WO2009113459A1 - Composition de polyorganosiloxane photosensible - Google Patents

Composition de polyorganosiloxane photosensible Download PDF

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Publication number
WO2009113459A1
WO2009113459A1 PCT/JP2009/054320 JP2009054320W WO2009113459A1 WO 2009113459 A1 WO2009113459 A1 WO 2009113459A1 JP 2009054320 W JP2009054320 W JP 2009054320W WO 2009113459 A1 WO2009113459 A1 WO 2009113459A1
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WIPO (PCT)
Prior art keywords
polyorganosiloxane
group
general formula
photosensitive
mass
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PCT/JP2009/054320
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English (en)
Japanese (ja)
Inventor
正志 木村
竜也 平田
Original Assignee
旭化成イーマテリアルズ株式会社
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Application filed by 旭化成イーマテリアルズ株式会社 filed Critical 旭化成イーマテリアルズ株式会社
Priority to JP2010502793A priority Critical patent/JP5199336B2/ja
Priority to CN200980108251.9A priority patent/CN101965542B/zh
Publication of WO2009113459A1 publication Critical patent/WO2009113459A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • G03F7/004—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
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers

Definitions

  • the present invention relates to the formation of surface protection films, interlayer insulating films, ⁇ -ray shielding films, etc. in insulating materials for electronic components and semiconductor devices, and photosensitive devices used in semiconductor devices equipped with image sensors, micromachines, or microactuators.
  • the present invention relates to a conductive polyorganosiloxane composition, a semiconductor device manufactured using the same, and the like.
  • Polyimide resins having excellent heat resistance, electrical properties, and mechanical properties are widely used for insulating materials for electronic parts, and surface protection films, interlayer insulation films, and ⁇ -ray shielding films for semiconductor devices.
  • This polyimide resin is usually provided in the form of a photosensitive polyimide precursor composition, which is applied to a substrate, soft baked, irradiated with actinic rays (exposure) through a desired patterning mask, and developed. And it has the characteristic that the hardening relief pattern which consists of a heat resistant polyimide resin can be formed easily by performing a thermosetting process. (For example, refer to Patent Document 1.)
  • Patent Document 2 discloses a photosensitive siloxane-based material that can be cured at a low temperature and has a small volume shrinkage during the heat curing process.
  • the surface of an electronic component or a semiconductor device is disclosed. Realizing performance that can stably form protective films, interlayer insulation films, ⁇ -ray shielding films, etc., such as applicability to various base materials, adhesion to underlying base materials, and mechanical properties at a practical level difficult.
  • the material disclosed in Patent Document 2 remains tacky and fluid even after being applied on a base material and then subjected to soft baking such as that performed with a conventional polyimide precursor composition. . Therefore, it is essential to keep the substrate level in order to prevent contamination of the device due to contact between the coated substrate and the device being transported, and to prevent the coating film from flowing on the substrate. It is undeniable that new constraints will be generated.
  • a semiconductor device in which an element having an optical function or a mechanical function is mounted in an integrated circuit or separately from it is put into practical use.
  • an element such as a transistor on a crystal substrate such as silicon using a conventionally known semiconductor process
  • an element (microstructure) having a function corresponding to the purpose of the semiconductor device is formed, It is manufactured by packaging these together.
  • a packaging technique for example, in Patent Document 3 below, a microstructure formed on a crystal substrate on which an integrated circuit is formed, a package material for covering the microstructure, A semiconductor device having a spacer for supporting the package material on the microstructure and an example thereof are disclosed in detail.
  • Patent Document 3 can be suitably used for various sensors such as microlens arrays and chemical sensors, or a wide range of semiconductor devices such as surface acoustic wave devices.
  • a spacer also expressed as a dam or a partition
  • the following three points can be considered as characteristics required for the spacer.
  • this spacer should be formed only in a portion necessary as a support, it is advantageous that the spacer itself is formed of a photosensitive member. This is because, if the spacer itself has photosensitivity, the latter can be omitted from the lithography process and the etching process that are usually used to leave the spacer only in a necessary portion.
  • a member having low heat resistance for example, an adhesive such as an epoxy resin, is used around the spacer, and the microstructure located under the spacer does not necessarily have high heat resistance. Therefore, secondly, it can be said that the process of forming the spacer is more preferable as the temperature is lower.
  • the spacer forms a closed space containing a microstructure, and if the description of Patent Document 3 is cited, it forms a “cavity”, so that the volatile components contained therein after the package is completed, etc. Is not preferred. That is, this spacer is required to be a low volatile component. Although it is considered that the above-described characteristics are required for the spacer, Patent Document 3 does not disclose a specific member suitably used for the spacer.
  • Problems to be solved by the present invention include the formation of surface protection films, interlayer insulation films, ⁇ -ray shielding films, etc. in recent electronic component insulation materials and semiconductor devices, and mounting image sensors, micromachines, or microactuators.
  • Requirements for resin compositions used in semiconductor devices and the like that is, excellent coating properties to various substrates and photosensitive properties, can be cured at a low temperature of 250 ° C. or less, and are volatile at 150 ° C. (Reduction rate) and volume shrinkage at 180 ° C. (remaining film ratio after curing) are small, and a soft bake film (hereinafter simply referred to as “soft bake film”) obtained by coating and soft baking the composition. It is to provide a photosensitive polyorganosiloxane composition that can reduce the tackiness of (ii).
