Photocurable resin composition, cured product thereof, permanent film, and method for producing permanent film

Abstract

To provide a photocurable resin composition having high fluidity and giving a cured product exhibiting high heat resistance.SOLUTION: (A) a photocurable organopolysiloxane having a hydrolyzable group represented by the following general formula (A1), (B) inorganic fine particles, and (C) a photopolymerization initiator, wherein in the general formula (A1), R11 is a single bond or a divalent organic group, Y is a carbon-carbon unsaturated bond-containing group, and * represents a bonding position with a silicone atom of the organopolysiloxane. ).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photocurable resin composition, a cured product thereof, a permanent film, and a method for producing the permanent film. [Background technology]

[0002] Nanoimprinting is an advanced version of the embossing technique well known for optical disc manufacturing. It involves pressing a mold with a concave-convex pattern into a resin, mechanically deforming it, to precisely transfer a fine pattern. Photo-nanoimprinting, in particular, is a technique in which light is irradiated through a transparent mold or transparent substrate to photo-cure a photocurable composition, resulting in transfer. Because it enables imprinting at room temperature, it is expected to improve dimensional stability and throughput.

[0003] One of the materials to which nanoimprinting can be applied is permanent film for semiconductor devices. Unlike etching resists used as processing materials, permanent films are materials that remain as insulating layers on semiconductor devices, storage media, etc. Therefore, nanoimprint compositions for permanent films are required to have fluidity and pattern formability in a solvent-free state, as well as heat resistance, such as durability to high-temperature annealing and evaluation of film shrinkage rates before and after heat treatment, for the cured film formed after imprinting.

[0004] As nanoimprint compositions for permanent films, compositions have been proposed in which inorganic particles such as organosilica sol are blended with a monomer having a photopolymerizable group or a polymer having a photopolymerizable group (e.g., Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-177194 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-160284 Summary of the Invention [Problem to be solved by the invention]

[0006] When using a monomer with a photopolymerizable group in a nanoimprint composition, the monomer is highly volatile, posing the risk of contaminating peripheral equipment, and also presents the problem of degrading the thermal and mechanical properties of the insulating material. Furthermore, the amount of inorganic fine particles that can be added is naturally limited in order to ensure the fluidity of the uncured coating film before imprinting and its ability to fill the mold.

[0007] The problem to be solved by the present invention is to provide a photocurable resin composition that has high fluidity and can produce a cured product that exhibits high heat resistance. The problem to be solved by the present invention is to provide a cured product and a permanent film that can exhibit high heat resistance. [Means for solving the problem]

[0008] That is, the present invention relates to the following photocurable resin composition, etc. 1. A photocurable resin composition containing the following components (A), (B) and (C): (A) A photocurable organopolysiloxane having a hydrolyzable group represented by the following general formula (A1): (B) Inorganic fine particles (C) Photopolymerization initiator [ka] (In the general formula (A1), R 11 is a single bond or a divalent organic group, Y is a group containing a carbon-carbon unsaturated bond, * indicates the bonding position to the silicon atom of the organopolysiloxane.) 2. The photocurable resin composition according to 1, wherein the hydrolyzable group is a group represented by the following general formula (A2): [ka] (In the general formula (A2), R 12 is a single bond or an alkylene group having 1 to 12 carbon atoms, R 13 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, * indicates the bonding position to the silicon atom of the organopolysiloxane.) 3. The photocurable resin composition according to 1 or 2, wherein the inorganic fine particles (B) are one or more inorganic fine particles selected from silica, alumina, titania and zirconia. 4. The photocurable resin composition according to any one of 1 to 3, wherein the content of the inorganic fine particles (B) is in the range of 10 to 200 parts by mass per 100 parts by mass of the photocurable organopolysiloxane (A). 5. The photocurable resin composition according to any one of 1 to 4, further comprising a polymerization inhibitor (D) and / or a surfactant (E). 6. A cured product of the photocurable resin composition according to any one of 1 to 5. 7. A permanent film which is a cured product of the photocurable resin composition according to any one of 1 to 5. 8. A method for producing a permanent film, comprising the steps of photocuring the photocurable resin composition according to any one of 1 to 5 to form a photocured film, and baking the photocured film at 300°C or higher. [Effects of the Invention]

[0009] According to the present invention, there can be provided a photocurable resin composition which has high fluidity and from which the resulting cured product exhibits high heat resistance. The present invention can provide a cured product and a permanent film that can exhibit high heat resistance. DETAILED DESCRIPTION OF THE INVENTION

[0010] An embodiment of the present invention will be described below. The present invention is not limited to the following embodiment, and can be implemented by making appropriate modifications within the scope that does not impair the effects of the present invention. The compounds in this specification may be derived from fossil resources or biological resources.

[0011] [Photocurable resin composition] The photocurable resin composition of the present invention is a composition containing a photocurable organopolysiloxane (A) having a hydrolyzable group, inorganic fine particles (B), and a photopolymerization initiator (C). In the present invention, the photocurable organopolysiloxane has the hydrolyzable group, which allows it to exhibit low viscosity and ensures flowability even when used as a composition containing inorganic fine particles. This flowability makes it possible to form patterns using nanoimprinting. Each component contained in the composition of the present invention will be described below.

