JP5882079B2 - Resin stamper - Google Patents

Description

  The present invention relates to a resin stamper suitable for manufacturing a plastic lens, a multilayer recording medium, and the like, and a method for manufacturing the resin stamper mainly in the optical field.

  In recent years, a transfer technique called an optical imprint method has been proposed. In the optical imprint method, after a photocurable resin is applied on a substrate made of a light-transmitting material, a mold having an uneven pattern on the surface is pressure-bonded to the photocurable resin, and at least one of the substrate and the mold is used. This is a method for obtaining a structure by curing a photocurable resin by irradiating light from the side.

  A technique known as nanoimprint lithography (NIL) is also a kind of optical imprint method for forming nanoscale patterns at high resolution in various fields such as electronics, photonics, magnetic devices, and biology. This is the most promising technology.

  Advantages of optical imprinting include simplicity, high throughput, and low cost. However, if the mold used for optical imprinting is not durable, the number of repeated uses of the mold is reduced, and as a result, the mold must be replaced many times, and the above advantages are lost.

  Examples of mold materials with excellent durability include metals and quartz. However, although metals are durable, there is a disadvantage that the material of the substrate cannot be selected because light irradiation from the substrate side is forced. Since quartz can transmit light, a substrate is not selected. However, a long time and high cost are required for manufacturing the structure, and there is a drawback that the structure is easily broken when it is peeled off.

  Therefore, an inexpensive resin stamper has been proposed as a mold to solve such a problem.

  Further, the following Patent Documents 1 to 6 report resinous stampers. The resinous stampers described in these Patent Documents 1 to 6 are molded by curing a radical polymerizable resin or a cationic resin, are manufactured at low cost, and are excellent in transparency and moldability.

Japanese Patent No. 4580411 JP 2010-231868 A JP 2009-12300 A Japanese Patent No. 2581116 JP 2010-5971 A Japanese Patent Publication No. 3-80089

  However, since the resin stampers described in Patent Documents 1 to 6 are made of an organic substance, it is considered that the light resistance is low and the hardness and durability are low. In addition, the resin stamper described in Patent Document 3 has a high hardness, but has a low light resistance due to the use of a cationic polymerization compound, and color deterioration occurs while repeatedly being irradiated with light as a resin stamper. There is a drawback that it will.

Under such circumstances, a resin stamper that has both durability and light resistance in addition to high hardness and can be used repeatedly is still desired.
Therefore, the problem to be solved by the present invention is to provide a single layer resin stamper having both durability and light resistance.

As a result of intensive studies and repeated experiments in order to solve such problems, the present inventors have found that the above-described problems can be solved by the present invention having the following configuration, and have completed the present invention.
That is, the present invention is as follows.

  [1] A single-layer resin stamper molded by irradiating a single layer made of a photosensitive resin containing a silicon-containing compound with ultraviolet light to cure the photosensitive resin, the pencil of the single-layer resin stamper A single-layer resin stamper having a hardness of H or higher.

  [2] The single-layer resin stamper according to [1], wherein the photosensitive resin includes inorganic oxide particles.

  [3] The single layer resin stamper according to [2], wherein the inorganic oxide particles are silica particles.

[4] The silicon-containing compound has the following general formula (1):
R ¹ _n1 SiX ¹ _4-n1 (1)
{In the formula, R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms which may contain nitrogen, sulfur, oxygen or fluorine, and X ¹ is a hydroxyl group, a halogen atom, or 1 to 6 carbon atoms. A group selected from the group consisting of an alkoxy group and an acetoxy group having 1 to 6 carbon atoms, n1 is an integer of 0 to 3, and when n1 is 2 or 3, a plurality of R ¹ are the same as each other Or when n1 is 0, 1 or 2, the plurality of X ¹ may be the same as or different from each other. }
The single-layer resin stamper according to any one of [1] to [3], which is a polysiloxane compound comprising at least one silane compound represented by formula (1) and / or a hydrolytic condensation product of the silane compound. .

[5] The silicon-containing compound has the following general formula (1):
R ¹ _n1 SiX ¹ _4-n1 (1)
{In the formula, R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms which may contain nitrogen, sulfur, oxygen or fluorine, and X ¹ is a hydroxyl group, a halogen atom, or 1 to 6 carbon atoms. A group selected from the group consisting of an alkoxy group and an acetoxy group having 1 to 6 carbon atoms, n1 is an integer of 0 to 3, and when n1 is 2 or 3, a plurality of R ¹ are the same as each other Or when n1 is 0, 1 or 2, the plurality of X ¹ may be the same as or different from each other. }
Any one of [1] to [3], which is a polysiloxane compound comprising a hydrolysis-condensation product of at least one silane compound represented by the formula: or a mixture of the silane compound and the polysiloxane compound. Single-layer resin stamper as described.

  [6] The single-layer resin stamper according to [4] or [5], wherein the silica particles are chemically bonded to the polysiloxane compound and / or a part of the silane compound by Si—O—Si bonds.

  [7] The single-layer resin stamper according to any one of [4] to [6], wherein the silica particles are chemically bonded to a part of the polysiloxane compound by Si—O—Si bonds.

  [8] The single-layer resin stamper according to any one of [4] to [7], wherein the polysiloxane compound and / or the silane compound has a photopolymerizable functional group.

  [9] The single-layer resin stamper according to any one of [4] to [8], wherein the polysiloxane compound has a photopolymerizable functional group.

  [10] The single-layer resin stamper according to any one of [1] to [9], wherein the photosensitive resin further includes a compound having no silicon and having a photopolymerizable functional group.

[11] The following steps:
A filling step of filling the matrix having the pattern with the photosensitive resin;
A laminating step of superimposing a matrix having a substrate or a pattern on a single layer made of the photosensitive resin;
[1] to [1] including a curing step of curing the photosensitive resin by irradiating ultraviolet light, and a peeling step of peeling a single layer made of the cured photosensitive resin from the matrix and / or the substrate. [10] The method for producing a single-layer resin stamper according to any one of [10].

  [12] The manufacturing method according to [11], further including a heating step of heating the single layer made of the cured photosensitive resin after the peeling step.

  The present invention provides a single layer resin stamper having both durability and light resistance in addition to high hardness.

  In a mode for carrying out the present invention (hereinafter, also referred to as “this embodiment”), the resin stamper cures the photosensitive resin by irradiating the layer including the photosensitive resin including the silicon-containing compound with ultraviolet light. It is molded by making it. Moreover, it is preferable that the layer containing the photosensitive resin containing a silicon-containing compound is a single layer. Furthermore, the photosensitive resin may include particles.

In the present embodiment, from the viewpoint of improving the hardness and durability of the resin stamper, the pencil hardness of the resin stamper is preferably H or higher, more preferably 2H or higher, and more preferably 4H or higher. Is more preferable, and 5 H or more and 9 H or less is particularly preferable.
Each component which comprises the photosensitive resin used by this embodiment is demonstrated in detail below.

<Photosensitive resin containing silicon-containing compound>
[Silicon-containing compound]
In the present embodiment, when the photosensitive resin contains a silicon-containing compound, the hardness and light resistance of the single-layer resin stamper can be improved.

  Examples of the silicon-containing compound include silicone, silicon resin, cyclic siloxane, organic silicon compound, silica inorganic filler, and the like, and it is preferable that these compounds have a photopolymerizable functional group. Moreover, when the photosensitive resin contains other components, it is preferable that at least one of the silicon-containing compound and / or other components has a photopolymerizable functional group. In this specification, a photopolymerizable functional group is mentioned in detail later.

Furthermore, from the viewpoint of handling as a silicon-containing compound, the simplicity of the production method, and from the viewpoint of compatibility between the silicon-containing compound and other components when other components are included, the silicon-containing compound is represented by the following general formula ( 1):
R ¹ _n1 SiX ¹ _4-n1 (1)
{In the formula, R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms which may contain nitrogen, sulfur, oxygen or fluorine, and X ¹ is a hydroxyl group, a halogen atom, or 1 to 6 carbon atoms. A group selected from the group consisting of an alkoxy group and an acetoxy group having 1 to 6 carbon atoms, n1 is an integer of 0 to 3, and when n1 is 2 or 3, a plurality of R ¹ are the same as each other Or when n1 is 0, 1 or 2, the plurality of X ¹ may be the same as or different from each other. }
It is preferable that it is a polysiloxane compound which consists of at least 1 type of silane compound represented by these, and / or the hydrolysis-condensation product of this silane compound. Further, from the viewpoint of heat resistance of the single-layer resin stamper, the silicon-containing compound is a polysiloxane compound comprising a hydrolytic condensation product of one or more silane compounds represented by the general formula (1), or the silane compound More preferably, it is a mixture of the polysiloxane compound.

In the general formula (1), R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms. Examples of the organic group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, butyl (eg, n-butyl, i-butyl, t-butyl, sec-butyl, etc.), pentyl (eg, , N-pentyl, i-pentyl, neopentyl, cyclopentyl, etc.), hexyl (eg, n-hexyl, i-hexyl, cyclohexyl, etc.), heptyl (eg, n-heptyl, i-heptyl, etc.), octyl (eg, n -Octyl, i-octyl, t-octyl, etc.), nonyl (eg n-nonyl, i-nonyl etc.), decyl (eg n-decyl, i-decyl etc.), undecyl (eg n-undecyl, i -Undecyl, etc.), dodecyl (eg, n-dodecyl, i-dodecyl, etc.), etc., acyclic or cyclic aliphatic hydrocarbon groups, vinyl, propenyl, Acyclic and cyclic alkenyl groups such as benzyl, phenethyl, 2-methylbenzyl Aralkyl groups such as 3-methylbenzyl and 4-methylbenzyl, araalkenyl groups such as PhCH = CH- groups, aryl groups such as phenyl, tolyl, styryl, or xylyl groups, 4-aminophenyl groups A polymerizable linking group such as a substituted aryl group such as 4-hydroxyphenyl group, 4-methoxyphenyl group, 4-vinylphenyl group, methacryloyl group, acryloyl group, styryl group, norbornyl group, glycidyl group, and mercapto group. And a group to be included.