  • the inventors of the present invention include a 5- or 6-membered nitrogen atom-containing heterocyclic group containing no photopolymerizable carbon-carbon double bond (including those having no aromaticity).
  • a 5- or 6-membered nitrogen atom-containing heterocyclic group containing no photopolymerizable carbon-carbon double bond including those having no aromaticity.
  • the present invention is the following [1] to [19]:
  • [1] Photosensitive polyorganosiloxane composition containing the following component (a) and component (b): (A) 100 parts by mass of polyorganosiloxane, wherein the polyorganosiloxane has the following general formula (1): ⁇ Wherein R is a monovalent group having 6 to 18 carbon atoms containing at least one aromatic group, and may be the same or different.
  • the catalyst is at least one metal alkoxide selected from the group consisting of a metal alkoxide represented by the general formula (4) and a metal alkoxide represented by the general formula (5).
  • the photosensitive polyorganosiloxane composition according to any one of [3] to [3].
  • the catalyst is at least one catalyst selected from the group consisting of a metal alkoxide represented by the general formula (4), a metal alkoxide represented by the general formula (5), and Ba (OH) 2 ;
  • a method for forming a polyorganosiloxane film comprising a step of applying the photosensitive polyorganosiloxane composition according to any one of [1] to [9] onto a substrate.
  • a step of forming a polyorganosiloxane film on a substrate by the method described in [10] above, a step of irradiating the film with an actinic ray through a patterning mask and photocuring an exposed portion, and using a developer A method for forming a polyorganosiloxane cured relief pattern, comprising: removing an uncured portion of the film; and heating the whole substrate.
  • a microstructure formed on a crystal substrate on which an integrated circuit is formed, a package material for covering the microstructure, and a spacer material for supporting the package material on the microstructure A semiconductor device in which the spacer material is the polyorganosiloxane cured relief pattern described in [12].
  • the photosensitive polyorganosiloxane composition of the present invention is excellent in applicability to various substrates, has a low soft bake film tackiness, has a volume shrinkage when cured at 180 ° C., and a soaking weight loss rate at 150 ° C. Is low, can be cured at a low temperature of 250 ° C. or less, and has excellent photosensitivity.
  • the polyorganosiloxane is composed of at least one silanol compound represented by the following general formula (1), at least one alkoxysilane compound represented by the following general formula (2), and the following general formula.
  • the at least one alkoxysilane compound represented by (3) comprises a metal alkoxide represented by the following general formula (4), a metal alkoxide represented by the following general formula (5), and Ba (OH) 2. It is obtained by a method of mixing with at least one catalyst selected from the group and polymerizing without adding water.
  • R is a monovalent group having 6 to 18 carbon atoms containing at least one aromatic group, and may be the same or different.
  • R ′ is a 5- to 6-membered nitrogen atom-containing heterocyclic group that does not contain a photopolymerizable carbon-carbon double bond (including those having no aromaticity) and has 2 to 11 organic groups
  • R ′′ is a methyl group or an ethyl group, and both may be the same or different.
  • R ′ ′′ is a C 2-17 organic group including a photopolymerizable carbon-carbon double bond group
  • R ′′ ′′ is a methyl group or an ethyl group, They may be the same or different.
  • ⁇ , ⁇ Wherein M is silicon, germanium, titanium or zirconium, and R ′ ′′ ′′ is an alkyl group having 1 to 4 carbon atoms, which may be the same or different.
  • R ′′ ′′ ′′ is an alkyl group having 1 to 4 carbon atoms, which may be the same or different.
  • the said catalyst is at least 1 metal alkoxide selected from the group which consists of the said General formula (4) and the said General formula (5). Further, in the process of polymerizing the polyorganosiloxane without adding water, at least one alkali metal hydroxide selected from the group consisting of potassium hydroxide and sodium hydroxide may be mixed as the catalyst.
  • R is a group having 6 to 18 carbon atoms including at least one aromatic group. Specifically, the following structure: It is preferable that it is at least 1 group chosen from the group represented by these.
  • R ′ is a 5- to 6-membered nitrogen atom-containing heterocyclic group containing no photopolymerizable carbon-carbon double bond (having no aromaticity) And an organic group having 2 to 11 carbon atoms.
  • the compound represented by the general formula (2) does not include a group having a photopolymerizable carbon-carbon double bond.
  • R ′′ is a methyl group or an ethyl group, and both may be the same or different.
  • Specific examples of R ′ include the following structures: It is preferable that it is at least 1 group chosen from the group represented by these.
  • R ′ ′′ is an organic group having 2 to 17 carbon atoms including a group having a photopolymerizable carbon-carbon double bond
  • R ′′ ′′ Are methyl groups or ethyl groups, which may be the same or different.
  • Specific examples of R ′ ′′ include the following structures: It is preferable that it is at least 1 group chosen from the group represented by these.
  • the photosensitive polyorganosiloxane is represented by the general formula (3), at least one silanol compound represented by the general formula (1), at least one alkoxysilane compound represented by the general formula (2). And at least 1 selected from the group represented by the metal alkoxide represented by the general formula (4), the metal alkoxide represented by the general formula (5), and Ba (OH) 2. It is obtained by a method in which a seed catalyst (hereinafter sometimes simply referred to as “catalyst”) is mixed and polymerized without adding water.