[0012] (Photocurable organopolysiloxane) An organopolysiloxane refers to a compound that contains a siloxane bond as a skeleton and has an organic group bonded to the silicon atom. The photocurable organopolysiloxane contained in the composition of the present invention (hereinafter, sometimes simply referred to as the "photocurable organopolysiloxane of the present invention") has a hydrolyzable group represented by the following general formula (A1):

[0013] [ka] (In the general formula (A1), R 11 is a single bond or a divalent organic group, Y is a group containing a carbon-carbon unsaturated bond, * indicates the bonding position to the silicon atom of the organopolysiloxane.)

[0014] The photocurable organopolysiloxane (A) having a hydrolyzable group represented by the general formula (A1) acts on the surface of the inorganic fine particles (B), suppressing uneven aggregation of the inorganic fine particles and maintaining stable dispersion of the inorganic fine particles. The stabilization of the dispersion state of the inorganic fine particles suppresses an increase in the viscosity of the entire composition, and a photocurable resin composition with excellent application properties and high fluidity can be obtained.

[0015] In the general formula (A1), examples of the group containing a carbon-carbon unsaturated bond for Y include a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl ether group, an allyl group, a styryl group, and a maleimide group.

[0016] R 11 The divalent organic group is preferably an alkylene group having 1 to 25 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms. Examples of the alkylene group having 1 to 12 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decylene group, an n-dodecylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, and a tetramethylethylene group.

[0017] R 11 The alkylene group having 1 to 12 carbon atoms is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group.

[0018] R 11 In the alkylene group having 1 to 12 carbon atoms, some of the -CH2- groups may be replaced by a carbonyl group (-C(=O)-), an ether bond (-O-), a phenylene group, an amide bond or a urethane bond, and a hydroxyl group or the like may further be substituted on the carbon atom.

[0019] The content of hydrolyzable groups in the photocurable organopolysiloxane of the present invention is, for example, in the range of 20 to 80 mass %, preferably in the range of 25 to 50 mass %, and more preferably in the range of 30 to 40 mass %.

[0020] The amount of hydrolyzable groups in the photocurable organopolysiloxane of the present invention can be confirmed by the method described in the Examples.

[0021] The number average molecular weight of the photocurable organopolysiloxane of the present invention is preferably in the range of 500 to 5,000. The number average molecular weight of the photocurable organopolysiloxane can be confirmed by GPC measurement.

[0022] When using a composition containing photocurable polysiloxane as a coating material for electronic devices, the application properties of the composition are an important performance factor. When a composition whose viscosity has been reduced by dilution with a solvent is used to coat electronic devices, the volatile components of the solvent may cause corrosion or deterioration of electrical and electronic components and the circuit boards on which they are mounted. Therefore, the photocurable polysiloxane alone is required to have a viscosity suitable for application, allowing it to conform to the finely textured surfaces of electronic components and heat sinks. The photocurable organopolysiloxane of the present invention exhibits coating properties sufficient to conform to the finely textured surfaces of electronic components and heat sinks as a resin alone. The viscosity of the photocurable organopolysiloxane of the present invention is preferably 150 mPas or less, more preferably 100 mPas or less. There is no particular lower limit to the viscosity, but it is, for example, 10 mPas or more. The viscosity of the photocurable organopolysiloxane can be confirmed by the method described in the examples.

[0023] The photocurable organopolysiloxane of the present invention is preferably a compound in which a group Y containing a carbon-carbon unsaturated bond and a silicon atom are linked by a bond represented by Si-ORY, and the silicon atom is part of a silicone oligomer.

[0024] The synthesis of the photocurable organopolysiloxane of the present invention is not particularly limited, and any known, commonly used method can be used, such as a synthesis method using a compound having a polymerizable unsaturated group and a hydroxyl group as a raw material, and a chlorosilane compound by dehydrochlorination, a synthesis method using an alkoxysilane compound by ester exchange, or a method in which a Lewis acid catalyst such as a boron compound is used to react with a silane hydride compound.

[0025] The photocurable organopolysiloxane of the present invention is preferably a compound having as reaction components a silicone oligomer having an alkoxysilyl group and a compound having a group containing a hydroxyl group and a carbon-carbon unsaturated bond. The compound having a group containing a hydroxyl group and a carbon-carbon unsaturated bond reacts with the alkoxysilyl group of the silicone oligomer to form a group represented by Si-ORY. Here, "reactive components" refers to components that constitute the structure of the photocurable organopolysiloxane, and does not include solvents, catalysts, or the like that do not constitute the structure.

[0026] The silicone oligomer can be prepared by a known polycondensation reaction using a hydrolyzable alkoxysilane compound as a reactant. The hydrolyzable alkoxysilane compounds used may be one type alone or two or more types.

[0027] The silicone oligomer having an alkoxysilyl group used in the production of the photocurable organopolysiloxane can be a commercially available product.

