30 minutes. PGME was added to the obtained polysiloxane solution so that the solid concentration was 40% by weight to obtain a polysiloxane (A-2) solution. The molar ratio of the repeating unit having an acryloyl group and the repeating unit having a hydrophilic group in the polysiloxane (A-2) was 35 mol% and 15 mol%, respectively. The weight average molecular weight of the polysiloxane (A-2) was 2,500.
　合成例３　ポリシロキサン（Ａ－３）溶液
　ｐ－スチリルトリメトキシシランを１３．４６ｇ（０．０６ｍｏｌ）、γ－アクリロイルプロピルトリメトキシシランを１４．０６ｇ（０．０６ｍｏｌ）、３－トリメトキシシリルプロピルコハク酸無水物を７．８７ｇ（０．０３ｍｏｌ）、メチルトリメトキシシランを２０．４３ｇ（０．１５ｍｏｌ）、ＴＢＣを０．１１４ｇ、ＰＧＭＥを５３．４９ｇ仕込み、室温で撹拌しながら、水１６．７４ｇにリン酸０．２７９ｇ（仕込みモノマーに対して０．５０重量％）を溶かしたリン酸を添加したこと以外は合成例１と同様の手順により、ポリシロキサン溶液を得た。得られたポリシロキサン溶液に、固形分濃度が４０重量％となるようにＰＧＭＥを追加し、ポリシロキサン（Ａ－３）溶液を得た。ポリシロキサン（Ａ－３）のスチリル基を有する繰り返し単位、アクリロイル基を有する繰り返し単位、親水性基を有する繰り返し単位のモル比は、それぞれ２０ｍｏｌ％、２０ｍｏｌ％、１０ｍｏｌ％であった。ポリシロキサン（Ａ－３）の重量平均分子量は、３，５００であった。 Synthesis Example 3 Polysiloxane (A-3) solution 13.46 g (0.06 mol) of p-styryltrimethoxysilane, 14.06 g (0.06 mol) of γ-acryloylpropyltrimethoxysilane, 3-trimethoxysilylpropyl 7.87 g (0.03 mol) of succinic anhydride, 20.43 g (0.15 mol) of methyltrimethoxysilane, 0.114 g of TBC and 53.49 g of PGME were charged, and water 16. A polysiloxane solution was obtained by the same procedure as in Synthesis Example 1 except that phosphoric acid in which 0.279 g of phosphoric acid (0.50 wt% with respect to the charged monomer) was dissolved in 74 g was added. PGME was added to the obtained polysiloxane solution so that the solid concentration was 40% by weight to obtain a polysiloxane (A-3) solution. The molar ratio of the repeating unit having a styryl group, the repeating unit having an acryloyl group, and the repeating unit having a hydrophilic group in the polysiloxane (A-3) was 20 mol%, 20 mol%, and 10 mol%, respectively. The weight average molecular weight of the polysiloxane (A-3) was 3,500.
　合成例４　ポリシロキサン（Ａ－４）溶液
　ｐ－スチリルトリメトキシシランを５３．８４ｇ（０．２４ｍｏｌ）、γ－アクリロイルプロピルトリメトキシシランを７．０３ｇ（０．０３ｍｏｌ）、３－トリメトキシシリルプロピルコハク酸無水物を７．８７ｇ（０．０３ｍｏｌ）、ＴＢＣを０．１１４ｇ、ＰＧＭＥを７２．８７ｇ仕込み、室温で撹拌しながら、水１６．７４ｇにリン酸０．３４４ｇ（仕込みモノマーに対して０．５０重量％）を溶かしたリン酸を添加したこと以外は合成例１と同様の手順により、ポリシロキサン溶液を得た。得られたポリシロキサン溶液に、固形分濃度が４０重量％となるようにＰＧＭＥを追加し、ポリシロキサン（Ａ－４）溶液を得た。ポリシロキサン（Ａ－４）のスチリル基を有する繰り返し単位、アクリロイル基を有する繰り返し単位、親水性基を有する繰り返し単位のモル比は、それぞれ８０ｍｏｌ％、１０ｍｏｌ％、１０ｍｏｌ％であった。ポリシロキサン（Ａ－４）の重量平均分子量は、４，０００であった。 Synthesis Example 4 Polysiloxane (A-4) solution 53.84 g (0.24 mol) of p-styryltrimethoxysilane, 7.03 g (0.03 mol) of γ-acryloylpropyltrimethoxysilane, 3-trimethoxysilylpropyl 7.87 g (0.03 mol) of succinic anhydride, 0.114 g of TBC and 72.87 g of PGME were charged, and while stirring at room temperature, 0.344 g of phosphoric acid was added to 16.74 g of water (0 to the charged monomers). A polysiloxane solution was obtained by the same procedure as in Synthesis Example 1 except that phosphoric acid in which .50 wt% was dissolved was added. PGME was added to the obtained polysiloxane solution so that the solid concentration was 40% by weight to obtain a polysiloxane (A-4) solution. The molar ratio of the repeating unit having a styryl group, the repeating unit having an acryloyl group, and the repeating unit having a hydrophilic group in the polysiloxane (A-4) was 80 mol%, 10 mol%, and 10 mol%, respectively. The weight average molecular weight of the polysiloxane (A-4) was 4,000.