  • a seed catalyst hereinafter sometimes simply referred to as “catalyst”
  • the metal alkoxide represented by the general formula (4) and the metal alkoxide represented by the general formula (5) catalyze a dealcoholization condensation reaction of a silanol compound (silanol group) and an alkoxysilane compound (alkoxysilyl group). , Itself behaves as an alkoxy group-containing compound and participates in the dealcoholization condensation reaction, and a part forms a polysiloxane or polysilsesquioxane structure in a form incorporated into the molecule.
  • the mixing ratio is basically that the silanol compound and the alkoxysilane compound are mixed at 1: 1 (molar ratio), and the alkoxysilane compound can be mixed at a ratio of 30 to 70 mol with respect to 50 mol of the silanol compound.
  • the tetravalent metal alkoxide represented by the general formula (4) when used as the metal alkoxide, the tetravalent metal alkoxide and the alkoxysilane compound are respectively converted at a molar ratio of 1: 2. It is preferable to replace (the amount of alkoxysilane compound is reduced by 2 mol for every 1 mol of the amount of tetravalent metal alkoxide mixed).
  • the trivalent metal alkoxide represented by the general formula (5) the trivalent metal alkoxide and the alkoxysilane compound are preferably converted at a molar ratio of 2: 3 and replaced.
  • Suitable silanol compounds include diphenyl silane diol, di-p-toluyl silane diol, di-p-styryl silane diol, dinaphthyl silane diol, etc., but in terms of price, availability, copolymerization and heat resistance, etc. In view of the above, diphenylsilanediol is particularly suitable.
  • N-trialkoxysilyl-1,2,4-triazole N-trialkoxysilylimidazole
  • N-trialkoxysilylpyrrole N-trialkoxysilylpyridine
  • N-trialkoxysilylpyrrolidine piperidinomethyltrialkoxysilane, 2-piperidinoethyltrialkoxysilane, 3-morpholinopropyltrialkoxysilane, 3-piperazinopropyltrialkoxysilane, 3-piperidinopropyltrialkoxysilane, 3- (4-methylpiperazinopropyl) tri Alkoxysilane, 3- (4-methylpiperidinopropyl) Trialkoxysilane, 4- (2-trialkoxysilyl-1,2,4-triazole, N-trialkoxysilylimidazole, N-trialkoxysilylpyrrole, N-trialkoxysilylpyridine, N-trialkoxysilylpyrrol
  • the present inventors have disclosed an alkoxysilane compound having a 5- to 6-membered nitrogen atom-containing heterocyclic group (including those having no aromaticity) that does not contain a photopolymerizable carbon-carbon double bond. It has been found that when used as a raw material for organosilane, the tackiness of the soft-baked film of the photosensitive polyorganosiloxane composition using the same is dramatically eliminated.
  • alkoxysilane compounds containing a photopolymerizable carbon-carbon double bond group include vinyltrimethoxysilane, vinyltriethoxysilane, 1-propenyltrimethoxysilane, 1-propenyltriethoxysilane, 2- Propenyltrimethoxysilane, 2-propenyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, p- Styryltrimethoxysilane, p-styryltriethoxysilane, p- (1-propenylphenyl) trimethoxysilane, p- (1-propenylphenyl) triethoxysilane, p- (2-propenyl) In order to obtain excellent
  • Propyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and 3-acryloyloxypropyltriethoxysilane are more preferable, and 3-methacryloyloxypropyltrimethoxy is considered in consideration of price, harmfulness, flexibility and high crosslinkability.
  • Silane is particularly preferred.
  • a polyorganosiloxane can be polymerized by appropriately mixing and heating the above-mentioned silanol compound, the above-mentioned two types of alkoxysilane compounds, and a catalyst.
  • the heating temperature and heating rate at this time are important parameters for controlling the degree of polymerization of the polyorganosiloxane to be produced.
  • the raw material mixture is heated to about 70 ° C. to 150 ° C. for polymerization.
  • the addition amount of the catalyst during the polymerization of the silanol compound is less than 2 mol%, the polymerization of the polyorganosiloxane may not sufficiently proceed when heated to the above preferable temperature range or more.
  • the silanol compound and the alkoxysilane compound are polymerized only by the action of potassium hydroxide or sodium hydroxide without adding the catalyst at the time of polymerization, it is avoided that a part of the polymer component having high crystallinity is generated. This is not preferable because it crystallizes and precipitates, resulting in white turbidity and precipitation, and the system becomes disproportionate. From the viewpoint of avoiding this “crystallization”, it is important to add the catalyst at the time of polymerization.
  • the lower limit of the addition amount of the catalyst is 0.1 mol% or more, more preferably 0.5 mol% or more with respect to the silanol compound, for the above reason.
  • the upper limit of the amount of catalyst added depends on the performance of the target polyorganosiloxane. In order to achieve excellent photosensitivity, the aforementioned alkoxysilane compound having a photopolymerizable carbon-carbon double bond is essential, and the upper limit of the polymerization addition amount of the metal alkoxide is calculated from the minimum required amount.
  • the amount is 30 mol% or less, more preferably 20 mol% or less, based on the silanol compound.
  • the ratio of the two alkoxysilane compounds used is important in achieving both the tack-removing effect of the soft bake film and the excellent photosensitive characteristics.