[0028] The compound having a hydroxyl group and a group containing a carbon-carbon unsaturated bond is preferably a (meth)acrylate compound having a hydroxyl group, and in this case, the polymerizable functional group in the organopolysiloxane is, for example, a functional group represented by the following general formula (A2):

[0029] [ka] (In the general formula (A2), R12 is a single bond or an alkylene group having 1 to 12 carbon atoms, R 13 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, * indicates the bonding position to the silicon atom of the organopolysiloxane.)

[0030] In the general formula (A2), R 12 The alkylene group having 1 to 12 carbon atoms is preferably an alkylene group having 1 to 5 carbon atoms, and R 13 is preferably a hydrogen atom or a methyl group.

[0031] The (meth)acrylate compound having a hydroxyl group is preferably a compound in which the "*" portion of the functional group represented by the general formula (A2) is a hydrogen atom.

[0032] Specific examples of the (meth)acrylate compound having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, tricyclodecane dimethanol acrylate, adamantanediol acrylate, β-carboxyethyl acrylate, and pentaerythritol triacrylate.

[0033] The (meth)acrylate compound having a hydroxyl group may be used alone or in combination of two or more kinds.

[0034] The photocurable organopolysiloxane can be produced by any of the methods described above without any particular limitations. However, a particularly convenient production method involves reacting a silicone oligomer with a compound having a hydroxyl group and a group containing a carbon-carbon unsaturated bond, for example, by heating in the presence of an acid catalyst (e.g., sulfuric acid).

[0035] (Inorganic fine particles) Examples of inorganic fine particles include silica, alumina, titania, zirconia, copper oxide, zinc oxide, indium oxide, zirconium hydroxide, aluminum oxide, calcium hydroxide, calcium carbonate, calcium sulfate, potassium carbonate, potassium hydrogen carbonate, potassium bromide, potassium chloride, potassium perchlorate, potassium cyanide, sodium nitrate, sodium bromide, sodium cyanide, sodium metasilicate, sodium sulfite, barium sulfate, barium carbonate, barium fluoride, barium chloride, and lithium. Examples of suitable inorganic fillers include barium hydrogen phosphate, barium sulfide, barium titanate, sodium fluoride, calcium fluoride, lanthanum fluoride, lithium fluoride, lithium niobate, magnesium fluoride, magnesium hydroxide, magnesium oxide, magnesium carbonate, synthetic quartz, strontium carbonate, strontium fluoride, cerium oxide, hafnium oxide, niobium pentoxide, tantalum pentoxide, tin oxide, indium tin oxide, beryllium oxide, kaolin clay, talc, magnesium silicate, sericite, wallasnite, mica, etc. Among these, at least one selected from silica, alumina, titania, and zirconia is preferred, and silica is more preferred. The surfaces of these particles may be coated with SiO2, Al2O3, or the like.

[0036] The average particle size of the inorganic particles is not particularly limited, but is, for example, in the range of 1 to 100 nm, preferably 2 to 50 nm, as primary particles. The average particle size of the inorganic fine particles can be measured using a transmission electron microscope or the BET method. The shape of the inorganic fine particles is not limited to spherical, but may be any shape such as scale, column, tubular, fibrous, hollow, porous, or beaded.

[0037] The content of the inorganic fine particles (B) in the composition of the present invention is, for example, in the range of 10 to 200 parts by mass, preferably in the range of 15 to 180 parts by mass, and more preferably in the range of 20 to 160 parts by mass, per 100 parts by mass of the photocurable organopolysiloxane (A).

[0038] (Photopolymerization initiator) The photopolymerization initiator may be appropriately selected from those that have absorption in the light source used for photocuring. Examples thereof include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, bis(2,4, Examples of compounds that can be used include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], 2-hydroxy-2-methyl-1-phenyl-propan-1-one, phenylglyoxylic acid methyl ester, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

[0039] Commercially available photopolymerization initiators can be used, such as OMNIRAD 1000, OMNIRAD 248, OMNIRAD 481, OMNIRAD 4817, OMNIRAD 4MBZ-flakes, OMNIRAD 500, OMNIRAD 659, OMNIRAD 73, OMNIRAD 784, OMNIRAD 81, OMNIRAD BDK, OMNIRAD MBS, OMNIRAD BP-flakes, OMNIRAD DETX, OMNIRAD EDB, OMNIRAD EHA, OMNIRAD EMK, OMNIRAD ITX, OMNIRAD MBF, OMNIRAD OMBB, OMNIRAD TPO, OMNIRAD 410, and OMNIRAD BL72. 3, BL724, BL750, BL751, BL1173, BL127, BL184, BL184FF, BL2022, BL2100, BL2959, BL369, BL369E, BL379, BL379EG, BL4265, BL754, BL819, BL819DW, BL907, BL907FF, BL127D, BL1001M, BL1001ONE, BL198, BL160, BL150, BL100F, BL100LT, BL100IT, BL100-46, BL100DP-250, BL100TZT, and BL100-55 (manufactured by IMG).

[0040] The content of the photopolymerization initiator (C) in the composition of the present invention is, for example, in the range of 0.01 to 10 parts by mass, and preferably in the range of 0.1 to 5 parts by mass, per 100 parts by mass of the photocurable organopolysiloxane (A).