　合成例５　ポリシロキサン（Ａ－５）溶液の合成
　３－トリメトキシシリルプロピルコハク酸無水物を７．８７ｇ（０．０３ｍｏｌ）、メチルトリメトキシシランを２０．４３ｇ（０．１５ｍｏｌ）、フェニルトリメトキシシランを１７．８５ｇ（０．０９ｍｏｌ）、３－グリシドキシプロピルトリメトキシシランを７．０９ｇ（０．０３ｍｏｌ）、ＰＧＭＥを４９．６１ｇ仕込み、室温で撹拌しながら、水１６．７４ｇにリン酸０．２６６ｇ（仕込みモノマーに対して０．５０重量％）を溶かしたリン酸添加したこと以外は合成例１と同様の手順により、ポリシロキサン溶液を得た。得られたポリシロキサン溶液に、固形分濃度が４０重量％となるようにＰＧＭＥを追加し、ポリシロキサン（Ａ－５）溶液を得た。ポリシロキサン（Ａ－５）の親水性基を有する繰り返し単位のモル比は、１０ｍｏｌ％であった。ポリシロキサン（Ａ－５）の重量平均分子量は、３，０００であった。 Synthesis Example 5 Synthesis of polysiloxane (A-5) solution 7.87 g (0.03 mol) of 3-trimethoxysilylpropyl succinic anhydride, 20.43 g (0.15 mol) of methyltrimethoxysilane, phenyltrimethoxy 17.85 g (0.09 mol) of silane, 7.09 g (0.03 mol) of 3-glycidoxypropyltrimethoxysilane, and 49.61 g of PGME were charged, and phosphoric acid was added to 16.74 g of water while stirring at room temperature. A polysiloxane solution was obtained by the same procedure as in Synthesis Example 1 except that phosphoric acid in which 0.266 g (0.50% by weight with respect to the charged monomer) was dissolved was added. PGME was added to the obtained polysiloxane solution so that the solid concentration was 40% by weight to obtain a polysiloxane (A-5) solution. The molar ratio of the repeating unit having a hydrophilic group in the polysiloxane (A-5) was 10 mol%. The weight average molecular weight of the polysiloxane (A-5) was 3,000.
　合成例６　ポリシロキサン（Ａ－６）溶液の合成
　ｐ－スチリルトリメトキシシランを１３．４６ｇ（０．０６ｍｏｌ）、γ－アクリロイルプロピルトリメトキシシランを１４．０６ｇ（０．０６ｍｏｌ）、メチルトリメトキシシランを１２．２６ｇ（０．０９ｍｏｌ）、テトラトリメトキシシランを１３．６８ｇ（０．０９ｍｏｌ）、ＴＢＣを０．０８２６ｇ、ＰＧＭＥを５１．５６ｇ仕込み、室温で撹拌しながら、水１７．８２ｇにリン酸０．２６７ｇ（仕込みモノマーに対して０．５０重量％）を溶かしたリン酸を添加したこと以外は合成例１と同様の手順により、ポリシロキサン溶液を得た。得られたポリシロキサン溶液に、固形分濃度が４０重量％となるようにＰＧＭＥを追加し、ポリシロキサン（Ａ－６）溶液を得た。ポリシロキサン（Ａ－６）のスチリル基を有する繰り返し単位、アクリロイル基を有する繰り返し単位のモル比は、それぞれ２０ｍｏｌ％、２０ｍｏｌ％であった。ポリシロキサン（Ａ－６）の重量平均分子量は、５，０００であった。 Synthesis Example 6 Synthesis of Polysiloxane (A-6) Solution 13.46 g (0.06 mol) of p-styryltrimethoxysilane, 14.06 g (0.06 mol) of γ-acryloylpropyltrimethoxysilane, methyltrimethoxysilane 12.26 g (0.09 mol), tetratrimethoxysilane 13.68 g (0.09 mol), TBC 0.0826 g and PGME 51.56 g were charged, and phosphoric acid was added to 17.82 g of water while stirring at room temperature. A polysiloxane solution was obtained by the same procedure as in Synthesis Example 1 except that phosphoric acid in which 0.267 g (0.50% by weight with respect to the charged monomer) was dissolved was added. PGME was added to the obtained polysiloxane solution so that the solid concentration was 40% by weight to obtain a polysiloxane (A-6) solution. The molar ratio of the repeating unit having a styryl group and the repeating unit having an acryloyl group in the polysiloxane (A-6) was 20 mol% and 20 mol%, respectively. The weight average molecular weight of the polysiloxane (A-6) was 5,000.
　合成例７　アクリル樹脂（ａ）溶液の合成
　５００ｍｌの三口フラスコに、２,２’－アゾビス（イソブチロニトリル）を３ｇ、ＰＧＭＥを５０ｇ仕込んだ。その後、メタクリル酸を３０ｇ、ベンジルメタクリレートを３５ｇ、トリシクロ［５．２．１．０２，６］デカン－８－イルメタクリレートを３５ｇ仕込み、室温でしばらく撹拌し、フラスコ内を窒素置換した後、７０℃で５時間加熱撹拌した。次に、得られた溶液にメタクリル酸グリシジルを１５ｇ、ジメチルベンジルアミンを１ｇ、ｐ－メトキシフェノールを０．２ｇ、ＰＧＭＥＡを１００ｇ添加し、９０℃で４時間加熱撹拌し、アクリル樹脂（ａ）溶液を得た。得られたアクリル樹脂（ａ）溶液に固形分濃度が４０重量％になるようにＰＧＭＥを加えた。アクリル樹脂（ａ）の重量平均分子量は、１０，０００であった。 Synthesis Example 7 Synthesis of Acrylic Resin (a) Solution A 500 ml three-necked flask was charged with 3 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGME. Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature. The mixture was stirred at 5 ° C. for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain an acrylic resin (a) solution. Got. PGME was added to the obtained acrylic resin (a) solution so that the solid concentration would be 40% by weight. The weight average molecular weight of the acrylic resin (a) was 10,000.
　各合成例の原料比率を表１に示す。 The raw material ratio of each synthesis example is shown in Table 1.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　（１）パターン加工性
　各実施例および比較例により得られた感光性シロキサン樹脂組成物または感光性アクリル樹脂組成物を、スピンコーター（商品名１Ｈ－３６０Ｓ、ミカサ（株）製）を用いて、シリコンウエハ上にスピンコートし、ホットプレート（商品名ＳＣＷ－６３６、大日本スクリーン製造（株）製）を用いて、１００℃で２分間プリベークし、膜厚２．０μｍの膜を作製した。 (1) Pattern processability Using a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), the photosensitive siloxane resin composition or photosensitive acrylic resin composition obtained in each example and comparative example was used. A silicon wafer was spin-coated, and prebaked at 100 ° C. for 2 minutes using a hot plate (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a film having a thickness of 2.0 μm.