In addition, in the organic group having 1 to 20 carbon atoms, a part of the main chain skeleton of the organic group is ether bond, ester group (bond), hydroxyl group, thiol group, thioether group, carbonyl group, carboxyl group, carboxylic acid anhydride. Physical bond, thiol group, thioether bond, sulfone group, acryloyl group, methacryloyl group, styryl group, vinyl group, aldehyde group, epoxy group, amino group, substituted amino group, amide group (bond), imide group (bond), imino Partially substituted with a substituent selected from a polar group (polar bond) such as a group, a urea group (bond), a urethane group (bond), an isocyanate group, a cyano group, or a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom It may be. In the general formula (1), when a plurality of R ¹ are present, the plurality of R ¹ may be the same as or different from each other.

In the general formula (1), X ¹ is selected from the group consisting of a hydroxyl group, a halogen atom that is a hydrolyzable substituent, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group having 1 to 6 carbon atoms. . Specific examples of X ^1, for example, a hydroxyl group, a chlorine atom, a bromine atom, a halogen atom such as iodine atom, a methoxy group, an ethoxy group, n- propyl group, iso- propyl group, n- butyloxy group, Examples thereof include alkoxy groups such as t-butyloxy group, n-hexyloxy group and cyclohexyloxy group, and acetoxy groups. Among these, halogen atoms such as chlorine atom, bromine atom and iodine atom, methoxy group, ethoxy group and the like These alkoxy groups and acetoxy groups are preferred because the reactivity of the condensation reaction is high when a polysiloxane compound is synthesized. When a plurality of X ¹ are present, the plurality of X ¹ may be the same as or different from each other.

In the general formula (1), n1 is an integer of 0 to 3, when n1 is 2 or 3, or a plurality of ^{R 1} are identical to each other, or different and have, and n1 is 0 In the case of 1 or 2, the plurality of X ¹ may be the same as or different from each other.

  Examples of the silane compound represented by the general formula (1) include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycid. Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxy Silane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanate Propyl Liethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-octanoylthio-1-propyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-triethoxysilyl -N- (1,3-dimethyl-butylidene), 3-acryloxypropyltrimethoxysilane, N- (p-vinylbenzyl) -N- (trimethoxysilylpropyl) ethylenediamine hydrochloride, 3-glycidoxypropylmethyl Dimethoxysilane, bis [3- (triethoxysilyl) propyl] disulfide, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-mercaptopropyltri Ethoxysilane, N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane , Phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, trimethylchlorosilane, dimethylchlorosilane, methyltrichlorosilane, dimethylchlorosilane, dichloromethylsilane, trichlorosilane, etc. Chlorosilanes containing unsaturated hydrocarbon groups such as alkylchlorosilane, dimethylvinylchlorosilane, methylvinyldichlorosilane, and vinyltrichlorosilane, Aromatic group-containing chlorosilanes such as phenylchlorosilane, diphenylmethylchlorosilane, dimethylphenylchlorosilane, diphenyldichlorosilane, phenylmethyldichlorosilane, phenyltrichlorosilane, dimethylcyclohexylchlorosilane, dicyclohexylmethylchlorosilane, dicyclohexyldichlorosilane, methylcyclohexyldichlorosilane, cyclohexyltri Aliphatic group-containing chlorosilanes such as chlorosilane, dimethylcyclopentylchlorosilane, dicyclopentylmethylchlorosilane, dicyclopentyldichlorosilane, methylcyclopentyldichlorosilane, cyclopentyltrichlorosilane, acryloxypropyldimethylchlorosilane, acryloxypropylmethyldichlorosilane, acryloxypro Le trichlorosilane, methacrolein dimethylchlorosilane, methacrolein propyl methyl dichlorosilane, methacrolein propyl trichlorosilane, styryl dimethylchlorosilane, styryl methyldichlorosilane, styryl trichlorosilane and the like.

  The silane compound represented by the general formula (1) may be used alone, but it is possible to control fluidity before curing, or to control refractive index, hardness, etc. It is preferable to use a silane compound.

  When a plurality of types of silane compounds are used, it is possible to use two or more types of silane compounds having different values of n1 among the silane compounds represented by the general formula (1). From the viewpoint of

[Production method of polysiloxane compound]
Hereinafter, the production of the polysiloxane compound will be described by taking as an example the case of using the silane compound represented by the general formula (1) and / or the condensate thereof, but the present invention is not limited thereto.

In the present embodiment, the polysiloxane compound is preferably produced by adding water to one or more silane compounds represented by the general formula (1) and / or a condensate thereof. The amount of water, preferably in the range of 0.1 to 10 equivalents (mole basis) of the total number of moles of the groups X ¹ of the silane compound represented by the general formula (1), more preferably The range is 0.4 equivalent to 8 equivalent. When the amount of water added is 0.1 equivalent or more, the molecular weight of the polysiloxane compound is increased. On the other hand, when the amount is 10 equivalents or less, the pot life of the polysiloxane compound solution produced by the condensation reaction is lengthened. It is preferable from the viewpoint. When group X ¹ of the silane compound represented by the above general formula (1) used in the condensation reaction are all hydroxyl groups, a silane compound may be condensed without addition of water.

  In the present embodiment, the production of a polysiloxane compound by a condensation reaction in the presence of a catalyst is preferable because the hydrolysis and condensation rates increase.

  Examples of the type of catalyst include an acid catalyst, a base catalyst, and a metal alkoxide. Specifically, examples of the acid catalyst include inorganic acids and organic acids. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, and the like. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, benzoic acid, and p-amino. Examples include benzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, citraconic acid, malic acid, and glutaric acid.

  Examples of the base catalyst include inorganic base catalysts and organic base catalysts. Examples of the inorganic base catalyst include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide and barium hydroxide. And alkali metal or alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate, and metal hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate. Examples of the organic base catalyst include trialkylamines such as ammonia, triethylamine, and ethyldiisopropylamine; N, N-dialkylaniline derivatives having 1 to 4 carbon atoms such as N, N-dimethylaniline and N, N-diethylaniline; Examples thereof include pyridine derivatives which may have an alkyl substituent having 1 to 4 carbon atoms, such as pyridine and 2,6-lutidine.

  Examples of the metal alkoxide include trimethoxy aluminum, triethoxy aluminum, tri-n-propoxy aluminum, tri-iso-propoxy aluminum, tri-n-butoxy aluminum, tri-iso-butoxy aluminum, tri-sec-butoxy. Aluminum, tri-tert-butoxyaluminum, trimethoxyboron, triethoxyboron, tri-n-propoxyboron, tri-iso-propoxyboron, tri-n-butoxyboron, tri-iso-butoxyboron, tri-sec-butoxy Boron, tri-tert-butoxyboron tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra- so-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetramethoxygermanium, tetraethoxygermanium, tetra-n-propoxygermanium, tetra-iso-propoxygermanium, tetra-n-butoxygermanium, tetra- iso-butoxygermanium, tetra-sec-butoxygermanium, tetra-tert-butoxygermanium, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetra-iso-propoxytitanium, tetra-n-butoxytitanium, tetra -Iso-butoxy titanium, tetra-sec-butoxytan, tetra-tert-butoxy titanium, tetramethoxy zirconium, tetraethoxy zirconium, tetra- - propoxy zirconium, tetra -iso- propoxy zirconium, tetra -n- butoxy zirconium, tetra -iso- butoxy zirconium, tetra -sec- butoxy zirconium, tetra--tert- butoxy zirconium, and the like.

  The catalysts listed above can be used singly or in combination of two or more. The amount of the catalyst used is such that the pH of the reaction system when producing the polysiloxane compound is adjusted to a range of 0.01 to 6.9, so that the weight average molecular weight of the polysiloxane compound. Is preferable because it can be controlled well. Moreover, you may adjust the pH with an acid or a base after manufacture of a polysiloxane compound.

  In this embodiment, the condensation reaction for producing the polysiloxane compound can be performed in an organic solvent. Examples of the organic solvent that can be used for the condensation reaction include alcohols, esters, ketones, ethers, aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, amide compounds, and the like.

  Examples of the alcohol include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol, and ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, B propylene glycol monopropyl ether, mono ethers of polyhydric alcohols such as propylene glycol monobutyl ether.

  Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, and γ-butyrolactone.

  Examples of the ketone include acetone, methyl ethyl ketone, methyl isoamyl ketone, and the like.

  Examples of the ether include, in addition to monoethers of the above polyhydric alcohols, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol diester. Polyhydric alcohol ether in which all hydroxyl groups of polyhydric alcohol such as butyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether are alkyl etherified, and tetrahydrofuran, 1,4-dioxane, anisole, propylene glycol monomethyl ether acetate ( Hereinafter, abbreviated as PGMEA). It is below.

  Examples of the aliphatic hydrocarbon compound include hexane, heptane, octane, nonane, decane, and the like.

  Examples of the aromatic hydrocarbon compound include benzene, toluene, xylene and the like.

  Examples of the amide compound include dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  Among the solvents listed above, alcohol solvents such as methanol, ethanol, isopropanol and butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Ether solvents such as monoethyl ether and PGMEA, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone are preferable because they are easily mixed with water.

  The solvents listed above may be used alone or in combination of a plurality of solvents. In addition, the condensation reaction for producing the polysiloxane compound can be performed in bulk without using the solvents listed above.

  The reaction temperature for producing the polysiloxane compound is not particularly limited, but is preferably in the range of −50 ° C. to 200 ° C., more preferably 0 ° C. to 150 ° C. It is preferable to perform the condensation reaction in the above reaction temperature range because the molecular weight of the polysiloxane compound can be well controlled.

  In addition, the polysiloxane compound may include an element that forms an oxide such as titanium, zirconium, aluminum, germanium, boron, phosphorus, nitrogen, carbon, gallium, or chromium.

In the condensation reaction in which the polysiloxane compound is produced using the silane compound in which the group X ¹ is a halogen atom in the general formula (1), an organic base compound is used as a catalyst or a silicon compound scavenger from the viewpoint of the condensation rate. Is preferred.

  Examples of organic base compounds used as catalysts or silicon compound scavengers include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, dia Zabicycloocran, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N Dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, and the like. These organic base compounds can be used individually by 1 type or in mixture of 2 or more types.