  • the silanol compound and the alkoxysilane compound are basically mixed at a 1: 1 (molar ratio), but of these, they do not contain a photopolymerizable carbon-carbon double bond.
  • the molar ratio of an alkoxysilane compound having a 6-membered nitrogen atom-containing heterocyclic group (including those having no aromaticity) and an alkoxysilane compound containing a photopolymerizable carbon-carbon double bond group is 70:30 to 30:70, and more preferably in the range of 60:40 to 40:60.
  • the molar ratio of the alkoxysilane compound containing a photopolymerizable carbon-carbon double bond group exceeds 30% of the total alkoxysilane compound, the excellent photosensitive properties expected by the present invention are achieved.
  • the molar ratio of the alkoxysilane compound having a 5- to 6-membered nitrogen atom-containing heterocyclic group (including those having no aromaticity) that does not contain a photopolymerizable carbon-carbon double bond is If it exceeds 30% of the silane compound, the tackiness of the soft-baked film of the photosensitive polyorganosiloxane composition can be reduced.
  • Photopolymerization initiator It is important to add a photopolymerization initiator to the photosensitive polyorganosiloxane composition for the purpose of imparting photosensitivity.
  • Photopolymerization initiators include the following: (1) Benzophenone derivatives such as benzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone, (2) 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl
  • the ⁇ -aminoalkylphenone compound (8) is more preferable particularly from the viewpoint of photosensitivity.
  • the addition amount is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to the component (a).
  • the addition amount is 0.1 parts by mass or more, light sufficient to allow photopolymerization to proceed sufficiently is supplied during exposure, and curing of the exposed part sufficiently proceeds, so that a practical relief pattern can be obtained.
  • the addition amount is 20 parts by mass or less, the exposure absorption near the surface of the coating film does not become too large, the exposure light beam reaches near the substrate surface, and the photopolymerization becomes uniform in the film thickness direction. A practical relief pattern can be obtained.
  • (C) Compound other than component (a) having two or more photopolymerizable unsaturated bond groups Photopolymerization for the purpose of improving film forming characteristics, photosensitive characteristics, and mechanical properties after curing (elongation after curing)
  • a compound other than the component (a) having two or more sex unsaturated bond groups can be added.
  • a polyfunctional (meth) acrylic acid ester compound that can be polymerized by the action of a photopolymerization initiator is preferable.
  • polyethylene glycol diacrylate [number of ethylene glycol units 2 to 20], polyethylene glycol diester, Methacrylate [number of ethylene glycol units 2-20], poly (1,2-propylene glycol) diacrylate [1,2-propylene glycol units number 2-20], poly (1,2-propylene glycol) dimethacrylate [1 , 2-Propylene glycol unit number 2 to 20], polytetramethylene glycol diacrylate [tetramethylene glycol unit number 2 to 10], polytetramethylene glycol dimethacrylate [tetramethylene glycol unit number 2 to 1] ], 1,4-cyclohexanediacrylate, 1,4-cyclohexanedimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate [number of ethylene glycol units 2 to 20
  • one or more compounds selected from the group consisting of ethoxylated bisphenol A dimethacrylate [ethylene glycol unit number 4 to 30] and polytetramethylene glycol dimethacrylate [tetramethylene glycol unit number 2 to 10] are preferable.
  • Ethoxylated bisphenol A dimethacrylate [number of ethylene glycol units 4 to 30] is represented by the following formula: As an example, Blemmer PDBE-200, 250, 450, 1300 manufactured by Nippon Oil & Fats Co., Ltd. represented by ⁇ wherein q + r ⁇ 4 to 30 ⁇ is given.
  • polytetramethylene glycol dimethacrylate those having a tetramethylene glycol unit number of 5 to 10 are preferable.
  • Bremer PDT-650 manufactured by Nippon Oil & Fats Co., Ltd. represented by ⁇ wherein s ⁇ 8 ⁇ is given.
  • PDBE-450, PDBE-1300, and PDT-650 are particularly preferable.
  • the addition amount is preferably 1 to 100 parts by mass, and more preferably 5 to 50 parts by mass with respect to the component (a). If the addition amount is 100 parts by mass or less, it is preferable because the stability of the resin liquid is high and quality variation is small.
  • silicone resin can be added to the photosensitive polyorganosiloxane composition for the purpose of further reducing tackiness and improving fluidity of the soft-baked film.
  • the silicone resin is, for example, “organosilane compound having 2 to 4 hydrolyzable groups such as alkoxysilyl group and chlorosilyl group” described in “Silicone Handbook” (1990) published by Nikkan Kogyo Shimbun. It is a “polymer having a three-dimensional network structure obtained by cohydrolyzing and polymerizing”.
  • the component (a) does not correspond to the (c) silicone resin.
  • a so-called straight silicone resin such as methyl, phenyl, phenylmethyl, phenylethyl, or phenylpropyl.
  • methylsilicone resins such as KR220L, KR242A, KC89, KR400, KR500 (manufactured by Shin-Etsu Chemical Co., Ltd.), 217 flakes (manufactured by Dow Corning Toray), SR-20, SR-21 (manufactured by Konishi Chemical Industries, Ltd.).