　作製した膜を、パラレルライトマスクアライナー（商品名ＰＬＡ－５０１Ｆ、キヤノン（株）製）を用いて、超高圧水銀灯を光源とし、１００μｍ、５０μｍ、４０μｍ、３０μｍ、２０μｍ、１５μｍ、１０μｍの各幅のライン＆スペースパターンを有するグレースケールマスクを介して、１００μｍのギャップで露光した。その後、自動現像装置（滝沢産業（株）製「ＡＤ－２０００（商品名）」）を用いて、０．０４５重量％水酸化カリウム水溶液で６０秒間シャワー現像し、次いで水で３０秒間リンスした。 Using the parallel light mask aligner (trade name PLA-501F, manufactured by Canon Inc.) and the ultrahigh pressure mercury lamp as the light source, the prepared film is 100 μm, 50 μm, 40 μm, 30 μm, 20 μm, 15 μm, 10 μm in width. It exposed with the gap of 100 micrometers through the gray scale mask which has a line & space pattern. Thereafter, using an automatic developing device (“AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), the film was shower-developed with 0.045 wt% potassium hydroxide aqueous solution for 60 seconds and then rinsed with water for 30 seconds.
　露光、現像後、１００μｍ幅のラインアンドスペースパターンを１対１の幅に形成する露光量を最適露光量とし、最適露光量における現像後の最小パターン寸法を解像度とした。また、現像後のパターンを目視および倍率を５０～１００倍に調整した顕微鏡により観察し、未露光部の溶け残り程度により、以下の基準により現像残渣を評価した。
５：目視では残渣が認められず、顕微鏡の観察において、５０μｍ以下の微細パターンも残渣が認められない。
４：目視では残渣認められず、顕微鏡観察において、５０μｍ超のパターンには残渣が認められないが、５０μｍ以下のパターンには残渣が認められる。
３：目視では残渣が認められないが、顕微鏡観察において、５０μｍ超のパターンに残渣が認められる。
２：目視で基板端部（厚膜部）に残渣が認められる。
１：目視で未露光部全体に残渣が認められる。 After exposure and development, the exposure amount for forming a line and space pattern having a width of 100 μm in a one-to-one width was taken as the optimum exposure amount, and the minimum pattern size after development at the optimum exposure amount was taken as the resolution. The developed pattern was observed visually and with a microscope whose magnification was adjusted to 50 to 100 times, and the development residue was evaluated according to the following criteria according to the degree of undissolved portion of the unexposed area.
5: A residue is not recognized visually, and a residue is also not recognized by the fine pattern below 50 micrometers in microscopic observation.
4: No residue is visually observed, and no residue is observed in a pattern of more than 50 μm by microscopic observation, but a residue is observed in a pattern of 50 μm or less.
3: Although a residue is not recognized visually, a residue is recognized by the pattern over 50 micrometers in microscopic observation.
2: A residue is visually recognized at the substrate end (thick film portion).
1: A residue is visually recognized in the whole unexposed part.
　（２）基板密着性
　各実施例および比較例により得られた感光性シロキサン樹脂組成物または感光性アクリル樹脂組成物を、スピンコーター（商品名１Ｈ－３６０Ｓ、ミカサ（株）製）を用いて、表面にＩＴＯまたはＭＡＭをスパッタリングしたガラス基板（以下、「ＩＴＯ基板」または「ＭＡＭ基板」という）上にスピンコートし、ホットプレート（商品名ＳＣＷ－６３６、大日本スクリーン製造（株）製）を用いて１００℃で２分間プリベークし、膜厚２．０μｍの膜を作製した。 (2) Substrate adhesion Using the spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), the photosensitive siloxane resin composition or photosensitive acrylic resin composition obtained in each example and comparative example was used. Spin coated onto a glass substrate (hereinafter referred to as “ITO substrate” or “MAM substrate”) with ITO or MAM sputtered on the surface, and using a hot plate (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) And prebaked at 100 ° C. for 2 minutes to produce a film having a thickness of 2.0 μm.
　作製した膜を、パラレルライトマスクアライナー（商品名ＰＬＡ－５０１Ｆ、キヤノン（株）製を用いて、超高圧水銀灯を光源として露光し、オーブン（商品名ＩＨＰＳ－２２２、エスペック（株）製）を用いて、空気中１２０℃で１時間キュアし、膜厚１．５μｍの硬化膜を作製した。 The prepared film was exposed using a parallel light mask aligner (trade name PLA-501F, manufactured by Canon Inc.) using an ultra-high pressure mercury lamp as a light source, and using an oven (trade name IHPS-222, manufactured by ESPEC Corporation). Then, it was cured in air at 120 ° C. for 1 hour to produce a cured film having a thickness of 1.5 μm.
　得られた硬化膜について、ＪＩＳ「Ｋ５６００－５－６（制定年月日＝１９９９／０４／２０）」に準じてＩＴＯ基板またはＭＡＭ基板と硬化膜との接着性（基板密着性）を評価した。すなわち、ＩＴＯ基板またはＭＡＭ基板上の硬化膜表面に、カッターナイフでガラス板の素地に到達するように、直交する縦横１１本ずつの平行な直線を１ｍｍ間隔で引いて、１ｍｍ×１ｍｍのマス目を１００個作製した。切られた硬化膜表面にセロハン粘着テープ（幅＝１８ｍｍ、粘着力＝３．７Ｎ／１０ｍｍ）を貼り付け、消しゴム（ＪＩＳ　Ｓ６０５０合格品）で擦って密着させ、テープの一端を持ち、板に直角を保ち瞬間的に剥離した際のマス目の残存数を目視によって計数した。マス目の剥離面積により、以下の基準により接着性を評価し、４以上を合格とした。
５：剥離面積＝０％
４：剥離面積＝１～４％
３：剥離面積＝５～１４％
２：剥離面積＝１５～３４％
１：剥離面積＝３５～６４％
０：剥離面積＝６５～１００％。 The obtained cured film was evaluated for adhesion (substrate adhesion) between the ITO substrate or MAM substrate and the cured film according to JIS “K5600-5-6 (established date = 1999/04/20)”. . In other words, on the surface of the cured film on the ITO substrate or MAM substrate, 11 parallel vertical and horizontal lines are drawn at 1 mm intervals so as to reach the substrate of the glass plate with a cutter knife. 100 pieces were produced. A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) is affixed to the cut cured film surface, and it is rubbed with an eraser (JIS S6050 passed product) to hold it, holding one end of the tape, and perpendicular to the plate The number of remaining squares when the film was peeled off instantaneously was kept visually. The adhesiveness was evaluated according to the following criteria based on the peeled area of the cells, and 4 or more was determined to be acceptable.