[0041] (polymerization inhibitor) The composition of the present invention preferably further contains a polymerization inhibitor (D). The polymerization inhibitor may be, for example, a known one, and is a compound represented by the following general formula (D1-1), (D1-2), (D2-1), (D2-2) or (D3-1):

[0042] [ka] (In the general formulae (D1-1), (D1-2), (D2-1), (D2-2) and (D3-1), X D1 ~X D8 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may have a substituent, or an aryl group having 4 to 20 carbon atoms which may have a substituent. X D9 is a tert-alkyl group having 4 to 20 carbon atoms which may have a substituent. . X D10 is an alkyl group having 1 to 20 carbon atoms which may have a substituent. X D11 ~X D13 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or an aryl group having 4 to 30 carbon atoms which may have a substituent. X D14 and X D15 are each independently a tert-alkyl group having 4 to 20 carbon atoms which may have a substituent. X D16 ~X D23 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. X D24is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. X D25 is a divalent group constituting a 5- to 7-membered heterocycle containing a nitrogen atom. X D26 ~X D29 are each independently an alkyl group having 1 to 6 carbon atoms. X D30 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may have a substituent, an alkoxy group having 1 to 18 carbon atoms which may have a substituent, or an oxy radical group.

[0043] In the general formulae (D1-1), (D1-2), (D2-1) and (D2-2), X D1 ~X D21 Adjacent groups may be bonded to each other to form a saturated or unsaturated ring. In the general formula (D3), X D26 ~X D30 may be bonded to adjacent groups or groups substituting the same carbon atom to form a saturated or unsaturated ring.

[0044] Examples of the compound represented by the general formula (D1-1) include 1,4-benzoquinone, 2-methyl-1,4-benzoquinone, 2-tert-butyl-1,4-benzoquinone, 2-phenyl-1,4-benzoquinone, 2,5-dimethyl-1,4-benzoquinone, 2,6-dimethyl-1,4-benzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, 2,6-di-tert-butyl-1,4-benzoquinone, 2,5-diphenyl-1,4-benzoquinone, 2,6-diphenyl-1,4-benzoquinone, 2,3, Benzoquinones such as 5-trimethyl-1,4-benzoquinone and 2,3,5,6-tetramethyl-1,4-benzoquinone; naphthoquinones such as 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2-tert-butyl-1,4-naphthoquinone, phylloquinone, and menaquinone; and anthraquinones such as 9,10-anthraquinone, 1,4-anthraquinone, 2-methyl-9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, and 2,3-dimethyl-9,10-anthraquinone.

[0045] Examples of the compound represented by the general formula (D1-2) include benzoquinones such as 1,2-benzoquinone, 4-methyl-1,2-benzoquinone, 4-tert-butyl-1,2-benzoquinone, 4-phenyl-1,2-benzoquinone, 3,5-dimethyl-1,2-benzoquinone, 3,5-di-tert-butyl-1,2-benzoquinone, and 3,5-diphenyl-1,2-benzoquinone; naphthoquinones such as 1,2-naphthoquinone, 4-methyl-1,2-naphthoquinone, and 4-tert-butyl-1,2-naphthoquinone; and anthraquinones such as 1,2-anthraquinone.

[0046] Examples of the compound represented by the general formula (D2-1) include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. ], hindered phenols such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene; and semi-hindered phenols such as 2-tert-butyl-5-methylphenol, 2,4-di-tert-butyl-5-methylphenol, and 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0047] Examples of the compound represented by the general formula (D2-2) include 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), 2,2'-dihydroxy-3,3'-di(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane, and 1'-hydroxy[2,2'-ethylidenebis[4,6-bis(1,1-dimethylpropyl)benzene]]-1-yl acrylate.

[0048] Examples of the compound represented by the general formula (D3) include tetramethylpiperidines such as 2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)butane-1,2,3,4-tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate; 1,2,2,6,6-pentamethylpiperidine; tetramethylpiperidine-1-alkyls such as 1-ethoxy-1,2,2,6,6-tetramethylpiperidine, tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl)butane-1,2,3,4-tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, and 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate; tetramethylpiperidine-1-alkoxys such as 1-ethoxy-2,2,6,6-tetramethylpiperidine and bis(1-undecoxy-2,2,6,6-tetramethyl-4-piperidin-4-yl)carbonate;2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acryloyloxy-2 , 2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-propargyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl, and other tetramethylpyrrolidine-1-oxyls; and tetramethylpyrrolidine-1-oxyls such as 3-carboxy-2,2,5,5-tetramethylpyrrolidine-1-oxyl.

[0049] The content of the polymerization inhibitor (D) in the composition of the present invention is, for example, in the range of 0.001 to 1 part by mass, and preferably in the range of 0.01 to 0.5 parts by mass, per 100 parts by mass of the photocurable organopolysiloxane (A) of the present invention.

[0050] (surfactant) The composition of the present invention preferably further contains a surfactant (E). The surfactant may be any of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant, but a nonionic surfactant is preferred.