  • Phenyl silicone resins such as KR213, KR9218 (manufactured by Shin-Etsu Chemical Co., Ltd.), 220 flakes, 223 flakes, 249 flakes (manufactured by Dow Corning Toray), SR-23 (Konishi Chemical) And the like, and phenylpropyl silicone resins such as Z-6018 (manufactured by Dow Corning Toray).
  • a silicone resin having a higher crosslinking density and a solid in a normal temperature range More preferably, an ethyl or phenylpropyl silicone resin is selected. Specifically, among the above, 217 flakes, SR-20, SR-21, SR-23, Z-6018 and the like are particularly preferable. These may be used singly or may be used in combination as appropriate.
  • the amount of silicone resin added is preferably 50 to 200 parts by mass relative to the component (a). From the viewpoint of tackiness and fluidity, 50 parts by mass or more is preferable, and from the viewpoint of photosensitive characteristics such as i-line photosensitivity, 200 parts by mass or less is preferable.
  • Organosilicon compound An organosilicon compound can be added to the photosensitive polyorganosiloxane composition for the purpose of improving adhesion to various substrates. (However, the following organic silicon compound containing a carboxyl group is excluded.) Examples of the organic silicon compound include the following.
  • alkoxy represents a methoxy group or an ethoxy group.
  • the addition amount is preferably 0 to 20 parts by mass with respect to the component (a) of the present invention from the viewpoint of the stability of the composition. More preferably, it is 0.1 to 15% by mass, and further preferably 3 to 10% by mass.
  • the photosensitive polyorganosiloxane composition has a polyvalent thiol compound having two or more thiol groups for the purpose of improving applicability (wetability) on various substrates as desired. Can be added.
  • polyvalent thiol compound examples include the following: (1) Divalent thiol compound 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, 2,3-dihydroxy-1,4-butanedithiol, 3,6-dioxa-1,8-octanedithiol, 3,7-dithia-1,9- Nonanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 2,3-diamino-1,4-benzenedithiol, 4,5-dimethyl-O-xylenedithiol, toluene 3,4-dithiol, 4,4'-biphen
  • the addition amount is preferably 1 to 50 parts by mass, and more preferably 10 to 30 parts by mass with respect to the component (a).
  • the addition amount is preferably 1 part by mass or more from the viewpoint of applicability (wetability) on various substrates, and is preferably 50 parts by mass or less from the viewpoint of heat resistance.
  • the photosensitive polyorganosiloxane composition may have the following general formula (6) for the purpose of improving applicability (wettability) on various substrates, if desired.
  • h is an integer of 1 or 2
  • Xa is a divalent aromatic group
  • h is a tetravalent aromatic group
  • Xc is a divalent organic group containing a carbon atom directly bonded to a silicon atom
  • d is an integer of 1 to 3
  • Re and Rf are alkyl groups of 1 to 4 carbon atoms, and the same Or may be different
  • g is 0, 1 or 2
  • Rb is a hydrogen atom or a monovalent hydrocarbon group.
  • An organosilicon compound containing a carboxyl group can be added.
  • the carboxyl group-containing organosilicon compound represented by the general formula (6) can be obtained by reacting a dicarboxylic anhydride or a tetracarboxylic dianhydride derivative with an organosilicon compound containing an amino group. it can.
  • Various structures can be used as the dicarboxylic acid anhydride or tetracarboxylic dianhydride derivative.
  • phthalic anhydride and benzophenone tetracarboxylic dianhydride are particularly suitable.
  • the organosilicon compound containing an amino group to be reacted with a dicarboxylic acid anhydride or a tetracarboxylic dianhydride derivative can be used in various structures, and examples thereof include the following (hereinafter referred to as alkoxy notation): Represents a methoxy group or an ethoxy group).
  • the addition amount is preferably 0.05 to 20 parts by mass, and preferably 1 to 10 parts by mass with respect to the component (a). More preferred. From the viewpoint of applicability (wettability) on various substrates, the amount added is preferably 0.05 parts by mass or more, and from the viewpoint of storage stability of the photosensitive polyorganosiloxane composition, it is preferably 20 parts by mass or less. In using these, it may be individual or a mixture of two or more.
  • Nonionic surfactant A nonionic surfactant is added to the photosensitive polyorganosiloxane composition as desired for the purpose of improving applicability (wetability) on various substrates. be able to.
  • As the surfactant it is preferable to add a nonionic surfactant as compared with an ionic surfactant from the viewpoint of preventing corrosion of the wiring metal.
  • Preferred nonionic surfactants include the following compounds: (1) Ether type polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polycyclic phenyl ether, polyoxypropylene alkyl ether, (2) Ester ether type polyoxyethylene glyceryl ether fatty acid ester, polyoxyethylene hydrogenated castor oil fatty acid ester, (3) Ester type Polyethylene glycol fatty acid ester, polyoxyethylene trimethylolpropane fatty acid ester, (4) Silicone surfactant dimethylsiloxane ethyleneoxy graft compound, dimethylsiloxane propyleneoxy graft compound, (hydroxyethyleneoxypropyl) methylsiloxane-dimethylsiloxane compound, (5) Fluorosurfactant Perfluoroalkyl carboxylic acid, perfluoroalkyl sulfonic acid, perfluoroalkyl group-containing oligomer (manufactured by Dainippon Ink
  • the addition amount is preferably 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (a). Is more preferable.