5: Peel area = 0%
4: Peeling area = 1 to 4%
3: Peel area = 5-14%
2: Peel area = 15-34%
1: Peeling area = 35-64%
0: peeling area = 65 to 100%.
　（３）耐薬品性
　ＩＴＯ基板およびＭＡＭ基板上に、前記（２）記載の方法と同様にして膜厚１．５μｍの硬化膜を形成した。レジスト剥離液であるＮ３００に、下記条件１～４の各条件で硬化膜を浸漬した後、ＪＩＳ「Ｋ５６００－５－６（制定年月日＝１９９９／０４／２０）」に準じて、上記（２）に記載の方法と同様にして基板密着性を評価した。マス目の剥離面積が５％以下である場合に、その条件における耐薬品性があると判断した。
条件１：５０℃、２分間
条件２：６０℃、２分間
条件３：７０℃、２分間
条件４：８０℃、２分間
　耐薬品性があると判断された条件をもとに、耐薬品性を以下の基準により評価し、１以上を合格とした。
４：条件１、２、３、４いずれも耐薬品性あり
３：条件１、２、３において耐薬品性あり
２：条件１、２のみにおいて耐薬品性あり
１：条件１のみにおいて耐薬品性あり
０：いずれの条件においても耐薬品性なし。 (3) Chemical resistance A cured film having a thickness of 1.5 μm was formed on the ITO substrate and the MAM substrate in the same manner as in the method described in (2) above. After immersing the cured film in the resist stripping solution N300 under the following conditions 1 to 4, the above (in accordance with JIS “K5600-5-6 (date of establishment = 1999/04/20)”) ( Substrate adhesion was evaluated in the same manner as described in 2). When the peeled area of the squares was 5% or less, it was judged that there was chemical resistance under the conditions.
Condition 1: 50 ° C., 2 minutes Condition 2: 60 ° C., 2 minutes Condition 3: 70 ° C., 2 minutes Condition 4: 80 ° C., 2 minutes Chemical resistance based on conditions judged to have chemical resistance Was evaluated according to the following criteria, and one or more was regarded as acceptable.
4: Conditions 1, 2, 3, 4 all have chemical resistance 3: Conditions 1, 2, and 3 have chemical resistance 2: Conditions 1 and 2 have chemical resistance 1: Conditions 1 have chemical resistance only Yes: No chemical resistance under any conditions.
　（４）硬度
　ＩＴＯ基板上に、前記（２）記載の方法と同様にして得られた膜厚１．５μｍの硬化膜を形成した。得られた硬化膜について、ＪＩＳ「Ｋ５６００－５－４（制定年月日＝１９９９／０４／２０）」に準拠して鉛筆硬度を測定した。 (4) Hardness A cured film having a thickness of 1.5 μm obtained in the same manner as in the method described in (2) above was formed on the ITO substrate. The resulting cured film was measured for pencil hardness in accordance with JIS “K5600-5-4 (established date = 1999/04/20)”.
　（５）保存安定性
　各実施例および比較例により得られた感光性シロキサン樹脂組成物または感光性アクリル樹脂組成物について、調合終了後に粘度（保管前粘度）を測定した。また、各実施例および比較例により得られた感光性シロキサン樹脂組成物または感光性アクリル樹脂組成物を密封容器に入れ、２３℃で７日保管後の粘度を同様に測定した。粘度変化率（｛｜保管後粘度－保管前粘度｜／保管前粘度｝×１００）から以下の基準により保存安定性を評価した。
Ａ：粘度変化率５％未満
Ｂ：粘度変化率５％以上１０％未満
Ｃ：粘度変化率１０％以上。 (5) Storage stability About the photosensitive siloxane resin composition or photosensitive acrylic resin composition obtained by each Example and the comparative example, the viscosity (viscosity before storage) was measured after completion | finish of preparation. Moreover, the photosensitive siloxane resin composition or the photosensitive acrylic resin composition obtained by each Example and the comparative example was put into the sealed container, and the viscosity after storing for 7 days at 23 degreeC was measured similarly. Storage stability was evaluated from the viscosity change rate ({| viscosity after storage−viscosity before storage | / viscosity before storage} × 100) according to the following criteria.
A: Viscosity change rate of less than 5% B: Viscosity change rate of 5% or more and less than 10% C: Viscosity change rate of 10% or more.