The amount of the organic base compound used as a catalyst or silicon compound scavenger is 0.1 to 20 times the equivalent of the silane compound in which the group X ¹ is a halogen atom in the general formula (1). The following is preferable from the viewpoint of facilitating the progress of the silylation reaction, and more preferably 0.5 times or more and 10 times or less. These organic base compounds serve as scavengers for halogenated silanes and generate by-product salts.

The reaction temperature of the condensation reaction using the silane compound in which the group X ¹ is a halogen atom in the general formula (1) is not particularly limited, but is preferably −78 ° C. or higher and 200 ° C. or lower, more preferably −20 It is in the range of not lower than 150 ° C.

Hydrochloric acid salt generated by a method such as washing with water, extraction, precipitation, ion exchange, filtration after the condensation reaction using the silane compound in which the group X ¹ is a halogen atom in the general formula (1), and the reaction system It is preferable to remove and purify the organic base compound therein. By these methods, it is preferable to adjust the pH of the polysiloxane compound comprising the hydrolysis-condensation product of the silane compound represented by the general formula (1) to 6 or more and 8 or less. It is preferable that the pH of the polysiloxane compound is 6 or more and 8 or less because the pot life of the photosensitive resin is increased.

[particle]
In the present embodiment, the photosensitive resin contained in the single-layer resin stamper preferably includes particles in order to have high hardness and improve durability. From the viewpoint of improving the hardness of the single-layer resin stamper, examples of the particles include particles containing titanium, zirconium, silicon, aluminum, germanium, boron, phosphorus, nitrogen, carbon, gallium, chromium and the like. Furthermore, from the viewpoint of obtaining compatibility with other components, the particles are more preferably particles containing an inorganic oxide. Examples of the inorganic oxide include oxides such as titanium, zirconium, silicon, aluminum, germanium, boron, phosphorus, nitrogen, carbon, gallium, and chromium. Among these oxides, silica particles are more preferable from the viewpoint of availability and easy reaction.

  Examples of the silica particles include fumed silica produced by a dry method, colloidal silica produced by a wet method, and the like.

  The fumed silica can be obtained by reacting a compound containing a silicon atom with oxygen and hydrogen in a gas phase. Examples of the compound containing a silicon atom as a raw material include silicon halide (for example, silicon tetrachloride).

  The colloidal silica can be synthesized by a sol-gel method in which a raw material compound is hydrolyzed and condensed, or by condensation of sodium silicate. In the sol-gel method, for example, alkoxysilicon (for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, etc.), a halogenated silane compound (for example, diphenyldichlorosilane, etc.), etc., for example, ammonia or amine Colloidal silica is obtained by hydrolytic condensation polymerization with a catalyst. The alkoxy silicon or halogenated silane compound may be used alone or in combination. From the viewpoint that the linear expansion coefficient is small, it is preferable that impurities such as metal or halogen in the alkoxysilicon or halogenated silane compound are small, and colloidal obtained from alkoxysilicon such as tetramethoxysilane and tetraethoxysilane by a wet method. Silica is more preferred.

  The average primary particle diameter of the silica particles is preferably 1 nm or more and 100 nm or less, more preferably 1 nm or more and 20 nm or less, and further preferably 2 nm or more and 15 nm or less. The average primary particle diameter of the silica particles is preferably 1 nm or more because the hardness of the cured product is improved. On the other hand, the average primary particle diameter of 100 nm or less is preferable because the transparency is improved.

  The average secondary particle diameter of the silica particles is preferably 2 nm or more and 250 nm or less, and more preferably 2 nm or more and 80 nm or less. The average secondary particle diameter of the silica particles is preferably 2 nm or more because the hardness of the cured product is improved. On the other hand, the average particle size of 250 nm or less is preferable because the transparency of the cured product in the wavelength region of 300 nm or less is improved. .

  The average primary particle diameter of the silica particles is a value obtained by calculation from the specific surface area of BET and / or a value obtained by observation with a scanning electron microscope, while the average secondary particle diameter of the silica particles is dynamic It is a value measured with a light scattering photometer.

  The silica particles may have a spherical shape, a rod shape, a plate shape, a fiber shape, or a shape in which two or more of these are combined, and preferably a spherical shape. In the present specification, the term “spherical” includes not only true sphere but also a substantially spherical shape such as a spheroid or oval.

  The silica particles may further contain an element that forms an oxide such as titanium, zirconium, aluminum, germanium, boron, phosphorus, nitrogen, carbon, gallium, or chromium.

  In this embodiment, it is preferable that the content rate of the particle | grains in photosensitive resin is 1 to 80 mass% on the basis of the total mass of photosensitive resin. The content is preferably 1% by mass or more from the viewpoint of improving the hardness of the single-layer resin stamper, and preferably 80% by mass or less from the viewpoint of controlling the viscosity of the photosensitive resin. The content is more preferably 10% by mass or more and 70% by mass or less, and further preferably 20% by mass or more and 60% by mass or less.

  In the present embodiment, the silica particles are preferably chemically bonded to a part of the polysiloxane compound and / or silane compound by Si—O—Si bond from the viewpoint of improving the crack resistance of the single layer resin stamper. . In particular, in order for silica particles to be stably present in the photosensitive resin, it is more preferable that the silica particles are chemically bonded to a part of the polysiloxane compound by Si—O—Si bonds.

  In order to form Si—O—Si bonds between the silica particles and a part of the polysiloxane compound and / or silane compound, the silica particles preferably have a silanol group and / or an alkoxyl group on the surface thereof. . A Si-O-Si bond is formed by the condensation reaction of the silanol group and / or alkoxy group present on the surface of the silica particles with the silanol group and / or alkoxy group in the polysiloxane compound. Further, the silica particles may be modified with other organic groups as long as the silica particles have a silanol group and / or an alkoxyl group.

The number of silanol groups present on the surface of the silica particles is preferably 0.5 to 15 / nm ² , and more preferably 1 to 3 / nm ² . From the viewpoint of the reactivity of the silica particles, the number of silanol groups present on the surface of the silica particles is preferably 0.5 / nm ² or more. On the other hand, from the viewpoint of lowering the water absorption rate of the single-layer resin stamper, It is preferably 15 / nm ² or less. The number of silanol groups can be determined, for example, from ²⁹ Si NMR by adding a relaxation promoting reagent to an aqueous solution or an organic solution.

  Examples of the solvent for dispersing the silica particles include alcohol solvents such as water, methanol, ethanol, isopropanol, and butanol, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and propylene glycol. Examples include ether solvents such as monomethyl ether, propylene glycol monoethyl ether, and PGMEA, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. These are preferable because silica particles having a silanol group can be easily dispersed. These can be used alone or in combination of two or more. The type of dispersion solvent used can vary depending on the surface modifying group of the silica particles used.

  As the silica particles, those suitable for the silica particles as described above can be preferably used, but there is no limitation, and commercially available products can also be used.

  As a commercial item, as colloidal silica, for example, LEVASIL series (manufactured by HC Starck Co., Ltd.), methanol silica sol IPA-ST, same MEK-ST, same NBA-ST, same XBA-ST, same DMAC-ST , ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL Industrial Co., Ltd.), Quateron PL Series (Fuso Chemical Co., Ltd.), OSCAL Series (Catalyst Chemical Industries Co., Ltd.), etc .; As silica powder particles, for example, Aerosil 130, 300, 380 TT600, OX50 (above, manufactured by Nippon Aerosil Co., Ltd.), Sildex H31, H32, H51, H52, H121, H122 (above, Asahi Glass ( ) Made), E220A, E220 (or more, Nippon Silica Kogyo (Ltd.)), SYLYSIA470 (manufactured by Fuji Silysia Chemical (Co., Ltd.)), SG-made flakes (Nippon Sheet Glass Co., Ltd.), and the like.

[Condensation method of polysiloxane compound and / or silane compound and silica particles]
The condensation method of the polysiloxane compound and / or the silane compound and the silica particles is performed by reacting the silica particles dispersed in a solvent with the polysiloxane compound and / or the silane compound represented by the general formula (1). Can be.

  As the solvent, water, an organic solvent, or a mixed solvent thereof can be used. The type of organic solvent used can vary depending on the dispersion medium of the silica particles used. When the dispersion medium of the silica particles used is aqueous, the silica particles are represented by the polysiloxane compound and / or the general formula (1) after adding water and / or alcohol solvent to the aqueous dispersion medium of the silica particles. The silane compound may be reacted with the silane compound, and after the solvent in the silica particle aqueous solution is once substituted with an alcohol solvent, the silica particle is replaced with the polysiloxane compound and / or the silane compound represented by the general formula (1). And may be reacted.

  In the condensation reaction between the polysiloxane compound and / or the silane compound represented by the general formula (1) and the silica particles, examples of the alcohol solvent that can be used as a solvent and a substitution solvent for the silica particles include methanol, ethanol, and n. Examples include -propanol, 2-propanol, n-butanol, methoxyethanol, ethoxyethanol, and the like, and these are preferable because they are easily mixed with water.

  As a dispersion medium for the silica particles used, for example, water or a solvent such as alcohol, ether, ketone, ester, or hydrocarbon can be used. Examples of the alcohol include methanol, ethanol, n-propanol, 2-propanol, n-butanol and the like. Examples of the ether solvent include dimethoxyethane and PGMEA. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, ethyl formate, propyl formate, and γ-butyrolactone. Examples of the hydrocarbon solvent include hexane, heptane, octane, nonane, decane, benzene, toluene, xylene and the like.

  The condensation reaction of the silica particles with the polysiloxane compound and / or the silane compound represented by the general formula (1) may be performed in either an acidic atmosphere or a basic atmosphere. In order to prevent gelation or cloudiness in the condensation reaction, the pH of the reaction system is preferably in the range of 3 to 10, and more preferably in the range of 5 to 9.

  In the present embodiment, a catalyst may be used in the condensation reaction between the silica particles and the polysiloxane compound and / or the silane compound represented by the general formula (1). As the catalyst, the same catalyst as that used in the production of the polysiloxane compound can be used. The catalyst may be removed after the production of the polysiloxane compound, but when the silica particles are reacted as they are without removing the catalyst after the production of the polysiloxane compound, the polysiloxane compound is reacted without adding the catalyst again. With the catalyst used at the time, the polysiloxane compound and / or the condensation reaction of the silane compound represented by the general formula (1) and the silica particles can be performed. Moreover, you may add a catalyst anew at the time of the condensation reaction of a polysiloxane compound and / or the silane compound represented by the said General formula (1), and a silica particle.