  • the addition amount is preferably 0.01 parts by mass or more from the viewpoint of improving applicability to various base materials, and the addition amount is preferably 10 parts by mass or less from the viewpoint of suppressing development residue residue, pattern lifting and peeling in lithography.
  • the photosensitive polyorganosiloxane composition can be adjusted by arbitrarily adding a solvent to adjust the viscosity.
  • Suitable solvents include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, tetrahydrofuran, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclohexane Pentanone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, tetramethyl urea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone , Methyl isobutyl ketone, anisole, ethyl acetate,
  • solvents can be appropriately added to the photosensitive polyorganosiloxane composition according to the coating film thickness and viscosity, but are preferably used in the range of 5 to 120 parts by mass with respect to the component (a).
  • a sensitizer for improving photosensitivity can be added to the photosensitive polyorganosiloxane composition as desired.
  • sensitizers include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylamino).
  • a polymerization inhibitor can be added to the photosensitive polyorganosiloxane composition for the purpose of improving the viscosity during storage and the stability of photosensitivity.
  • examples of such polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid.
  • 2,6-di-tert-butyl-p-methylphenol 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N- Ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt ,Screw Or the like can be used 4-hydroxy-3,5-di-tert- butyl) phenyl methane.
  • the addition amount is preferably 0.001 to 5 parts by mass, and more preferably 0.01 to 1 part by mass with respect to the component (a).
  • the photosensitive polyorganosiloxane composition includes an ultraviolet absorber, a coating film smoothness imparting agent, etc., as long as it does not inhibit various characteristics of the photosensitive polyorganosiloxane composition.
  • Various additives can be appropriately blended.
  • the suitable example of the method of forming a hardening relief pattern using the photosensitive polyorganosiloxane composition of this invention is shown below.
  • the composition is applied on various desired base materials in addition to a silicon wafer, a ceramic substrate, an aluminum substrate, and the like.
  • a spin coater, a die coater, a spray coater, dipping, printing, a blade coater, roll coating, or the like can be used as the coating apparatus or coating method.
  • the coated substrate is soft baked at 80 to 200 ° C.
  • a soft baked film having a thickness of 10 to 100 microns, for example, using an exposure projection apparatus such as a contact aligner, mirror projection, or stepper. Actinic rays are irradiated through a desired photomask.
  • X-rays, electron beams, ultraviolet rays, visible rays and the like can be used as the actinic rays, but in the present invention, those having a wavelength of 200 to 500 nm are preferably used.
  • the light source wavelength is particularly preferably UV-i ray (365 nm), and the aligner or stepper is particularly preferable as the exposure projection apparatus.
  • post-exposure baking PEB with any combination of temperature and time (preferably temperature 40 ° C. to 200 ° C., time 10 seconds to 360 seconds), if necessary, for the purpose of improving photosensitivity, A pre-development bake may be applied.
  • the good solvent of the photosensitive polyorganosiloxane composition of this invention can be used individually or by mixing a good solvent and a poor solvent suitably.
  • Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, ⁇ -acetyl-gammabutyrolactone, cyclopenta
  • N-methyl-2-pyrrolidone N-acetyl-2-pyrrolidone
  • N, N-dimethylacetamide N, N-dimethylformamide
  • dimethyl sulfoxide gamma butyrolactone, ⁇ -acetyl-gammabutyrolactone
  • cyclopenta Non, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone and the like are used as the poor solvent, and m
  • the film is washed with a rinse solution, and the developer solution is removed to obtain a coating film with a relief pattern.
  • a rinse solution As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, isobutyl alcohol, propylene glycol monomethyl ether, or the like can be used alone or in an appropriate mixture, or can be used in a stepwise combination.
  • the relief pattern thus obtained is converted into a cured relief pattern at a curing temperature of 150 to 250 ° C., which is much lower than the conventional polyimide precursor composition.
  • This heat curing can be performed using a hot plate, an inert oven, a temperature rising oven in which a temperature program can be set, and the like. Air may be used as the atmospheric gas for heat curing, and an inert gas such as nitrogen or argon may be used as necessary.
  • the above-mentioned cured relief pattern is applied between a micro structure such as a surface protective film, an interlayer insulating film, an ⁇ -ray shielding film, and a micro lens array of a semiconductor device formed on a substrate such as a silicon wafer and the package material.
  • a micro structure such as a surface protective film, an interlayer insulating film, an ⁇ -ray shielding film, and a micro lens array of a semiconductor device formed on a substrate such as a silicon wafer and the package material.
  • Various semiconductor devices including an optical element such as a CMOS image sensor are used as any one selected from the group consisting of the supports (partition walls) and other processes are applied to a known semiconductor device manufacturing method. Can be manufactured.
  • the electronic component and semiconductor device which have the coating film which consists of resin which hardened the photosensitive polyorganosiloxane composition mentioned above can be obtained.
  • a semiconductor device can be formed using a cured relief pattern of the photosensitive polyorganosiloxane composition of the present invention as the spacer material.
  • specific examples of the integrated circuit include an integrated circuit using a crystal substrate including silicon, lithium niobate, lithium tartrate, or quartz, and an integrated circuit including a photodiode.
  • a microstructure means a micron-sized mechanical, photomechanical, or electromechanical device. Specifically, a microlens is mentioned.