　実施例１
　黄色灯下にて、（Ｂ）光ラジカル重合開始剤として、エタノン,１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム)（“イルガキュア”（登録商標）ＯＸＥ－０２（商品名）、ＢＡＳＦジャパン（株）製）０．０８０ｇおよびビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（“イルガキュア”（登録商標）－８１９（商品名）、ＢＡＳＦジャパン（株）製）０．１６０ｇ、エチレンビス（オキシエチレン）ビス[３－(５－ｔｅｒｔ－ブチル－４－ヒドロキシ－ｍ－トリル）プロピオネート]（“イルガノックス”（登録商標）－２４５（商品名）、ＢＡＳＦジャパン（株）製）のＰＧＭＥ１０重量％溶液０．１２０ｇ、テトラキス（アセチルアセトナート）ジルコニウム（ＩＶ）（ＺＣ－１５０（商品名）、マツモトファインケミカル（株）製）のＰＧＭＥ２重量％溶液３．９９８ｇ、（Ｃ）多官能モノマーとして、ペンタエリスリトールアクリレート（“ライトアクリレート”（登録商標）ＰＥ－３Ａ（商品名）、共栄社化学（株）製）０．４００ｇを、ＰＧＭＥ１．６６７ｇとＰＧＭＥＡ３．２００ｇの混合溶剤に溶解させ、シリコーン系界面活性剤（商品名“ＢＹＫ”（登録商標）－３３３、ビックケミー・ジャパン（株）製）のＰＧＭＥ１重量％希釈溶液０．２００ｇ（濃度１００ｐｐｍに相当）を加え、撹拌した。その後、（Ａ）ポリシロキサンとして、ポリシロキサン（Ａ－１）溶液６．１６７ｇ、（Ｄ）リン酸エステルアミン塩として、事前にリン酸誘導体化合物（ｄ１）Ｐ－１Ｍとアミン化合物（ｄ２）モノエタノールアミンを（ｄ２／ｄ１）＝０．５／９．５の重量割合で反応させて得られた反応物の濃度２０重量％のＰＧＭＥ溶液３．９９８ｇを加え撹拌した。次いで０．４５μｍのフィルターでろ過を行い、感光性シロキサン樹脂組成物（Ｐ－１）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－１）について、前述の方法により、パターン加工性、基板密着性、耐薬品性、硬度、保存安定性を評価した。 Example 1
Under a yellow light, (B) as radical photopolymerization initiator, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl) Oxime) (“Irgacure” (registered trademark) OXE-02 (trade name), manufactured by BASF Japan Ltd.) 0.080 g and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“Irgacure” ( Registered trademark) -819 (trade name), manufactured by BASF Japan Ltd.) 0.160 g, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (“ Irganox ”(registered trademark) -245 (trade name), BASF Japan Ltd.) PGME 10% by weight solution 0.120 g, tetrakis (acetyl) 3.998 g of a 2% by weight PGME solution of Settonate Zirconium (IV) (ZC-150 (trade name), manufactured by Matsumoto Fine Chemical Co., Ltd.), (C) Pentaerythritol acrylate (“Light Acrylate” (registered trademark) as a polyfunctional monomer ) PE-3A (trade name) manufactured by Kyoeisha Chemical Co., Ltd. (0.400 g) was dissolved in a mixed solvent of PGME 1.667 g and PGMEA 3.200 g, and a silicone-based surfactant (trade name “BYK” (registered trademark)) was dissolved. 0.200 g (corresponding to a concentration of 100 ppm) of PGME 1% by weight diluted with PGME (-333, manufactured by Big Chemie Japan Co., Ltd.) and stirred. Then, 6.167 g of polysiloxane (A-1) solution as (A) polysiloxane, (D) phosphoric acid ester amine salt as phosphoric acid derivative compound (d1) P-1M and amine compound (d2) mono 3.998 g of a PGME solution having a concentration of 20% by weight obtained by reacting ethanolamine at a weight ratio of (d2 / d1) = 0.5 / 9.5 was added and stirred. Next, filtration was performed with a 0.45 μm filter to obtain a photosensitive siloxane resin composition (P-1). The resulting photosensitive siloxane resin composition (P-1) was evaluated for pattern processability, substrate adhesion, chemical resistance, hardness, and storage stability by the methods described above.
　実施例２
　ポリシロキサン（Ａ－１）溶液の代わりにポリシロキサン（Ａ－２）溶液６．１６７ｇを用いた以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－２）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－２）を用いて、実施例１と同様にして評価を行った。 Example 2
A photosensitive siloxane resin composition (P-2) was obtained in the same manner as in Example 1 except that 6.167 g of the polysiloxane (A-2) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive siloxane resin composition (P-2).
　実施例３
　ポリシロキサン（Ａ－１）溶液の代わりにポリシロキサン（Ａ－３）溶液６．１６７ｇを用いた以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－３）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－３）を用いて、実施例１と同様にして評価を行った。 Example 3
A photosensitive siloxane resin composition (P-3) was obtained in the same manner as in Example 1 except that 6.167 g of the polysiloxane (A-3) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-3).
　実施例４
　ポリシロキサン（Ａ－１）溶液の代わりにポリシロキサン（Ａ－４）溶液６．１６７ｇを用いた以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－４）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－４）を用いて、実施例１と同様にして評価を行った。 Example 4
A photosensitive siloxane resin composition (P-4) was obtained in the same manner as in Example 1 except that 6.167 g of the polysiloxane (A-4) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive siloxane resin composition (P-4).
　実施例５
　ポリシロキサン（Ａ－１）溶液の代わりにポリシロキサン（Ａ－５）溶液６．１６７ｇを用いた以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－５）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－５）を用いて、実施例１と同様にして評価を行った。 Example 5
A photosensitive siloxane resin composition (P-5) was obtained in the same manner as in Example 1 except that 6.167 g of the polysiloxane (A-5) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-5).
　実施例６
　ポリシロキサン（Ａ－１）溶液の代わりにポリシロキサン（Ａ－６）溶液６．１６７ｇを用いた以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－６）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－６）を用いて、実施例１と同様にして評価を行った。 Example 6
A photosensitive siloxane resin composition (P-6) was obtained in the same manner as in Example 1 except that 6.167 g of the polysiloxane (A-6) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-6).
　実施例７
　リン酸誘導体化合物（ｄ１）Ｐ－１Ｍの代わりに２－アクリロイロキシエチルアシッドホスフェート（Ｐ－１Ａ（商品名）、共栄社化学（株）製）を用いた以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－７）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－７）を用いて、実施例１と同様にして評価を行った。 Example 7
The same procedure as in Example 1 was conducted except that 2-acryloyloxyethyl acid phosphate (P-1A (trade name), manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of the phosphoric acid derivative compound (d1) P-1M. A photosensitive siloxane resin composition (P-7) was obtained. The obtained photosensitive siloxane resin composition (P-7) was used for evaluation in the same manner as in Example 1.
　実施例８
　アミン化合物（ｄ２）モノエタノールアミンの代わりにトリエタノールアミンを用いた以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－８）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－８）を用いて、実施例１と同様にして評価を行った。 Example 8
Amine compound (d2) A photosensitive siloxane resin composition (P-8) was obtained in the same manner as in Example 1 except that triethanolamine was used instead of monoethanolamine. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-8).