[0051] Examples of nonionic surfactants include polyoxyalkylene alkyl ether surfactants, polyoxyalkylene fatty acid ester surfactants, sorbitan fatty acid ester surfactants, polyoxyalkylene alkylamine surfactants, Pluronic (registered trademark) surfactants (triblock copolymers of polyethylene oxide and polypropylene oxide), fluorine-based surfactants, silicone-based surfactants, and acrylic polymerization surfactants.

[0052] Examples of anionic surfactants include alkylbenzene sulfonate surfactants, alkyl alcohol sulfate ester salt surfactants, polyoxyalkylene alkyl ether sulfate surfactants, alkyl alcohol phosphate ester salt surfactants, polyoxyalkylene alkyl ether phosphate surfactants, polyoxyalkylene alkyl ether acetate surfactants, and fluorine-containing surfactants, and either acid or neutralized types may be used.

[0053] Examples of cationic surfactants include tetraalkylammonium halide surfactants, alkylpyridinium halide surfactants, and alkylimidazoline halide surfactants.

[0054] Examples of amphoteric surfactants include alkyl betaine surfactants, alkyl imidazolinium betaine surfactants, and lecithin surfactants.

[0055] The content of the surfactant (E) in the composition of the present invention is, for example, in the range of 0.001 to 10 parts by mass, preferably in the range of 0.01 to 8 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass, relative to 100 parts by mass of the photocurable organopolysiloxane of the present invention.

[0056] The composition of the present invention may contain a solvent, which can adjust the viscosity of the composition and the coating film thickness. Examples of solvents that can be used include aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane, and cyclopentane; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and anisole; alcohols such as methanol, ethanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alkyl ethers; ethers such as 1,2-dimethoxyethane, tetrahydrofuran, and dioxane; and N-methylpyrrolidone, dimethylformamide, and dimethylacetamide.

[0057] The content of the solvent in the composition of the present invention is not particularly limited, and may be appropriately set according to the target viscosity and coating film thickness.

[0058] The composition of the present invention may contain a photocurable organopolysiloxane (A), inorganic fine particles (B), a photopolymerization initiator (C), an optional polymerization inhibitor (D), an optional surfactant (E), and an optional solvent, or may consist essentially of these components. Here, "substantially consisting of" means that the total of the photocurable organopolysiloxane (A), inorganic fine particles (B), photopolymerization initiator (C), optional polymerization inhibitor (D), optional surfactant (E), and optional solvent is 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the composition.

[0059] The composition of the present invention may contain other ingredients as long as the effects of the present invention are not impaired. Examples of other ingredients include organopolysiloxanes other than the curable organopolysiloxane (A), photosensitizers, ultraviolet absorbers, antioxidants, adhesion aids, etc.

[0060] The components in the photocurable resin composition of the present invention have been explained above, and each component may be used alone or in combination of two or more.

[0061] [Cured product] The photocurable resin composition of the present invention can be cured to form a cured product by irradiating it with light. For example, the photocurable resin composition of the present invention can be applied to a substrate to form a coating film, and the coating film can be irradiated with light to form a cured layer on the substrate. The cured layer containing inorganic fine particles has high heat resistance and is therefore suitable for permanent film applications such as protective films for semiconductor devices, interlayer insulating films, and permanent resist films.

[0062] The substrate may be appropriately selected depending on the purpose, and examples thereof include quartz, sapphire, glass, plastic, ceramic materials, vapor-deposited films (CVD, PVD, sputtering), magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, Fe, and stainless steel, paper, polymer substrates such as SOG (Spin On Glass), SOC (Spin On Carbon), polyester films, polycarbonate films, and polyimide films, TFT array substrates, PDP electrode plates, conductive substrates such as ITO and metals, insulating substrates, and semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. The shape of the substrate is not particularly limited, and may be any shape depending on the purpose, such as a flat plate, a sheet, or a three-dimensional shape having curvature entirely or partially, etc. There are also no limitations on the hardness, thickness, etc. of the substrate.

[0063] As a method for coating the photocurable resin composition of the present invention, various methods can be used, such as spraying, spin coating, dipping, roll coating, blade coating, doctor roll method, doctor blade method, curtain coating, slit coating, screen printing, and inkjet method. Spin coating is preferred because it can provide a coating film with good in-plane uniformity in thickness.

[0064] Examples of light sources for irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, carbon arcs, mercury-xenon lamps, excimer lasers (XeCl, KrF, ArF, etc.), ultraviolet or visible light lasers, and ultraviolet or visible light LEDs. The amount of light irradiation can be set appropriately, for example, 10 to 10,000 mJ / cm 2 The range is.

[0065] A baking step may be performed to heat the substrate after coating with the photocurable organopolysiloxane composition and before irradiation with light. Various baking methods can be used, including proximity, adsorption, conveyor, and microwave induction heating, and combinations of these methods are also possible. The baking conditions are not particularly limited, but for example, the baking temperature is in the range of 70 to 180° C., and the baking time is in the range of 0.3 to 10 minutes.

[0066] The photocured product obtained by light irradiation may be further baked. The baking temperature may be set to, for example, 300° C. or higher, and the baking time may be, for example, in the range of 1 to 30 minutes. The upper limit of the baking temperature is not particularly limited, but is, for example, 600° C. Since the photocured film of the present invention has high heat resistance, thermal shrinkage can be minimized even when baked at a high temperature of 300° C. or higher.