  When an acid catalyst is added during the production of the polysiloxane compound, the polysiloxane compound is subjected to a condensation reaction between the silica particles and the polysiloxane compound and / or the silane compound represented by the general formula (1). The condensation reaction may be carried out by adding a base catalyst to neutralize the condensation reaction system or adjusting to basicity.

  The reaction temperature for producing the polysiloxane compound and / or the condensation reaction product of the silane compound represented by the general formula (1) and the silica particles is not particularly limited, but is preferably −50 ° C. or more and 200 ° C. or less. More preferably, it is the range of 0 degreeC or more and 150 degrees C or less. Controlling the condensation rate (polysiloxane-silica condensation rate) between the polysiloxane compound and / or the silane compound represented by the general formula (1) and the silica particles by performing the condensation reaction within the above reaction temperature range. Can do.

  After the condensation reaction that occurs during the synthesis of the polysiloxane compound and / or after the condensation reaction of the polysiloxane compound and / or the silane compound represented by the general formula (1) and the silica particles, washing by distillation, extraction, or ion It is preferable to adjust the pH of the produced silica particle-containing condensation reaction product to 6 or more and 8 or less by removing the catalyst by a method such as exchange. When the pH of the silica particle-containing condensation reaction product is 6 or more and 8 or less, the pot life of the photosensitive resin containing the silica particle-containing condensation reaction product is preferably increased.

  The water used for the condensation reaction of the polysiloxane compound and / or the silane compound represented by the above general formula (1) and the silica particles is added by the method such as distillation after adding the solvent listed above. It is preferable that the water content in the condensation reaction product containing silica particles is reduced to 1% by mass or less (based on the total mass of the condensation reaction product containing silica particles). Adjusting the moisture in the silica particle-containing condensation reaction product in this way is preferable because when the condensation reaction product is cured, there is little decrease in mass, shrinkage is reduced, and cracks are less likely to occur. The water content in the silica particle-containing condensation reaction product can be measured by, for example, a gas chromatogram or a Karl Fischer method.

  Also, when curing the photosensitive resin, the content of the solvent contained in the silica particle-containing condensation reaction product is such that the decrease in mass is small, shrinkage is reduced, and cracks are less likely to occur. The content is preferably 1% by mass or less based on the total mass of the reaction product. The content of the solvent can be measured using, for example, a gas chromatogram.

  In the present specification, the “reaction component” means a component that forms a condensation structure in the silica particle-containing condensation reaction product. The content of the silica particles in the reaction component is preferably 1% by mass or more and 80% by mass or less based on the total mass of the reaction component. The content of the silica particles is preferably 1% by mass or more from the viewpoint of improving the hardness of the single-layer resin stamper, and is preferably 80% by mass or less from the viewpoint of controlling the viscosity of the silica particle-containing condensation reaction product. The content of the silica particles is more preferably 10% by mass to 70% by mass, and further preferably 20% by mass to 60% by mass. The content rate of the silica particles is represented by mass% of the reaction component of the silica particles in the silica particle-containing condensation reaction product, and the mass% of the reaction component of the silica particles is calculated from the mass of the silica particles used for the reaction. The reaction component other than silica particles contains a polysiloxane compound and / or a silane compound represented by the general formula (1), and the content of reaction components other than silica particles in the silica particle-containing condensation reaction product is 20 It is preferable that they are mass% or more and 99 mass% or less.

The content of reaction components other than silica particles in the silica particle-containing condensation reaction product is 100% by mol of the reaction components excluding silica particles, and the mol ratio of the raw materials used in the reaction and mol% from ¹ HNMR and ²⁹ SiNMR measurements. Can be calculated as

  In the present specification, the condensation rate of the condensation reaction product is defined as the bond in which the silicon in the condensation reaction product forms a siloxane bond, a direct bond with a hydroxyl group, and a direct bond with the hydrolyzable group. Defined as the ratio of the number of bonds forming the siloxane bond to the total number. The condensation rate of the condensation reaction product is preferably 40 mol% or more and 100 mol% or less, more preferably 50 mol%, from the viewpoint of obtaining good effects of increasing hardness and reducing tackiness by forming a condensed structure. It is 100 mol% or less, more preferably 60 mol% or more and 100 mol% or less.

The condensation rate of the condensation product is calculated by confirming the components of M0, M1, D0, D1, D2, T0, T1, T2, T3, Q0, Q1, Q2, Q3, and Q4 by analyzing with ²⁹ SiNMR. it can. Here, M is a Si atom having one bond that is bonded to an O atom, D is a Si atom having two bonds that are bonded to an O atom, and T is an O atom. Si atom having three bond hands bonded to each other, Q means Si atom having four bond hands bonding to an O atom, and the numbers 0 to 4 are Si atoms. Means the number of Si-O-Si bonds involved. For example, the D1 component means a component having a Si atom involved in one Si—O—Si bond among Si atoms having two bonds bonded to an O atom. .

The condensation rate of the condensation reaction product can be calculated as follows from the area ratio of each silicon peak of ²⁹ SiNMR.
For example, the peak area of the D1 component is represented as (D1).
Condensed silicon area:
{(M1) + (D1) + (D2) × 2 + (T1) + (T2) × 2 + (T3) × 3 + (Q1) + (Q2) × 2 + (Q3) × 3 + (Q4) × 4}
Total silicon area:
{(M0) + (M1)} + {(D0) + (D1) + (D2)} × 2 + {(T0) + (T1) + (T2) + (T3)} × 3 + {(Q0) + ( Q1) + (Q2) + (Q3) + (Q4)} × 4
Condensation rate = [(condensed silicon area) / (total silicon area)] × 100

  In the present embodiment, the mass average molecular weight of the silica particle-containing condensation reaction product is preferably in the range of 1,000 to 200,000, more preferably in the range of 1,000 to 100,000. The mass average molecular weight of the silica particle-containing condensation reaction product can be determined, for example, by gel permeation chromatography (GPC) in terms of standard polymethyl methacrylate. When the mass average molecular weight of the silica particle-containing condensation reaction product is 1,000 or more, the single-layer resin stamper has high heat resistance, and further the pot life of the photosensitive resin containing the silica particle-containing condensation reaction product is increased. When the mass average molecular weight is 200,000 or less, the viscosity of the photosensitive resin containing the silica particle-containing condensation reaction product can be lowered, so that the mold filling property is improved and the shape transfer property is improved.

  When the silica particles and the polysiloxane compound and / or the silane compound represented by the general formula (1) are subjected to a condensation reaction, the silica particles and the polysiloxane compound and / or the silane compound may be reacted at the same time. A silane compound may be further reacted with the condensation reaction product obtained by reacting the particles with the polysiloxane compound, or the polysiloxane compound may be further reacted after reacting the silica particles with the silane compound.

[Photopolymerizable functional group]
In the present embodiment, the photosensitive resin preferably has a photopolymerizable functional group. In this specification, the “photopolymerizable functional group” means a functional group that can be polymerized by irradiating light, and the polymerization reaction by light irradiation is one kind of functional group in the presence of a photopolymerization initiator. The thing which occurs by group, or the thing which superposition | polymerization occurs by combining two or more types of functional groups is also included. Examples of the photopolymerization include radical polymerization, cationic polymerization, and addition reaction by enethiol reaction.

  Examples of the photopolymerizable functional group include (meth) acryloyl group, epoxy group, glycidyl group, oxetane, vinyl ether, mercapto group, styryl group, norbornyl group, vinyl group, allyl group, and other unsaturated carbon bonds. Group and the like. In addition, a hydrogen atom or a part of the main chain skeleton of these various hydrocarbon groups may be, for example, a hydrocarbon group, an ether bond, an ester group (bond), a hydroxyl group, a thioether group, a carbonyl group, a carboxyl group, or a carboxylic acid anhydride. Product bond, thioether bond, sulfone group, aldehyde group, amino group, substituted amino group, amide group (bond), imide group (bond), imino group, urea group (bond), urethane group (bond), isocyanate group, cyano It may be partially substituted with a substituent selected from a polar group (polar bond) such as a group or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

  Among the photopolymerizable functional groups, the photopolymerizable functional group is preferably a (meth) acryloyl group, a styryl group, a norbornyl group, an epoxy group, a mercapto group, and is curable from the viewpoint of reactivity during synthesis. In view of the above, a (meth) acryloyl group and / or a styryl group is more preferable. The type of photopolymerization is preferably radical polymerization from the viewpoint of curability.

  In the present embodiment, components other than the silicon-containing compound in the photosensitive resin may have a photopolymerizable functional group, and when the photosensitive resin contains particles, the photopolymerizable functional group on the particle surface. May be modified. In particular, from the viewpoint of curability when molding a single layer resin stamper, it is preferable that the silicon-containing compound has a photopolymerizable functional group. Further, from the viewpoint of improving crack resistance, the polysiloxane compound and / or silane compound preferably has a photopolymerizable functional group, and from the viewpoint of further improving the heat resistance stability, the polysiloxane compound is a photopolymerizable functional group. It is preferable to have.

In particular, at least one of the silane compound represented by the above general formula (1) and the condensate thereof is capable of photoradical polymerization (for example, a carbon double bond group, a carbon triple bond group, etc.). It is preferable that the ratio of the silicon atom to which the unsaturated carbon bonding group which can be contained and photoradically polymerized has couple | bonded is 5 mol% or more and 80 mol% or less among all the silicon atoms contained in these components. More preferably, it is more than mol% and 70 mol% or less, More preferably, it is 15 mol% or more and 50 mol% or less. By setting the above ratio to 5 mol% or more, the cured product can be made to have high hardness, while by setting it to 80 mol% or less, the single layer resin stamper has high heat resistance, high light resistance and low shrinkage. Can be sex. Further, the ratio can be calculated from the molar ratio of the reactants, the molar ratio of the starting materials used in the reaction, can be calculated from the ¹ HNMR analysis and ²⁹ Si NMR analysis of a solution or a solid.