　実施例９
　リン酸誘導体化合物（ｄ１）Ｐ－１Ｍの代わりにエチルアシッドフォスフェート（ＪＰ５０２（商品名）、城北化学工業（株）製）を用いた以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－９）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－９）を用いて、実施例１と同様にして評価を行った。 Example 9
The same procedure as in Example 1 was carried out except that ethyl acid phosphate (JP502 (trade name), manufactured by Johoku Chemical Industry Co., Ltd.) was used instead of the phosphoric acid derivative compound (d1) P-1M. A product (P-9) was obtained. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-9).
　実施例１０
　アミン化合物（ｄ２）モノエタノールアミンの代わりにトリエチルアミンを用いた以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－１０）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－１０）を用いて、実施例１と同様にして評価を行った。 Example 10
Amine compound (d2) A photosensitive siloxane resin composition (P-10) was obtained in the same manner as in Example 1 except that triethylamine was used instead of monoethanolamine. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive siloxane resin composition (P-10).
　実施例１１
　ポリシロキサン（Ａ－１）溶液の量を７．１６６ｇとし、リン酸誘導体化合物（ｄ１）Ｐ－１Ｍとアミン化合物（ｄ２）モノエタノールアミンとの重量割合（ｄ２／ｄ１）＝０．５／９．５の反応物のＰＧＭＥ溶液の量を１．９９９ｇとし、混合溶剤を、ＰＧＭＥ２．６６７ｇとＰＧＭＥＡ３．２００ｇとした以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－１１）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－１１）を用いて、実施例１と同様にして評価を行った。 Example 11
The amount of the polysiloxane (A-1) solution was 7.166 g, and the weight ratio (d2 / d1) of the phosphoric acid derivative compound (d1) P-1M and the amine compound (d2) monoethanolamine (d2 / d1) = 0.5 / 9 Photosensitive siloxane resin composition (P-11), except that the amount of the PGME solution of the reaction product of .5 was 1.999 g and the mixed solvent was 2.667 g of PGME and 3.200 g of PGMEA. Got. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-11).
　実施例１２
　ポリシロキサン（Ａ－１）溶液の量を５．１６７ｇとし、リン酸誘導体化合物（ｄ１）Ｐ－１Ｍとアミン化合物（ｄ２）モノエタノールアミンとの重量割合（ｄ２／ｄ１）＝０．５／９．５の反応物のＰＧＭＥ溶液の量を５．９９７ｇとし、混合溶剤を、ＰＧＭＥ０．６７８ｇとＰＧＭＥＡ３．２００ｇとした以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－１２）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－１２）を用いて、実施例１と同様にして評価を行った。 Example 12
The amount of the polysiloxane (A-1) solution was 5.167 g, and the weight ratio (d2 / d1) of the phosphoric acid derivative compound (d1) P-1M and the amine compound (d2) monoethanolamine (d2 / d1) = 0.5 / 9 Photosensitive siloxane resin composition (P-12), except that the amount of the PGME solution of the reaction product of .5 was 5.997 g and the mixed solvent was 0.678 g of PGME and 3.200 g of PGMEA. Got. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-12).
　実施例１３
　リン酸誘導体化合物（ｄ１）Ｐ－１Ｍとアミン化合物（ｄ２）モノエタノールアミンとの重量割合（ｄ２／ｄ１）＝０．５／９．５の反応物のＰＧＭＥ溶液の代わりに、事前にリン酸誘導体化合物（ｄ１）Ｐ－１Ｍとアミン化合物（ｄ２）モノエタノールアミンを（ｄ２／ｄ１）＝０．１／９．９の重量割合で反応させて得られた反応物の濃度２０重量％のＰＧＭＥ溶液３．９９９ｇを用いた以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－１３）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－１３）を用いて、実施例１と同様にして評価を行った。 Example 13
Phosphoric acid derivative compound (d1) P-1M and amine compound (d2) monoethanolamine in weight ratio (d2 / d1) = 0.5 / 9.5 PGME having a concentration of 20% by weight of a reaction product obtained by reacting the derivative compound (d1) P-1M and the amine compound (d2) monoethanolamine at a weight ratio of (d2 / d1) = 0.1 / 9.9 A photosensitive siloxane resin composition (P-13) was obtained in the same manner as in Example 1 except that 3.999 g of the solution was used. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-13).
　実施例１４
　リン酸誘導体化合物（ｄ１）Ｐ－１Ｍとアミン化合物（ｄ２）モノエタノールアミンとの重量割合（ｄ２／ｄ１）＝０．５／９．５の反応物のＰＧＭＥ溶液の代わりに、事前にリン酸誘導体化合物（ｄ１）Ｐ－１Ｍとアミン化合物（ｄ２）モノエタノールアミンを（ｄ２／ｄ１）＝１／９の重量割合で反応させて得られた反応物の濃度２０重量％のＰＧＭＥ溶液３．９９９ｇを用いた以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－１４）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－１４）を用いて、実施例１と同様にして評価を行った。 Example 14
Phosphoric acid derivative compound (d1) P-1M and amine compound (d2) monoethanolamine in weight ratio (d2 / d1) = 0.5 / 9.5 Derivative compound (d1) P-1M and amine compound (d2) monoethanolamine were reacted at a weight ratio of (d2 / d1) = 1/9. A photosensitive siloxane resin composition (P-14) was obtained in the same manner as in Example 1 except that was used. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-14).
　実施例１５
　ポリシロキサン（Ａ－１）溶液の量を５．９６７ｇとし、（Ｅ）熱ラジカル発生剤としてジメチル２，２’－アゾビス（イソブチレート）０．０８０ｇを添加し、混合溶剤を、ＰＧＭＥ１．７９７ｇとＰＧＭＥＡ３．２００ｇとした以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－１５）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－１５）を用いて、実施例１と同様にして評価を行った。 Example 15
The amount of the polysiloxane (A-1) solution was 5.967 g, (E) 0.080 g of dimethyl 2,2′-azobis (isobutyrate) was added as a thermal radical generator, and the mixed solvent was PGME 1.797 g and PGMEA 3 A photosensitive siloxane resin composition (P-15) was obtained in the same manner as in Example 1 except that the amount was 200 g. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-15).