[0067] As described above, the cured product obtained from the photocurable resin composition of the present invention is resistant to high-temperature baking at 300° C. or higher. For example, when the cured product obtained from the photocurable resin composition of the present invention is used as a permanent film, this heat resistance makes it possible to expand the range of materials that can be used in devices that include permanent films.

[0068] When the photocurable resin composition of the present invention is used for photoimprinting, a mold on which a pattern has been formed in advance is pressed against a coating film of the photocurable resin composition formed on the above-mentioned substrate, and the coating film is cured by irradiating it with light while the mold is in contact, thereby obtaining a cured film on which a pattern has been formed. The baking step may be carried out before the mold is brought into contact with the substrate, or after the mold is pressed against the substrate.

[0069] Examples of materials for the optical imprinting mold include light-transmitting materials such as quartz, ultraviolet-transmitting glass, sapphire, diamond, silicone materials such as polydimethylsiloxane, fluororesins, cycloolefin resins, and other light-transmitting resin materials. Furthermore, as long as the substrate used is a light-transmitting material, the imprinting mold may be made of a light-opaque material. Examples of light-opaque materials include metal, SiC, and mica. Among these, a quartz mold is particularly preferred because it transmits ultraviolet light well, has high hardness, and has high surface smoothness. The mold for photoimprinting can be selected from any shape such as a flat surface, a belt, a roll, or a roll belt.

[0070] The photoimprinting mold may be subjected to a release treatment to improve the releasability between the photocurable composition and the mold surface. Examples of the release treatment include treatment with a silicone-based or fluorine-based silane coupling agent.

[0071] The light irradiation method can be a method of irradiating light from the mold side when the mold is made of a light-transmitting material, or a method of irradiating light from the substrate side when the substrate is made of a light-transmitting material.

[0072] If there is a concern about the conformability of the pattern to be formed, the composition may be heated to a temperature at which sufficient fluidity is obtained upon light irradiation. The temperature when heated is preferably 0 to 300° C., more preferably 0 to 200° C., even more preferably 0 to 150° C., and particularly preferably 25 to 80° C. Within this temperature range, the pattern shape formed from the photocurable composition is maintained with good precision.

[0073] After curing, the mold is released to obtain a cured film having a concave-convex pattern formed by transferring the concave-convex pattern of the mold. In order to prevent deformation such as warping of the substrate and to increase the precision of the concave-convex pattern, the release step is preferably carried out after the temperature of the cured film has cooled to around room temperature (25°C).

[0074] If residue of the cured product is found on the mold after it is released, it is advisable to wash the mold with a cleaning liquid. The cleaning liquid used for cleaning the mold may be appropriately selected depending on the material of the mold, and either an acid cleaning liquid or an alkaline cleaning liquid may be used.

[0075] Examples of the acid cleaning solution include sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, acetic acid, phosphoric acid, aqua regia, dilute hydrofluoric acid, sulfuric acid / hydrogen peroxide, and hydrochloric acid / hydrogen peroxide. Examples of the alkaline cleaning solution include caustic alkalis such as caustic soda and caustic potash, inorganic alkalis such as various silicates, phosphates, and carbonates, as well as organic alkalis such as tetramethylammonium hydroxide, ammonia water, ammonia hydrogen water, and ammonia / hydrogen peroxide.

[0076] Since the alkaline cleaning solution may dissolve SiO2, an acid cleaning solution is preferred when the mold is made of glass or quartz, and sulfuric acid / hydrogen peroxide is particularly preferred. In particular, when cleaning a quartz mold having a fine pattern of 100 nm or less, the alkaline cleaning solution may dissolve SiO2 and damage the rectangular shape of the mold. Therefore, by using an acid cleaning solution, the mold can be cleaned without damaging the fine pattern, allowing it to be used repeatedly.

[0077] The cleaning method is not particularly limited, but examples thereof include spraying, showering, immersion, heated immersion, ultrasonic immersion, spinning, bubbling, shaking, brushing, steaming, and polishing, and the spinning method is particularly preferred in order to prevent re-adhesion of cleaned contaminants.

[0078] The laminate produced using the photocurable resin composition of the present invention may be prepared by applying a resist material to a substrate and curing it in situ to form a resist film, or by peeling off the resist film formed on the temporary substrate and attaching it to a substrate to form a laminate. If the resist film is patterned, the laminate can be dry-etched to obtain a patterned product in which the pattern is transferred to the substrate by dry etching.

[0079] The gas used for dry etching may be any known gas, such as oxygen atom-containing gases such as oxygen, carbon monoxide, and carbon dioxide; inert gases such as helium, nitrogen, and argon; chlorine-based gases such as chlorine and boron trichloride; fluorine gas, fluorocarbon-based gases, hydrogen gas, and ammonia gas. These gases may be used alone or in appropriate mixtures. By etching using these etching gases, a desired pattern can be formed on a substrate. [Example]

[0080] The present invention will be specifically described below with reference to examples and comparative examples. The present invention is not limited to the following examples.