<Other photosensitive resin components>
[Compound having photopolymerizable functional group in molecule]
In this embodiment, a photosensitive material having excellent characteristics including improved refractive index, improved curability, improved adhesion, improved flexibility of a single-layer resin stamper, and improved handling properties by reducing the viscosity of the photosensitive resin. In order to provide the photosensitive resin, it is preferable that the photosensitive resin further includes a compound having no photopolymerizable functional group and no silicon in the molecule in addition to the silicon-containing compound having the photopolymerizable functional group. . The compound having no silicon in the molecule and having a photopolymerizable functional group can be added to the photosensitive resin alone or as a mixture of two or more.

  Examples of the photopolymerizable functional group contained in the compound having no silicon in the molecule and having a photopolymerizable functional group include (meth) acryloyl group, epoxy group, glycidyl group, oxetane, vinyl ether, mercapto group, And a styryl group, a norbornyl group, a vinyl group, an allyl group, and other groups having an unsaturated carbon bond. A hydrogen atom or a part of the main chain skeleton of these various hydrocarbon groups is, for example, a hydrocarbon group, an ether bond, an ester group (bond), a hydroxyl group, a thioether group, a carbonyl group, a carboxyl group, or a carboxylic acid anhydride bond. , Thioether bond, sulfone group, aldehyde group, amino group, substituted amino group, amide group (bond), imide group (bond), imino group, urea group (bond), urethane group (bond), isocyanate group, cyano group, etc. May be partially substituted with a substituent selected from a polar group (polar bond) or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom. From the viewpoint of curability of the photosensitive resin, a (meth) acryloyl group and / or styryl group is more preferable, and from the viewpoint of low shrinkage during curing of the photosensitive resin, an epoxy group and / or a mercapto group is more preferable, and From the viewpoint of easy adjustment of viscosity or refractive index due to the large number of compounds, a (meth) acryloyl group is more preferable.

  Examples of the compound having a (meth) acryloyl group in the molecule include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-ethylhydroxyethyl phthalate, 2- (meth) acrylic acid. Leuoxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl phthalate, 2-ethyl, 2-butyl-propanediol (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, benzyl (meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, caprolactone (meth) acrylate, cetyl (meth) acrylate, ethylene oxide (EO) modification Cresol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, dimethylol Dicyclopentane di (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxy Phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobornyl (meth) acrylate, isobutyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, isostearyl (meth) acrylate, iso Myristyl (meth) acrylate, Lauroxy polyethylene glycol (meth) acrylate, Lauryl (meth) acrylate, Methoxydipropylene glycol (meth) acrylate, Methoxytripropylene glycol (meth) acrylate, Methoxypolyethylene glycol (meth) acrylate, Methoxytriethylene Glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate G

Octoxy polyethylene glycol-polypropylene glycol (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin (ECH) modified phenoxy (meth) acrylate, phenoxydiethylene glycol (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) (meth) acrylate, poly (propylene glycol-tetra Methylene glycol) (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene Glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, t-butyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tridecyl ( (Meth) acrylate, di (meth) acrylated isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ( (Meth) acryloxy polyethylene glycol (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tricyclodecane dimethanol di ( ) Acrylate, paraphenylphenoxyethyl (meth) acrylate, paraphenylphenyl (meth) acrylate, phenylglycidyl ether (meth) acrylate, phenol (meth) acrylate modified with 3 to 15 moles of ethylene oxide, 1 to 15 moles Cresol (meth) acrylate modified with ethylene oxide, nonylphenol (meth) acrylate modified with 1 to 20 mol of ethylene oxide, nonylphenol (meth) acrylate modified with 1 to 15 mol of propylene oxide, 1 to 30 Di (meth) acrylate containing 1 mol of ethylene glycol chain, di (meth) acrylate containing 1 to 30 mol of propylene glycol chain, bisphenol A modified with 1 to 30 mol of ethylene oxide Di (meth) acrylate, bisphenol A di (meth) acrylate modified with 1 to 30 moles of propylene oxide, bisphenol F di (meth) acrylate modified with 1 to 30 moles of ethylene oxide, and 1 to 30 moles of Bisphenol F di (meth) acrylate modified with propylene oxide, ditrimethylolpropane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate Rate, trimethylolpropane tri (meth) acrylate modified with 1-15 moles of propylene oxide, trimethylolpropane tri (meth) acrylate modified with 1-20 moles of ethylene oxide, 1-20 moles of ethylene oxide Modified pentaerythritol tetra (meth) acrylate, glyceryl tri (meth) acrylate modified with 1 to 20 mol of ethylene oxide, glyceryl tri (meth) acrylate modified with 1 to 20 mol of propylene oxide, glycerol tri ( (Meth) acrylate, ethylated pentaerythritol tri (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, dipentaerythritol penta (meth) modified with 1 mol of alkyl group Acrylate, dipentaerythritol tetra (meth) acrylate modified with 2 mol alkyl group, dipentaerythritol tri (meth) acrylate modified with 3 mol alkyl group, pentaerythritol ethoxytetra (meth) acrylate, n-hexyl (Meth) acrylate, n-decyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether Di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane dimethylol di (meth) acrylate, dicyclopentanyl dimethylol di (meth) acrylate and the like.

  The amount of the compound having a (meth) acryloyl group in the molecule is preferably 900 parts by mass or less, more preferably 5 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the silicon-containing compound. . It is preferable to add a compound having a (meth) acryloyl group in the molecule because cracks due to temperature impact of the single-layer resin stamper can be prevented. Moreover, if the addition amount of the compound having a (meth) acryloyl group in the molecule is 900 parts by mass or less with respect to 100 parts by mass of the silicon-containing compound, the single-layer resin stamper has more excellent high refractive index and high transparency. And high heat resistance is preferable.

  In the present embodiment, the photosensitive resin does not have silicon in the molecule and includes a compound having a carbocycle and / or a heterocycle as a compound having a photopolymerizable functional group. From the viewpoints of improving the Abbe number, reducing the shrinkage rate, and improving the hardness of the single-layer resin stamper.

Examples of the compound having a carbocycle and / or a heterocycle include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-ethylhydroxyethyl phthalate, 2- (meth) acryloyloxyethyl hexa Hydrophthalate, 2- (meth) acryloyloxypropyl phthalate, benzyl (meth) acrylate, EO-modified cresol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, ethoxylated phenyl (meth) acrylate, isobornyl (meth) acrylate, paracumyl fe Xylethylene glycol (meth) acrylate, ECH-modified phenoxy (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, tricyclo Decandimethanol di (meth) acrylate, paraphenylphenoxyethyl (meth) acrylate, paraphenylphenyl (meth) acrylate, phenylglycidyl ether (meth) acrylate, phenol (meth) acrylate modified with 3 to 15 moles of ethylene oxide , Cresol (meth) acrylate modified with 1 to 15 moles of ethylene oxide, 1 to 20 moles of ethylene oxide Modified nonylphenol (meth) acrylate, nonylphenol (meth) acrylate modified with 1 to 15 mol of propylene oxide, bisphenol A di (meth) acrylate modified with 1 to 30 mol of ethylene oxide, 1 to 30 mol of Bisphenol A di (meth) acrylate modified with propylene oxide, bisphenol F di (meth) acrylate modified with 1 to 30 mol of ethylene oxide, and bisphenol F di (meth) modified with 1 to 30 mol of propylene oxide ) Acrylate, bisphenol A diglycidyl ether di (meth) acrylate, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane dimethylol di (meth) acrylate, dicyclopentanyl dimethylol di (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, di (meth) acrylated Isocyanurate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, imide (meth) acrylate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, etc. Is mentioned.

  Among these compounds having carbocycles and / or heterocycles, (meth) acrylate compounds having carbocycles and / or heterocyclic compounds are dicyclocyclopropylenes from the viewpoint of improving the refractive index and Abbe number and availability. Pentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, isobornyl (meth) ) It is preferably at least one compound selected from the group consisting of acrylates.

  Moreover, you may add a reactive oligomer for viscosity adjustment as a compound which does not have silicon in the said molecule | numerator, and has a photopolymerizable functional group. Examples of the reactive oligomer include unsaturated polyester, polyene / thiol, polybutadiene, and polystyrylethyl methacrylate. These reactive oligomers include monofunctional unsaturated compounds and polyfunctional unsaturated compounds. Either monofunctional unsaturated compounds or polyfunctional unsaturated compounds may be used, or both of them may be used in combination. Alternatively, a plurality of types of monofunctional unsaturated compounds and / or polyfunctional unsaturated compounds may be mixed and used. When adding a reactive oligomer, although the addition amount of a reactive oligomer is dependent on the amount of other additive components, 900 mass parts or less are preferable with respect to 100 mass parts of silicon containing compounds. If the addition amount of the reactive oligomer is 900 parts by mass or less, the single-layer resin stamper can have more excellent high refractive index, high permeability, and high heat resistance.

  In this embodiment, the lower limit of the photopolymerizable functional group equivalent of the photosensitive resin is preferably 0.5 mmol (mmol) / g or more from the viewpoint of crack resistance of the single-layer resin stamper, and is 1.0 mmol / g. More preferably, it is more preferably 1.2 mmol / g or more. In addition, the upper limit of the photopolymerizable functional group equivalent of the photosensitive resin is preferably 4.5 mmol / g or less, preferably 4.0 mmol / g or less, from the viewpoint of volume shrinkage during curing by light irradiation. More preferably, it is more preferably 3.5 mmol / g or less.

In this specification, the “photopolymerizable functional group equivalent” is the number of moles of photopolymerizable functional group per 1 g of the photosensitive resin, and the photopolymerizable functional group does not contain a silicon-containing compound and / or silicon. It is derived from a compound having a photopolymerizable functional group in other molecules. The photopolymerizable functional group equivalent derived from the silicon-containing compound is calculated by dividing the molar amount of the photopolymerizable functional group in the raw material used to produce the silicon-containing compound by the weight of the obtained silicon-containing compound. it can. The photopolymerizable functional group equivalent derived from a compound having a photopolymerizable functional group in another molecule can be calculated by dividing the number of photopolymerizable functional groups in the molecule by the molecular weight. The photopolymerizable functional group equivalent of a silicon-containing compound is X (A), and the photopolymerizable functional group equivalent of a compound having a photopolymerizable functional group in another molecule is X (B). When the weight ratio of the compound is Y (A) and the weight ratio of the compound having a photopolymerizable functional group in the other molecule is Y (B), the photopolymerizable functional group equivalent in the photosensitive resin is represented by the following formula. :
Photopolymerizable functional group equivalent in photosensitive resin = X (A) × Y (A) + X (B) × Y (B)
Can be calculated according to

[Photopolymerization initiator]
It is preferable to add a photopolymerization initiator to the photosensitive resin according to the present invention for the purpose of imparting photosensitivity. By adding a photopolymerization initiator, photoradical polymerization and / or photocationic polymerization of the photosensitive resin can be advanced. Preferred photopolymerization initiators include the following compounds having absorption at a wavelength of 365 nm.