　実施例１６
　ポリシロキサン（Ａ－１）溶液の代わりにポリシロキサン（Ａ－２）溶液を用いた以外は実施例１５と同様に行い、感光性シロキサン樹脂組成物（Ｐ－１６）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－１６）を用いて、実施例１と同様にして評価を行った。 Example 16
A photosensitive siloxane resin composition (P-16) was obtained in the same manner as in Example 15 except that the polysiloxane (A-2) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-16).
　実施例１７
　ポリシロキサン（Ａ－１）溶液の代わりにポリシロキサン（Ａ－５）溶液を用いた以外は実施例１５と同様に行い、感光性シロキサン樹脂組成物（Ｐ－１７）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－１７）を用いて、実施例１と同様にして評価を行った。 Example 17
A photosensitive siloxane resin composition (P-17) was obtained in the same manner as in Example 15 except that the polysiloxane (A-5) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-17).
　実施例１８
　ポリシロキサン（Ａ－１）溶液の代わりにポリシロキサン（Ａ－６）溶液を用いた以外は実施例１５と同様に行い、感光性シロキサン樹脂組成物（Ｐ－１８）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－１８）を用いて、実施例１と同様にして評価を行った。 Example 18
A photosensitive siloxane resin composition (P-18) was obtained in the same manner as in Example 15 except that the polysiloxane (A-6) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-18).
　実施例１９
　ポリシロキサン（Ａ－１）溶液の量を５．９６７ｇとし、（Ｅ）熱ラジカル発生剤としてジメチル２，２’－アゾビス（イソブチレート）０．０８０ｇを添加し、混合溶剤をＰＧＭＥ１．７９７ｇとＰＧＭＥＡ３．２００ｇとした以外は実施例９と同様に行い、感光性シロキサン樹脂組成物（Ｐ－１９）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－１９）を用いて、実施例１と同様にして評価を行った。 Example 19
The amount of the polysiloxane (A-1) solution is 5.967 g, (E) 0.080 g of dimethyl 2,2′-azobis (isobutyrate) is added as a thermal radical generator, and the mixed solvent is PGME 1.797 g and PGMEA3. A photosensitive siloxane resin composition (P-19) was obtained in the same manner as in Example 9 except for 200 g. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-19).
　実施例２０
　ポリシロキサン（Ａ－１）溶液の量を５．９６７ｇとし、（Ｅ）熱ラジカル発生剤としてジメチル２，２’－アゾビス（イソブチレート）０．０８０ｇを添加し、混合溶剤を、ＰＧＭＥ１．７９７ｇとＰＧＭＥＡ３．２００ｇとした以外は実施例１０と同様に行い、感光性シロキサン樹脂組成物（Ｐ－２０）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－２０）を用いて、実施例１と同様にして評価を行った。 Example 20
The amount of the polysiloxane (A-1) solution was 5.967 g, (E) 0.080 g of dimethyl 2,2′-azobis (isobutyrate) was added as a thermal radical generator, and the mixed solvent was PGME 1.797 g and PGMEA 3 A photosensitive siloxane resin composition (P-20) was obtained in the same manner as in Example 10 except that the amount was 200 g. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-20).
　比較例１
　ポリシロキサン（Ａ－１）溶液の量を８．１６６ｇとし、（Ｄ）リン酸エステルアミン塩を添加せず、混合溶剤を、ＰＧＭＥ３．６７６ｇとＰＧＭＥＡ３．２００ｇとした以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－２１）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－２１）を用いて、実施例１と同様にして評価を行った。 Comparative Example 1
Example 1 except that the amount of the polysiloxane (A-1) solution was 8.166 g, (D) the phosphate ester amine salt was not added, and the mixed solvent was PGME 3.676 g and PGMEA 3.200 g. And a photosensitive siloxane resin composition (P-21) was obtained. Evaluation was performed in the same manner as in Example 1 by using the obtained photosensitive siloxane resin composition (P-21).
　比較例２
　（Ｄ）リン酸エステルアミン塩を添加せず、リン酸誘導体化合物（ｄ１）Ｐ－１ＭのＰＧＭＥ２０重量％溶液の量を３．９９９ｇとした以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－２２）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－２２）を用いて、実施例１と同様にして評価を行った
　比較例３
　アミン化合物（ｄ２）としてモノエタノールアミンの代わりに４級アンモニウムカチオンであるテトラエチルアンモニウムを用いた以外は実施例１と同様に行い、感光性シロキサン樹脂組成物（Ｐ－２３）を得た。得られた感光性シロキサン樹脂組成物（Ｐ－２３）を用いて、実施例１と同様にして評価を行った。 Comparative Example 2
(D) A photosensitive siloxane resin was prepared in the same manner as in Example 1 except that the phosphate ester amine salt was not added and the amount of the phosphoric acid derivative compound (d1) P-1M in 20% by weight of PGME was changed to 3.999 g. A composition (P-22) was obtained. The obtained photosensitive siloxane resin composition (P-22) was used for evaluation in the same manner as in Example 1. Comparative Example 3
A photosensitive siloxane resin composition (P-23) was obtained in the same manner as in Example 1 except that tetraethylammonium, which is a quaternary ammonium cation, was used as the amine compound (d2) instead of monoethanolamine. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive siloxane resin composition (P-23).
　比較例４
　ポリシロキサン（Ａ－１）溶液の代わりにアクリル樹脂（ａ）溶液６．１６７ｇを用いたた以外は実施例１と同様に行い、感光性アクリル樹脂組成物（Ｐ－２４）を得た。得られた感光性アクリル樹脂組成物（Ｐ－２４）を用いて、実施例１と同様にして評価を行った。 Comparative Example 4
A photosensitive acrylic resin composition (P-24) was obtained in the same manner as in Example 1 except that 6.167 g of the acrylic resin (a) solution was used instead of the polysiloxane (A-1) solution. Evaluation was performed in the same manner as in Example 1 using the obtained photosensitive acrylic resin composition (P-24).