  • the packaging material is preferably transparent and may be formed of glass.
  • the photosensitive polyorganosiloxane composition of the present invention is applied directly or via a thin film layer on a microstructure formed on a crystal substrate on which an integrated circuit is formed.
  • a step of forming a film, a step of irradiating the coating film with an actinic ray through a patterning mask having an opening only in a portion where the spacer material is to be formed, and photocuring the exposed portion, and the coating film using a developer The manufacturing method which includes the process of removing the uncured part of this, and the process of heating a coating film with this base material is mentioned. Each process can be performed by the above-mentioned method.
  • Example 1 (Preparation of photosensitive polyorganosiloxane composition C-1) 100 parts by mass of polyorganosiloxane POS-1 obtained in Synthesis Example 1, 4 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4,4′- 0.4 parts by mass of bis (diethylamino) benzophenone, 30 parts by mass of ethoxylated bisphenol A dimethacrylate [number of ethylene glycol units 30; PDBE-1300 manufactured by NOF Corporation], 15 parts by mass of 3-methacryloxypropyltrimethoxysilane 150 parts by mass of silicone resin (Toray Dow Corning 217 flakes) and 40 parts by mass of N-methyl-2-pyrrolidone were weighed and mixed, and filtered through a Teflon (registered trademark) filter having a pore size of 0.2 microns.
  • a varnish-like photosensitive polyorganosiloxane composition C-1 was
  • Example 2 (Preparation of photosensitive polyorganosiloxane composition C-2) A varnish-like photosensitive polyorganosiloxane composition C-2 was obtained in the same manner as in Example 1 except that 150 parts by mass of SR-20 manufactured by Konishi Chemical was used as the silicone resin.
  • Example 3 (Preparation of photosensitive polyorganosiloxane composition C-3) 100 parts by mass of polyorganosiloxane POS-2 obtained in Synthesis Example 2, 4 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4,4′- 0.4 parts by mass of bis (diethylamino) benzophenone, 30 parts by mass of polytetramethylene glycol dimethacrylate (tetramethylene glycol unit number 8 PDT-650 manufactured by NOF Corporation), 15 parts by mass of 3-methacryloxypropyltrimethoxysilane, 150 parts by mass of silicone resin (Toray Dow Corning 217 flakes) and 40 parts by mass of N-methyl-2-pyrrolidone were weighed and mixed, and filtered through a Teflon (registered trademark) filter having a pore size of 0.2 microns.
  • a varnish-like photosensitive polyorganosiloxane composition C-3 was obtained
  • Example 4 (Preparation of photosensitive polyorganosiloxane composition C-4) A varnish-like photosensitive polyorganosiloxane composition C-4 was obtained in the same manner as in Example 1 except that POS-3 of Synthesis Example 3 was used as the polyorganosiloxane.
  • Example 5 (Preparation of photosensitive polyorganosiloxane composition C-5) A varnish-like photosensitive polyorganosiloxane composition C-5 was obtained in the same manner as in Example 1 except that POS-4 of Synthesis Example 4 was used as the polyorganosiloxane.
  • Example 6 (Preparation of photosensitive polyorganosiloxane composition C-6) A varnish-like photosensitive polyorganosiloxane composition C-6 was obtained in the same manner as in Example 1 except that POS-5 of Synthesis Example 5 was used as the polyorganosiloxane.
  • Example 7 (Preparation of photosensitive polyorganosiloxane composition C-7) A varnish-like photosensitive polyorganosiloxane composition C-7 was obtained in the same manner as in Example 1 except that POS-6 of Synthesis Example 6 was used as the polyorganosiloxane.
  • Example 8 (Preparation of photosensitive polyorganosiloxane composition C-8) A varnish-like photosensitive polyorganosiloxane composition C-8 was obtained in the same manner as in Example 1 except that POS-9 of Synthesis Example 9 was used as the polyorganosiloxane.
  • Example 9 (Preparation of photosensitive polyorganosiloxane composition C-9) A varnish-like photosensitive polyorganosiloxane composition C-9 was obtained in the same manner as in Example 1 except that POS-11 of Synthesis Example 11 was used as the polyorganosiloxane.
  • Example 10 (Preparation of photosensitive polyorganosiloxane composition C-10) A varnish-like photosensitive polyorganosiloxane composition C-10 was obtained in the same manner as in Example 1 except that POS-12 of Synthesis Example 12 was used as the polyorganosiloxane.
  • Example 11 (Preparation of photosensitive polyorganosiloxane composition C-11) A varnish-like photosensitive polyorganosiloxane composition C-11 was obtained in the same manner as in Example 1 except that POS-10 of Synthesis Example 10 was used as the polyorganosiloxane.
  • Example 12 (Preparation of photosensitive polyorganosiloxane composition C-12) 100 parts by mass of polyorganosiloxane POS-1 obtained in Synthesis Example 1, 4 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4,4′- 0.4 parts by mass of bis (diethylamino) benzophenone and 40 parts by mass of N-methyl-2-pyrrolidone are weighed and mixed, filtered through a Teflon (registered trademark) filter with a pore size of 0.2 microns, and varnish-like photosensitive. Polyorganosiloxane composition C-12 was obtained.