(Photo radical polymerization initiator)
(1) Benzophenone derivatives: for example, benzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone,

(2) Acetophenone derivatives: for example, trichloroacetophenone, 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-methyl) Propionyl) -benzyl] -phenyl} -2-methylpropan-1-one, methyl phenylglyoxylate, (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -Phenyl} -2-methyl-propan-1-one) (IRGACURE (registered trader) manufactured by BASF Corporation ) 127),

(3) Thioxanthone derivatives: for example, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone,

(4) Benzyl derivatives: for example, benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal,

(5) Benzoin derivatives: for example, benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1phenylpropan-1-one,

(6) Oxime compounds: for example, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2 -(O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl) Oxime)] (IRGACURE (registered trademark) OXE01 manufactured by BASF Corporation), ethanone, 1- [9-ethyl-6- 2-methylbenzoyl) -9H- carbazol-3-yl] -, 1- (O- acetyloxime) (manufactured by BASF Ltd. IRGACURE (R) OXE02),

(7) α-hydroxy ketone compounds: for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane,

(8) α-aminoalkylphenone compounds: for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE (registered trademark) 369 manufactured by BASF Corporation), 2- Dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one,

(9) Phosphine oxide compounds: for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN (registered trademark) TPO manufactured by BASF Corporation),

(10) Titanocene compound: for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium,

(11) Benzoate derivatives: for example, ethyl-p- (N, N-dimethylaminobenzoate),

(12) Acridine derivative: For example, 9-phenylacridine.

(Photocationic polymerization initiator)
Examples of the cationic photopolymerization initiator include PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbCl ₆ ²⁻ , BF ₄ −, SnCl ₆ ⁻ , FeCl ₄ ⁻ , BiCl ₅ ^{2− and the} like as anions. An aryldiazonium salt is mentioned. Further, as anions, PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbCl ₆ ²⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , FSO ₃ ⁻ , F ₂ PO ₂ ⁻ , B (C Diaryl iodonium salts, triaryl sulfonium salts, and triaryl selenonium salts having ₆ F ₅ ) ₄ ^{— and the} like can be used. Further, as the cationic photopolymerization initiator, for example, dialkylphenacylsulfonium salt, dialkyl-4-hydroxyphenylsulfonium salt, α-hydroxy having PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ^— or the like as an anion. Methylbenzoin sulfonic acid ester, N-hydroxyimide sulfonate, α-sulfonyloxy ketone, sulfonic acid ester such as β-sulfonyloxy ketone, iron allene compound, silanol-aluminum complex, o-nitrobenzyl-triphenylsilyl ether Etc. Further, examples of the cationic photopolymerization initiator include aryl diazonium salts having PF ₆ ⁻ , AsF ₆ ^{— and the} like.

  As a commercial item of a photocationic polymerization initiator, SP-150, SP-152, SP-170, SP-172 (Optomer made by ADEKA Co., Ltd.) etc. are mentioned, for example.

  Among the photoradical initiators listed above, the above (2) acetophenone derivative, (8) α-aminoalkylphenone compound, or (9) phosphine oxide compound is preferable from the viewpoint of high sensitivity. Furthermore, from the viewpoint of high transparency and high sensitivity of the single-layer resin stamper, the above (9) phosphine oxide compound, among them, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (LUSFIRIN (manufactured by BASF Corporation) (Registered trademark) TPO) is preferred.

  Among the photocationic initiators listed above, iodonium salt type initiators are particularly preferable from the viewpoint of compatibility with the polysiloxane compound. An iodonium salt type initiator is available, for example, as iodonium {4- {2methylpropyl} phenyl}} {4-methylphenylhexafluorophosphate} (manufactured by BASF Corporation, IRGACURE (registered trademark) 250). .

  A radical photopolymerization initiator can be used individually by 1 type or in combination of 2 or more types. Moreover, a photocationic polymerization initiator can be used individually by 1 type or in combination of 2 or more types. Furthermore, although a photo radical initiator and a photo cation initiator may be used in combination, the use of only a photo radical initiator is preferable from the viewpoint of curability.

  In addition to the photopolymerization initiator, for example, a photopolymerization initiation assistant, a sharpening agent, a thermal radical initiator, and the like may be further used in combination. Examples of the thermal radical initiator include various organic peroxides such as ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and peroxyester. An oxide can be used.

  Although the addition amount of a photoinitiator is dependent on the quantity of another additive, 0.01 mass part or more and 50 mass parts or less are preferable with respect to 100 mass parts of silicon containing compounds, and 0.05 mass part or more and 10 mass parts or more. The amount is more preferably equal to or less than part by weight, and further preferably equal to or greater than 0.1 part by weight and equal to or less than 5 parts by weight. When the photopolymerization initiator is added in an amount of 0.01 parts by mass or more, active species sufficient for photopolymerization to proceed sufficiently during exposure are supplied, and curing of the exposed part proceeds sufficiently. On the other hand, if it is 50 parts by mass or less, the exposure absorption near the surface of the coating film does not become too large, and the exposure light beam reaches the vicinity of the substrate surface, so that photopolymerization occurs in the film. Since it becomes uniform in the thickness direction, a practical single-layer resin stamper can be obtained, and coloring after photocuring or baking by heat is small.

[Antioxidant and / or UV absorber]
In this embodiment, from the viewpoint of improving heat resistance and light resistance, an antioxidant and / or an ultraviolet absorber may be added to the photosensitive resin. Examples of the antioxidant and / or ultraviolet absorber include the following substances (1) to (10).

(1) Hindered phenol antioxidant: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert) -Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionamide], benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C ₇ -C ₉ side chain alkyl ester, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-trii ) Tri-p-cresol, calcium diethylbis [[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -o -Cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5 -Reactivity of triazine-2,4,6- (1H, 3H, 5H) -trione, N-phenylbenzenamine and 2,4,4-trimethylpentene 2,4,6-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, 2,4-dimethyl-6- (1-methyl) Pentadecyl) phenol,

(2) Phosphorus heat stabilizer: tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorus acid,

(3) Sulfur-based heat stabilizer: didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate

(4) Benzotriazole UV absorber: 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl- 1-phenylethyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2,2'-methylenebis [6 -(2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], methyl 3- (3- (2H-benzotriazol-2-yl) ) The reaction product of -5-tert-butyl-4-hydroxyphenyl) propionate and ethylene glycol 300, 2-(2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol,

(5) Cyanoacrylate UV absorber: 2,2-bis {[2-cyano-3,3-diphenylacryloyl] methyl} propane-1,3-diyl bis (2-cyano-3,3-diphenylacrylic) Rat), ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate,

(6) Triazine ultraviolet absorber: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol,

(7) Benzophenone ultraviolet absorbers: octabenzone, 2,2'-dihydroxy-4,4'-dimethoxybenphenone, 2,2'-4,4'-tetrahydrobenphenone,

(8) Hindered amine photothermal stabilizer: dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine And N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5 -Triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] , polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-olefin _(C 20 _{~C 24)} · maleic anhydride-4-amino-2,2,6 , 6-Tetramethyl Peridine copolymer, bis (1,2,2,6,6-pentamethyl-4-piperidine) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (2,2,6,6- Tetramethyl-4-piperidyl) sebacate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N′-diformylhexamethylenediamine,

(9) Other heat stabilizers: 3,4-dihydro-2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) -2H-benzopyran-6-ol, 2 ′ , 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide,

(10) Other ultraviolet absorbers: 2-ethylhexyl-4-methoxycinnamate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

  From the viewpoint of solubility in a photosensitive resin, the antioxidant and / or ultraviolet absorber is more preferably the above (1) hindered phenol-based antioxidant and (7) hindered amine-based photothermal stabilizer. Bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (IRGANOX (registered trademark) 245 manufactured by BASF Corporation), pentaerythritol tetrakis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate] (IRGANOX (registered trademark) 1010 manufactured by BASF Corporation) and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ( IRGANOX (registered trademark) 1076 manufactured by BASF Corporation Preferred.

  Antioxidants and / or ultraviolet absorbers can be used singly or in combination of two or more.

  Although the addition amount of antioxidant and / or ultraviolet absorber depends on the amount of other additives, it is preferably 50 parts by mass or less, more than 0 part by mass and 5 parts by mass with respect to 100 parts by mass of the silicon-containing compound. Is more preferably 0.1 parts by mass or more and 2 parts by mass or less.

  By adding an antioxidant and / or an ultraviolet absorber, in addition to thermal stability in a nitrogen atmosphere, thermal stability in an air atmosphere can be improved, while on the other hand, from the viewpoint of handling of a photosensitive resin Therefore, the addition amount of the antioxidant and / or the ultraviolet absorber is preferably 50 parts by mass or less.

[Other additive components]
In the present embodiment, an adhesion aid may be added to the photosensitive resin as a compound having a photopolymerizable functional group in the molecule in order to improve adhesion with various support substrates. Examples of the adhesion assistant include a silane coupling agent. More specifically, for example, an alkoxysilane containing a hydrogen atom directly bonded to a silicon atom, an alkoxy containing an epoxy group and / or a thiol group. Organic alkoxysilane compounds such as alkoxysilanes containing unsaturated bonds such as silane and vinyl groups, compounds obtained by hydrolysis of some or all of these organic alkoxysilane compounds, and condensates thereof .

  More specifically, examples of the adhesion assistant include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacrylic Loxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2- (amino Til) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureido Propyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, Lutris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-octanoylthio-1-propyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-triethoxysilyl-N- ( 1,3-dimethyl-butylidene), 3-acryloxypropyltrimethoxysilane, N- (p-vinylbenzyl) -N- (trimethoxysilylpropyl) ethylenediamine hydrochloride, 3-glycidoxypropylmethyldimethoxysilane, bis [3- (Triethoxysilyl) propyl] disulfide, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-mercaptopropyltriethoxysilane, N- ( 1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane and the like.