　実施例１～２０、比較例１～４の組成を表２～４に、評価結果を表５に示す。 Tables 2 to 4 show the compositions of Examples 1 to 20 and Comparative Examples 1 to 4, and Table 5 shows the evaluation results.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　本発明の感光性シロキサン樹脂組成物を硬化して得られる硬化膜は、タッチパネルの保護膜などの各種ハードコート膜の他、タッチセンサー用絶縁膜、液晶や有機ＥＬディスプレイのＴＦＴ用平坦化膜、金属配線保護膜、絶縁膜、反射防止膜、光学フィルター、カラーフィルター用オーバーコート、柱材などに好適に用いられる。 Cured films obtained by curing the photosensitive siloxane resin composition of the present invention include various hard coat films such as touch panel protective films, insulating films for touch sensors, flattened films for TFTs of liquid crystals and organic EL displays, It is suitably used for metal wiring protective films, insulating films, antireflection films, optical filters, color filter overcoats, pillar materials, and the like.

Claims (14)

  1. （Ａ）ポリシロキサン、（Ｂ）光ラジカル重合開始剤、（Ｃ）多官能モノマーおよび（Ｄ）リン酸誘導体アミン塩を含有する感光性シロキサン樹脂組成物。 A photosensitive siloxane resin composition comprising (A) polysiloxane, (B) a photoradical polymerization initiator, (C) a polyfunctional monomer, and (D) a phosphoric acid derivative amine salt.
  2. 前記（Ｃ）リン酸誘導体アミン塩が下記一般式（１）で表される構造を有するリン酸誘導体化合物とアミン化合物の塩である請求項１記載の感光性シロキサン樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （上記一般式（１）中、Ｒ１はラジカル重合性基を有する１価の有機基を示す。Ｒ２は水素、炭素数１～２０のアルキル基またはラジカル重合性基を有する１価の有機基を示す。）     The photosensitive siloxane resin composition according to claim 1, wherein the (C) phosphoric acid derivative amine salt is a salt of a phosphoric acid derivative compound having a structure represented by the following general formula (1) and an amine compound.
    Figure JPOXMLDOC01-appb-C000001
     (In the general formula (1), R 1 represents a monovalent organic group having a radical polymerizable group. R 2 represents a monovalent organic group having hydrogen, an alkyl group having 1 to 20 carbon atoms, or a radical polymerizable group. Group.)
  3. 前記アミン化合物が下記一般式（２）で表される構造を有する請求項２記載の感光性シロキサン樹脂組成物。
    Figure JPOXMLDOC01-appb-C000002
     （上記一般式（２）中、Ｒ３はヒドロキシル基を含有する炭素数１～２０の１価の有機基を示す。Ｒ４およびＲ５はそれぞれ独立に水素、炭素数１～２０のアルキル基またはヒドロキシル基を有する炭素数１～２０の１価の有機基を示す。）     The photosensitive siloxane resin composition of Claim 2 in which the said amine compound has a structure represented by following General formula (2).
    Figure JPOXMLDOC01-appb-C000002
     (In the general formula (2), R 3 represents a monovalent organic group having 1 to 20 carbon atoms containing a hydroxyl group. R 4 and R 5 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms. Or a monovalent organic group having 1 to 20 carbon atoms and having a hydroxyl group.)
  4. 前記（Ａ）ポリシロキサンが少なくとも（ａ１）ラジカル重合性基および（ａ２）親水性基を有する請求項１～３のいずれか記載の感光性シロキサン樹脂組成物。 The photosensitive siloxane resin composition according to any one of claims 1 to 3, wherein the (A) polysiloxane has at least (a1) a radical polymerizable group and (a2) a hydrophilic group.
  5. 前記（Ａ）ポリシロキサンが（ａ１）ラジカル重合性基としてスチリル基を有する繰り返し単位を全繰り返し単位中２０～８５モル％含有する請求項４記載の感光性シロキサン樹脂組成物。 The photosensitive siloxane resin composition according to claim 4, wherein the (A) polysiloxane contains (a1) 20 to 85 mol% of repeating units having a styryl group as a radical polymerizable group in all repeating units.
  6. 前記（Ａ）ポリシロキサンが（ａ２）親水性基としてカルボキシル基および／またはカルボン酸無水物基を有する請求項４または５記載の感光性シロキサン樹脂組成物。 The photosensitive siloxane resin composition according to claim 4 or 5, wherein the (A) polysiloxane has (a2) a carboxyl group and / or a carboxylic anhydride group as a hydrophilic group.
  7. さらに（Ｅ）熱ラジカル発生剤を含む、請求項６記載の感光性シロキサン樹脂組成物。 The photosensitive siloxane resin composition according to claim 6, further comprising (E) a thermal radical generator.
  8. 請求項１～７のいずれか記載の感光性シロキサン樹脂組成物の硬化物からなる硬化膜。 A cured film comprising a cured product of the photosensitive siloxane resin composition according to any one of claims 1 to 7.
  9. 請求項８記載の硬化膜を基材上に有する積層体。 A laminate having the cured film according to claim 8 on a substrate.
  10. 前記基材が金属配線を有する請求項９記載の積層体。 The laminate according to claim 9, wherein the substrate has metal wiring.
  11. 前記金属配線がモリブデン、チタン、クロム、銅および／または銀を含有する請求項１０記載の積層体。 The laminate according to claim 10, wherein the metal wiring contains molybdenum, titanium, chromium, copper and / or silver.
  12. 請求項９～１１のいずれか記載の積層体を有するタッチパネル用部材。 A touch panel member comprising the laminate according to any one of claims 9 to 11.
  13. 前記積層体中の硬化膜が層間絶縁膜である請求項１２記載のタッチパネル用部材。 The member for touchscreens of Claim 12 whose cured film in the said laminated body is an interlayer insulation film.
  14. 請求項１～７のいずれか記載の感光性シロキサン樹脂組成物を基材上に塗布する工程および塗布膜を８０～１５０℃で加熱する工程をこの順に含む積層体の製造方法。 A method for producing a laminate comprising the steps of applying the photosensitive siloxane resin composition according to any one of claims 1 to 7 on a substrate and heating the coating film at 80 to 150 ° C in this order.
PCT/JP2018/007150 2017-03-15 2018-02-27 Photosensitive siloxane resin composition, cured film and member for touch panels WO2018168435A1 (en)

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