  • Teflon registered trademark
  • This resin film is cut to a width of 3.0 mm using a dicing saw (manufactured by Disco, model name DAD-2H / 6T), immersed in a 10% hydrochloric acid aqueous solution and peeled off from the silicon wafer, and a strip-shaped film sample It was.
  • This film sample was allowed to stand in an atmosphere of 23 ° C. and 55% RH for 24 hours, and then subjected to a tensile test using a Tensilon tensile tester based on ASTM D-882-88 to evaluate the elongation.
  • the results are shown in Table 2 below.
  • Comparative Example 1 is a case where only sodium hydroxide is used as a catalyst during the polymerization of polyorganosiloxane, but the system becomes cloudy during the polymerization, whereby the varnish composition cannot be filtered and is not practical.
  • Comparative Example 2 a 5- to 6-membered nitrogen atom-containing heterocyclic group containing no photopolymerizable carbon-carbon double bond in the polyorganosiloxane structure (including those having no aromaticity) is used.
  • Comparative Example 3 and Comparative Example 4 include a 5- to 6-membered nitrogen atom-containing heterocyclic group containing no photopolymerizable carbon-carbon double bond in the structure of the polyorganosiloxane (including those having no aromaticity). .) And is not a case where the silicone resin, which is one of the requirements of the present invention, is added to the photosensitive polyorganosiloxane composition. As a matter of course, the examples of the present invention Also, it is inferior to Comparative Example 2.
  • Example 13 (Preparation of photosensitive polyorganosiloxane composition C-17)
  • 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H)- Trion) (Karenz MT NR1 manufactured by Showa Denko KK) was weighed and mixed with 25 parts by mass, filtered through a Teflon (registered trademark) filter having a pore size of 0.2 microns, and a varnish-like photosensitive polyorganosiloxane composition.
  • C-15 was obtained.
  • Example 14 (Preparation of carboxyl group-containing organosilicon compound S-1 solution) A 1 L round bottom flask was charged with 29.6 g (0.2 mol) of phthalic anhydride and 195 g of N-methyl-2-pyrrolidone, and stirring was started. The solution was cooled to 0 ° C., and a solution of 44.2 g (0.2 mol) of 3-aminopropyltriethoxysilane in 100 g of N-methyl-2-pyrrolidone was added. This was returned to room temperature and stirred for 4 hours to obtain an N-methyl-2-pyrrolidone solution containing 20 wt% of carboxyl group-containing organosilicon compound S-1. The structure of S-1 is shown below.
  • Example 15 (Preparation of photosensitive polyorganosiloxane composition C-19)
  • a nonionic surfactant (trade name: PolyFox product number PF-656, manufactured by OMNOVA Solutions, Inc.) represented by formula (1) is filtered through a Teflon (registered trademark) filter having a pore size of 0.2 microns, and then varnished.
  • a polyorganosiloxane composition C-19 was obtained.
  • the photosensitive polyorganosiloxane compositions C-1, C-17, C-18, and C-19 obtained in Examples 13 to 15 of the present invention and Comparative Example 1 were compared with a spin coater (Tokyo Electron).
  • Application spin coating
  • edge cutting edge rinsing
  • initial film thickness A 45 micron coating was obtained.
  • the outer periphery of the wafer on which this coating film was formed was observed, the distance from the wafer edge to the outermost periphery of the coating film was measured, and the coating property (wetting property) was evaluated.
  • Examples 13 to 15 of the present invention it is possible to obtain a photosensitive polyorganosiloxane composition that is more excellent in coatability (wetting property) on the substrate than in Comparative Example 1 of the present invention.
  • the evaluation of tack property, photosensitive property, low temperature curing property, low volatility, and volume shrinkage of the pre-baked films of Examples 13 to 15 was the same as that of Example 1.
  • the photosensitive polyorganosiloxane composition of the present invention is equipped with an image sensor, a micromachine, or a microactuator for forming an insulating material for an electronic component, a surface protective film, an interlayer insulating film, an ⁇ -ray shielding film, etc. in a semiconductor device. It can be suitably used as a semiconductor device or the like and a resin composition used for forming the semiconductor device.

Abstract

L'invention porte sur une composition de polyorganosiloxane photosensible comprenant un composant (a) : 100 parties en masse d'un polyorganosiloxane dans lequel le polyorganosiloxane a été obtenu par mélange d'un composé de silanol représenté par la formule générale (1) : R2Si(OH)2, un composé alcoxysilane représenté par la formule générale (2) : R'Si(OR'')3 et un composé alcoxysilane représenté par la formule générale (3) : R'''Si(OR'''')3 dans une plage de rapports molaires spécifique avec un catalyseur sélectionné dans le groupe constitué par des alcoxydes de métal représentés par la formule générale (4) : M(OR''''')4, des alcoxydes de métal représentés par la formule générale (5) : M'(OR'''''')3 et Ba(OH)2 et polymérisation du mélange sans l'addition d'eau, et un composant (b) : 0,1 à 20 parties en masse d'un initiateur de photopolymérisation. Les groupes dans les formules générales (1) à (5) sont tels que définis dans les revendications.
PCT/JP2009/054320 2008-03-10 2009-03-06 Composition de polyorganosiloxane photosensible WO2009113459A1 (fr)

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CN108137976A (zh) * 2015-08-19 2018-06-08 耶路撒冷希伯来大学伊森姆研究发展有限公司 3d可聚合陶瓷油墨
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