  Although the addition amount of the said silane coupling agent is dependent on the quantity of another additive, 0.01 mass part or more and 10 mass parts or less are preferable with respect to 100 mass parts of silicon containing compounds, 0.05 mass part or more 5 parts by mass or less is more preferable. The addition amount of the silane coupling agent is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the silicon-containing compound from the viewpoint of improving adhesiveness, and is 10 parts by mass or less from the viewpoint of storage stability. preferable.

  In this embodiment, an inorganic filler may be further added to the photosensitive resin regardless of the presence or absence of the adhesion aid. The inorganic filler preferably has an average particle size of a wavelength or less used depending on the application of the photosensitive resin or resin stamper in order to avoid an adverse effect on light transmittance, and the average particle size is preferably 100 nm or less. is there. Inorganic fillers can be used in resins, for example, to improve mechanical properties and / or improve thermal conductivity. Although the minimum of the average particle diameter of an inorganic filler is not specifically limited, It is preferable that it is 0.1 nm or more so that photosensitive resin may have a low viscosity and favorable moldability. In this specification, the average particle diameter of the inorganic filler is a value obtained by calculation from the specific surface area of BET. The addition amount of the inorganic filler may be selected according to the application of the present invention and depends on the amount of other additives, but for example, 1 part by mass to 60 parts by mass with respect to 100 parts by mass of the silicon-containing compound. More preferably, they are 5 mass parts-60 mass parts, More preferably, they are 5 mass parts-40 mass parts.

  In this embodiment, the viscosity can also be adjusted by adding a solvent to the photosensitive resin, regardless of the presence or absence of an adhesion assistant and / or an inorganic filler. Suitable solvents include, for example, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, tetrahydrofuran, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine. , Cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether, PGMEA, methyl ethyl ketone, methyl Examples include isobutyl ketone, anisole, ethyl acetate, ethyl lactate, and butyl lactate. These can be used alone or in combination of two or more. Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, or PGMEA is particularly preferable. These solvents can be appropriately added to the photosensitive resin in accordance with the coating film thickness and viscosity of the photosensitive resin. The amount of these solvents added is preferably 900 with respect to 100 parts by mass of the silicon-containing compound. The range is less than or equal to part by mass, more preferably between 0.01 and 900 parts by mass.

  In this embodiment, a sensitizer for improving photosensitivity can be further added to the photosensitive resin. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylaminobenzylidene) cyclohexanone. 2,6-bis (4′-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) chalcone, 4,4′-bis (diethylamino) chalcone, 2- (4′-dimethylaminocinnamylidene) indanone, 2- (4′-dimethylaminobenzylidene) indanone, 2- (p-4′-dimethylaminobiphenyl) benzo Thiazole, 1,3-bis (4-dimethylaminobenzyl) Den) acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethyl Aminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, N, N-bis (2-hydroxyethyl) aniline, 4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, 4-diethylaminobenzoic acid Amyl, benztriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3,4-tetrazole, 1- ( tert-butyl) -5-mercapto-1,2,3,4-tetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2 -(P-dimethylaminostyryl) naphtho (1,2-p) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like.

  Moreover, a sensitizer can be used individually by 1 type or in combination of 2 or more types. Although the addition amount of a sensitizer is dependent on the quantity of another additive, it is preferable that it is 10 mass parts or less with respect to 100 mass parts of silicon containing compounds, and it is 1 mass part-5 mass parts. More preferred.

  In the present embodiment, a polymerization inhibitor can be further added to the photosensitive resin in order to improve the stability during storage and / or the photosensitivity. Examples of the polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2, 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N -Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis ( 4-hide Carboxymethyl-3,5-di-tert- butyl) phenyl methane, and the like. Although the addition amount of a polymerization inhibitor is dependent on the quantity of another additive, it is preferable that it is 5 mass parts or less with respect to 100 mass parts of silicon containing compounds, and is 0.01 mass part-1 mass part. It is more preferable.

  In this embodiment, a lubricant, an antistatic agent, a release agent, a foaming agent, a nucleating agent, a coloring agent, a crosslinking agent, a dispersion aid, a plasticizer, a flame retardant, and the like can be further added to the photosensitive resin. These materials are mixed with the photosensitive resin and any other components using known methods (eg, centrifugation, etc.), and the resulting mixture is foamed using known methods (eg, vacuum defoaming, etc.). It is preferable to be removed.

(Method for producing photosensitive resin)
In this embodiment, a silicon-containing compound and various additive components are put in a glass container, a plastic container or the like, and generally known stirring devices such as a web rotor, a magnetic stirrer, a motor-driven stirrer, and a stirring blade are used. The photosensitive resin can be prepared by mixing uniformly using

  The temperature during mixing of the silicon-containing compound and various additive components is preferably 20 ° C. or higher and 80 ° C. or lower. The temperature at the time of mixing is preferably 20 ° C. or higher because the mixed components can be uniformly mixed. On the other hand, it is preferably 80 ° C. or lower because deterioration of each mixed component can be prevented.

<Molding method of single layer resin stamper>
In this embodiment, the following steps:
A filling step of filling the matrix having the pattern with the photosensitive resin;
A laminating step of superimposing a matrix having a substrate or a pattern on a single layer made of the photosensitive resin;
Production of a single layer resin stamper comprising a curing step of curing the photosensitive resin by irradiating with ultraviolet light, and a peeling step of peeling a single layer of the cured photosensitive resin from the matrix and / or the substrate A method is provided.

  The filling step can be performed by filling the photosensitive resin into a matrix having an arbitrary pattern by a known method such as coating or dropping. Further, the laminating step can be performed by laminating a matrix having a base material or a pattern on a single layer made of the photosensitive resin, and pressing and transferring the matrix. Preferably, the curing step is performed after the laminating step by using a light source having a wavelength region of 200 nm to 500 nm from the matrix side and / or the substrate side, more specifically from the side having at least light transmittance, from the ultraviolet light side. It can be performed by irradiating light such as to cure the photosensitive resin. Further, the peeling step can be performed by releasing a single layer made of a cured photosensitive resin from the mother die and the substrate. Further, as an alternative manufacturing method of a single layer resin stamper, there is a method in which the photosensitive resin is coated on a substrate by a known method such as coating or dropping, and a mother die is pressed against the obtained photosensitive resin coating. It may be done.

  Moreover, in the said hardening process, it is preferable to irradiate the light which has a wavelength range of 200 nm-500 nm, and it is more preferable to irradiate the light which has a wavelength range of 300 nm-450 nm.

  Examples of light having a wavelength region of 200 nm to 500 nm include a xenon flash lamp, a xenon short arc lamp, an ultra high pressure UV lamp, a high pressure UV lamp, a deep UV lamp, a low pressure UV lamp, a KrCl or XeCl excimer lamp, a metal halide lamp, and the like. Can be mentioned. The irradiation time of light having a wavelength region of 200 nm to 500 nm is not limited. For example, the photosensitive resin can be cured by irradiation in the range of 1 second to 20 minutes.

  Further, in the curing step, in order to cure the photosensitive resin by irradiating light, it is necessary that light having a wavelength region of 200 nm to 500 nm is transmitted between the light source and the photosensitive resin. It is necessary to irradiate light from the side of a transparent medium (for example, a transparent matrix, a transparent substrate, or no substrate) that transmits light from a light source necessary for curing. Examples of the material for the transparent matrix and the substrate include glass, quartz, plastic film, and transparent resin. In order to improve the releasability from the matrix, it is preferable to apply a mold release agent to the matrix or to contain a mold release agent or a mold release component in the matrix and / or the photosensitive resin. In this embodiment, the resin stamper may use the substrate as a support, and in that case, in order to improve the adhesion of the substrate, an adhesion assistant may be applied to the support.

  In the curing step, the curing reaction atmosphere of the photosensitive resin may be, for example, by covering with a substrate, a matrix, a plastic film, a glass wafer, a metal plate, or using an inert gas, decompressing, or pressurizing. From the viewpoint of improving the curing reaction rate, it is preferable to reduce the oxygen concentration to 1% or less by a known method such as the above, and it is more preferable to set the oxygen concentration to 5000 ppm or less. Specific examples of the inert gas include inert gases such as nitrogen, helium, neon, argon, krypton, xenon, and carbon dioxide. The curing step can be performed under an atmosphere of these inert gases, or under reduced pressure or under pressure. These inert gases can be used alone or in combination of two or more.

  In this embodiment, the method for producing a single-layer resin stamper includes the cured photosensitivity in order to stabilize optical characteristics such as refractive index and transmittance of the single-layer resin stamper after the curing step or after the peeling step. It is preferable to include a heating step of heating the single layer made of resin or the obtained single layer resin stamper itself. The heating temperature when performing the heating step is preferably 130 ° C. or higher and 300 ° C. or lower in order to eliminate the thermal deterioration of the resin stamper and stabilize the optical characteristics. The heating time is not particularly limited, but is preferably in the range of about 1 minute to 10 hours.

  The single-layer resin stamper obtained by the present invention has a feature of high hardness, and if necessary, its durability can also be improved by electroforming nickel (Ni). The shape of the concavo-convex pattern of the resin stamper is not particularly limited, and examples thereof include lenses, lines & spaces, cylinders, cones, prisms, pyramids, honeycombs, and the like, which may be selected according to the application of the present invention. it can.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these. In addition, the following Examples 1-4 are only reference examples.

<Preparation of photosensitive resin containing silicon-containing compound>
[Example 1]
In a 500 mL eggplant-shaped flask, 34.35 g (0.148 mol) 3-methacryloxypropyl (methyl) dimethoxysilane (hereinafter abbreviated as MEDMO), methyltrimethoxysilane (hereinafter abbreviated as MTMS) 20. 13 g (0.148 mol) and 10 g of ethanol were added and stirred. Separately, 26.6 g of distilled water and 0.004 g of 10% hydrochloric acid were placed in a container, mixed, and then dropped into the 500 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 80 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 1 containing a polysiloxane compound.