[0081] Synthesis Example 1: Preparation of Photocurable Organopolysiloxane A reaction vessel was charged with 200 parts by mass of alkoxysilane compound (a-1) ("KR-500" manufactured by Shin-Etsu Chemical Co., Ltd., trifunctional monomer base, viscosity: 25 mPas, methoxy group content: 28% by mass), 90 parts by mass of 2-hydroxyethyl acrylate, and paratoluenesulfonic acid monohydrate (0.0145 parts by mass). The mixture was heated to 120°C and stirred for 3 hours while distilling off the produced methanol to allow the reaction to proceed, yielding 265.22 parts by mass of photocurable organopolysiloxane (A-1).

[0082] (Hydrolyzable Group Content) Regarding the obtained photocurable organopolysiloxane 1H-NMR measurement was carried out, and the content of hydrolyzable groups was calculated from the detected spectral intensity. Specifically, in Example 1, 2-hydroxyethyl acrylate was used to prepare the photocurable organopolysiloxane, and the content of hydrolyzable groups bonded to the polysiloxane resin was calculated from the intensity ratio of the peak (δ=3.97, CH2-O-Si) in the spectrum resulting from the bonding of 2-hydroxyethyl acrylate and silicone oligomer via Si-O-C bond to the peak derived from a standard substance added to the measurement sample in advance. As a result, the content of hydrolyzable groups was found to be 33 mass%.

[0083] Furthermore, the above 1 H-NMR was carried out under the following conditions. Measurement equipment: Bruker Japan "AVANCE NEO 400" Magnetic field strength: 400MHz Accumulation count: 16 times Solvent: deuterated chloroform (CDCl3) Sample concentration: 30 mg / 0.6 ml

[0084] (Examples 1-3 and Comparative Examples 1-4: Preparation and Evaluation of Photocurable Resin Compositions) Components (A) to (F) shown in Table 1 were mixed in the amounts shown in Table 1 to prepare a photocurable resin composition. The photocurable resin compositions obtained were evaluated as follows, and the results are shown in Table 1.

[0085] The components shown in Table 1 are as follows: Organopolysiloxane (A-2): Organopolysiloxane represented by the following general formula (A-2): [ka] Organopolysiloxane (A-3): a silicone oligomer having an alkoxy group (a methoxy group and an ethoxy group) and an acryloyl group ("KR-513" manufactured by Shin-Etsu Chemical Co., Ltd.). Organopolysiloxane (A-3) does not have a group represented by general formula (A1) of the present invention. Inorganic fine particles (B-1): propylene glycol monomethyl ether acetate dispersion of organosilica sol ("PMA-ST" manufactured by Nissan Chemical Co., Ltd., average particle size of organosilica sol: 12 nm, amount of organosilica sol: 30% by mass) Inorganic fine particles (B-2): Zirconium oxide methanol dispersion ("SZR-M" manufactured by Sakai Chemical Industry Co., Ltd., average particle size of zirconium oxide: 3 nm, amount of zirconium oxide: 30% by mass) Inorganic fine particles (B-3): propylene glycol monomethyl ether dispersion of organosilica sol ("PGM-ST" manufactured by Nissan Chemical Co., Ltd., average particle size of organosilica sol: 12 nm, amount of organosilica sol: 30% by mass) Photopolymerization initiator (C-1): a compound represented by the following general formula (C-1) ("OMNIRAD379EG" manufactured by IGM Resins BV) Photopolymerization initiator (C-2): a compound represented by the following general formula (C-2) ("IRGACURE184" manufactured by IGM Resins BV) Photopolymerization initiator (C-3): a compound represented by the following general formula (C-3) ("IRGACURE907" manufactured by IGM Resins BV) Photopolymerization initiator (C-4): a compound represented by the following general formula (C-4) ("Runtecure 1108" manufactured by IGM Resins BV) Polymerization inhibitor (D-1): 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) ("Nonflex EBP" manufactured by Seiko Chemical Co., Ltd.) Surfactant (E-1): Nonionic surfactant (NOF Corporation "Nonion S-202") Multifunctional (meth)acrylate compound (F-1): pentaerythritol tetraacrylate ("Aronix M-450" manufactured by Toagosei Co., Ltd.) Multifunctional (meth)acrylate compound (F-2): Aliphatic urethane acrylate ("PU610" manufactured by Miwon Specialty Chemical)

[0086] [ka]

[0087] (Coating property evaluation) The photocurable resin composition was diluted with propylene glycol monomethyl ether acetate to a concentration of 20% by mass and spin-coated onto a 6-inch silicon wafer at 2000 rpm for 30 seconds. The resulting coating film was visually inspected for the presence or absence of striations (uneven linear patterns that radiate outward from the outer edge of the wafer) and evaluated according to the following criteria. Excellent (A): No visible striations Good (B): Slight striations are visible Insufficient (C): Striations are visible

[0088] (Evaluation of fluidity of uncured coating film) The coating film formed in the coating property evaluation was baked on a hot plate at 80° C. for 60 seconds, and the coating film was wiped with a swab and evaluated according to the following criteria. Excellent (A): Sticky, leaves marks on the coating, and resin adheres to the swab Good (B): There is a slight stickiness and the coating leaves a mark when touched, but no resin adheres to the swab Insufficient (C): No stickiness and the film has completely hardened

[0089] (UV curing evaluation) The coating film formed in the coating property evaluation was irradiated with 100 mJ / cm using a UV irradiation device (Minae Electric Manufacturing Co., Ltd.). 2 The resulting UV-cured film was immersed together with the substrate in propylene glycol monomethyl ether acetate for 1 minute, and the film thickness before and after immersion was measured using a microspectrophotometric film thickness meter ("OPTM-A1" manufactured by Otsuka Electronics Co., Ltd.) to calculate the rate of change in film thickness. Based on this rate of change, the film was evaluated according to the following criteria. Excellent (A): Almost no change in film thickness observed (less than 1%) Good (B): Slight change in film thickness observed (1% to less than 5%) Insufficient (C): Change in film thickness observed (5% or more)

[0090] (Evaluation of the heat shrinkage rate of UV cured films) The coating film formed in the coating property evaluation was irradiated with 100 mJ / cm using a UV irradiation device (Minae Electric Manufacturing Co., Ltd.). 2 The film was then UV-cured at an exposure dose of 1000 ppm. The film was then baked on a hot plate at 350°C for 5 minutes. The thickness of the cured film before and after baking was measured using a microspectrophotometer (OPTM-A1, manufactured by Otsuka Electronics Co., Ltd.), and the thermal shrinkage was calculated. The calculated thermal shrinkage was evaluated according to the following criteria. Excellent (A): Heat shrinkage rate is 10% or less Good (B): Heat shrinkage rate is 10% or more but less than 20%, insufficient Insufficient (C): Heat shrinkage rate is 20% or more

[0091] (Nanoimprint pattern formation evaluation) The photocurable resin composition was diluted with propylene glycol monomethyl ether acetate, spin-coated onto a silicon wafer substrate, and baked on a hot plate at 80°C for 60 seconds. The baked coating had a thickness of 250 nm. The silicon wafer substrate was placed on the lower stage of a nanoimprinting system NM-0401 manufactured by Meisho Kiko. A quartz mold (NTT Advanced Technology Corporation, NIM-PH350) with a 350 nm line / space pattern and a 350 nm groove depth was fixed to a glass base and then placed on the upper stage of the system. The upper stage was lowered to contact the mold with the UV-curable composition, and a pressure of 300 N was applied over 10 seconds. After 30 seconds, the mold was exposed from the backside to an LED light source with a peak wavelength of 365±5 nm at 100 mJ / cm². The upper stage was then raised over 10 seconds, and the mold was peeled off to obtain a sample with a pattern formed in the center of the substrate. The pattern formability was evaluated according to the following criteria. Excellent (A): A pattern with good rectangularity can be obtained. Good (B): A pattern with good rectangularity is obtained for the most part, but some poor rectangularity is observed. Insufficient (C): Poor rectangularity is occasionally observed, and pattern collapse is confirmed.

[0092] [Table 1]

[0093] The results of Examples 1 to 3 in Table 1 show that by using organopolysiloxanes having specific hydrolyzable groups, the compositions exhibit high fluidity and the resulting cured products have excellent heat resistance. On the other hand, for example, organopolysiloxanes (A-2) and (A-3) contain Si-OR 11 It can be seen that the fluidity is poor because the polymer does not have the structure represented by -Y.

Claims

1. A photocurable resin composition comprising the following components (A), (B), and (C): (A) A photocurable organopolysiloxane having a hydrolyzable group represented by the following general formula (A1): (B) Inorganic fine particles (C) Photopolymerization initiator 【Chemistry 1】 (In the general formula (A1), R １１ is a single bond or a divalent organic group, Y is a group containing a carbon-carbon unsaturated bond, * indicates the bonding position with the silicon atom of the organopolysiloxane.)

2. The photocurable resin composition according to claim 1, wherein the hydrolyzable group is a group represented by the following general formula (A2): 【Chemistry 2】 (In the general formula (A2), R １２ is a single bond or an alkylene group having 1 to 12 carbon atoms, R １３ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, * indicates the bonding position with the silicon atom of the organopolysiloxane.)

3. 2. The photocurable resin composition according to claim 1, wherein the inorganic fine particles (B) are one or more inorganic fine particles selected from the group consisting of silica, alumina, titania, and zirconia.

4. 2. The photocurable resin composition according to claim 1, wherein the content of the inorganic fine particles (B) is in the range of 10 to 200 parts by mass per 100 parts by mass of the photocurable organopolysiloxane (A).

5. The photocurable resin composition according to claim 1, further comprising a polymerization inhibitor (D) and / or a surfactant (E).

6. A cured product of the photocurable resin composition according to any one of claims 1 to 5.

7. A permanent film which is a cured product of the photocurable resin composition according to any one of claims 1 to 5.

8. A step of photocuring the photocurable resin composition according to any one of claims 1 to 5 to form a photocured film; baking the photocured film at 300°C or higher; A method for producing a permanent film comprising the steps of:

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