  After refluxing, 60 g of PGMEA was added, a distillation column was set, ethanol and water were removed, and a PGMEA solution was obtained. Using a vacuum pump, the solvent was removed under reduced pressure to obtain polymer 1 as a condensation reaction product.

  To the obtained polymer 1 (99.5% by mass), 0.5% by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN (registered trademark) TPO manufactured by BASF Corporation) was used as a photopolymerization initiator. ) And stirred with a web rotor until dissolved at room temperature to prepare a photosensitive resin (P-1).

[Example 2]
To a 500 mL eggplant-shaped flask, 33.60 g (0.247 mol) of MTMS, 30.99 g (0.164 mol) of cyclohexylmethyldimethoxysilane (hereinafter abbreviated as CyMDMS) and 10 g of ethanol were added and stirred. Separately, 38.49 g of distilled water and 0.004 g of 10% hydrochloric acid were placed in a container, mixed, and then dropped into the 500 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 80 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 2 containing a polysiloxane compound. After refluxing, 60 g of PGMEA was added, a distillation column was set, ethanol and water were removed, and a PGMEA solution was obtained. Using a vacuum pump, the solvent was removed under reduced pressure to obtain polymer 2 as a condensation reaction product.

  50% by mass of tricyclodecane dimethanol diacrylate and 0.5% by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine as a photopolymerization initiator were added to the obtained polymer 2 (49.5% by mass). Oxide (LUCIRIN (registered trademark) TPO manufactured by BASF Corporation) was added and stirred with a web rotor until dissolved at room temperature to prepare a photosensitive resin (P-2).

[Example 3]
To polymer 1 (94.5% by mass) obtained in Example 1, 5% by mass of zinc oxide particles (manufactured by SIGMA-ALDRICH), 0.5% by mass of 2,4,6-trimethyl as a photopolymerization initiator Benzoyl-diphenyl-phosphine oxide was added and stirred with a web rotor until dissolved at room temperature to prepare a photosensitive resin (P-3).

[Example 4]
MEDMO 25.76 g (0.111 mol), MTMS 15.10 g (0.111 mol), and ethanol 10 g were added to a 500 mL eggplant-shaped flask and stirred. Separately, 19.96 g of distilled water and 0.004 g of 10% hydrochloric acid were placed in a container, mixed, and then dropped into the 500 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 80 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 3 containing a polysiloxane compound.

  In a 500 mL eggplant-shaped flask, 50 g (silica particles) of PL-1SL (manufactured by Fuso Chemical Industries, water-dispersed silica particles having an average primary particle diameter of 12 nm and a concentration of 20 mass%) and 50 g of ethanol were added and stirred. Then, the reaction liquid 3 cooled to room temperature using the dropping funnel was dripped at the said eggplant flask over 20 minutes, and it stirred at room temperature for 30 minutes. After stirring, a condenser tube was set and refluxed at 80 ° C. for 4 hours under a nitrogen stream.

  After refluxing, 60 g of PGMEA was added, a distillation column was set, ethanol and water were removed, and a PGMEA solution was obtained.

  To this polymer, 15 g of PGMEA, 25 g of toluene and 2.14 g (0.027 mol) of pyridine were added and mixed, and 2.67 g (0.025 mol) of trimethylchlorosilane (hereinafter abbreviated as TMCS) was added over 5 minutes while stirring. It was dripped. After stirring for 3 hours at room temperature, 10 g of water was added to the resulting reaction solution and stirred, and 20 g of acetonitrile and extraction were repeated three times to wash the polymer. Using a vacuum pump, the solvent was removed under reduced pressure to obtain polymer 3 which is a silica particle-containing condensation reaction product.

  To the obtained polymer 3 (99.5% by mass), 0.5% by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN (registered trademark) TPO manufactured by BASF Corporation) was used as a photopolymerization initiator. ) And stirred with a web rotor until dissolved at room temperature to prepare a photosensitive resin (P-4).

[Example 5]
In a 500 mL eggplant-shaped flask, 25.20 g (0.185 mol) of MTMS, 23.24 g (0.123 mol) of CyMDMS, and 10 g of ethanol were added and stirred. Separately, 28.87 g of distilled water and 0.004 g of 10% hydrochloric acid were placed in a container, mixed, and then dropped into the 500 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 80 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 4 containing a polysiloxane compound.

  In a 500 mL eggplant-shaped flask, 50 g of PL-1SL (silica particles) and 100 g of ethanol were added and stirred. Then, the reaction liquid 4 cooled to room temperature using the dropping funnel was dripped at the said eggplant flask over 20 minutes, and it stirred at room temperature for 30 minutes. After stirring, a condenser tube was set and refluxed at 80 ° C. for 4 hours under a nitrogen stream. After refluxing, 60 g of PGMEA was added, a distillation column was set, ethanol and water were removed, and a PGMEA solution was obtained. Using a vacuum pump, the solvent was removed under reduced pressure to obtain polymer 4 as a silica particle-containing condensation reaction product.

  50% by mass of tricyclodecane dimethanol diacrylate and 0.5% by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine as a photopolymerization initiator were added to the obtained polymer 4 (49.5% by mass). Oxide was added and stirred with a web rotor until dissolved at room temperature to prepare a photosensitive resin (P-5).

[Example 6]
Polymer 3 (94.5% by mass) obtained in Example 4 was mixed with 5% by mass of tricyclodecane dimethanol diacrylate and 0.5% by mass of 2,4,6-trimethylbenzoyl-- as a photopolymerization initiator. Diphenyl-phosphine oxide was added and stirred with a web rotor until dissolved at room temperature to prepare a photosensitive resin (P-6).

[Example 7]
To a 500 mL eggplant-shaped flask, MEDMO 5.88 g (0.025 mol), 3-methacryloxypropyltrimethoxysilane 7.54 g (0.030 mol), CyMDMS 6.67 g (0.035 mol), and ethanol 10 g were added and stirred. . Separately, 7.65 g of distilled water and 0.004 g of 10% hydrochloric acid were placed in a container, mixed, and then added dropwise to the 500 mL eggplant flask using a dropping funnel over 10 minutes. After completion of the dropping, a cooling tube was set and refluxed at 80 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 5 containing a polysiloxane compound.

  In a 500 mL eggplant-shaped flask, PL-1SL 120 g (silica particles) and ethanol 100 g were added and stirred. Then, the reaction liquid 5 cooled to room temperature using the dropping funnel was dripped at the said eggplant flask over 20 minutes, and it stirred at room temperature for 30 minutes. After stirring, a condenser tube was set and refluxed at 80 ° C. for 4 hours under a nitrogen stream.

  After refluxing, 60 g of PGMEA was added, a distillation column was set, ethanol and water were removed, and a PGMEA solution was obtained.

  To this polymer, 15 g of PGMEA, 25 g of toluene and 0.88 g (0.011 mol) of pyridine were added and mixed, and 1.10 g (0.010 mol) of TMCS was added dropwise over 5 minutes while stirring. After stirring for 3 hours at room temperature, 10 g of water was added to the resulting reaction solution and stirred, and 20 g of acetonitrile and extraction were repeated three times to wash the polymer. Using a vacuum pump, the solvent was removed under reduced pressure to obtain polymer 5 as a silica particle-containing condensation reaction product.

  40% by mass of tricyclodecane dimethanol diacrylate and 0.5% by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine as a photopolymerization initiator were added to the obtained polymer 5 (59.3% by mass). Oxide, 0.2 wt% ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] was added and stirred with a web rotor until dissolved at ambient temperature, A photosensitive resin (P-7) was prepared.

[Example 8]
In a 500 mL eggplant-shaped flask, 14.40 g (0.062 mol) of MEDMO, 14.52 g (0.062 mol) of 3-acryloxypropyltrimethoxysilane, 4.20 g (0.031 mol) of MTMS, and 10 g of ethanol were added and stirred. . Separately, 14.50 g of distilled water and 0.004 g of 10% hydrochloric acid were placed in a container, mixed, and then dropped into the 500 mL eggplant flask over 10 minutes using a dropping funnel. After completion of dropping, a cooling tube was set and refluxed at 80 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 6 containing a polysiloxane compound.

  In a 500 mL eggplant-shaped flask, 60 g of PL-1SL (silica particles) and 70 g of ethanol were added and stirred. Then, the reaction liquid 6 cooled to room temperature using the dropping funnel was dripped at the said eggplant flask over 20 minutes, and it stirred at room temperature for 30 minutes. After stirring, a condenser tube was set and refluxed at 80 ° C. for 4 hours under a nitrogen stream.

  After refluxing, 60 g of PGMEA was added, a distillation column was set, ethanol and water were removed, and a PGMEA solution was obtained.

  To this polymer, 15 g of PGMEA, 25 g of toluene and 4.49 g (0.057 mol) of pyridine were added and mixed, and 5.60 g (0.052 mol) of TMCS was added dropwise over 5 minutes while stirring. After stirring for 3 hours at room temperature, 10 g of water was added to the resulting reaction solution and stirred, and 20 g of acetonitrile and extraction were repeated three times to wash the polymer. Using a vacuum pump, the solvent was removed under reduced pressure to obtain polymer 6 as a silica particle-containing condensation reaction product.

  10% by mass of tricyclodecane dimethanol diacrylate and 0.5% by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine as a photopolymerization initiator were added to the obtained polymer 6 (89.3% by mass). Oxide, 0.2 wt% ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] was added and stirred with a web rotor until dissolved at ambient temperature, Photosensitive resin (P-8) was prepared.

[Example 9]
In a 500 mL eggplant-shaped flask, 14.74 g (0.063 mol) of MEDMO, 14.21 g (0.063 mol) of p-styryltrimethoxysilane, 4.32 g (0.032 mol) of MTMS, and 10 g of ethanol were added and stirred. Separately, 14.84 g of distilled water and 0.004 g of 10% hydrochloric acid were placed in a container, mixed, and then added dropwise to the above 500 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 80 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 7 containing a polysiloxane compound.

  In a 500 mL eggplant-shaped flask, 60 g of PL-1SL (silica particles) and 70 g of ethanol were added and stirred. Then, the reaction liquid 5 cooled to room temperature using the dropping funnel was dripped at the said eggplant flask over 20 minutes, and it stirred at room temperature for 30 minutes. After stirring, a condenser tube was set and refluxed at 80 ° C. for 4 hours under a nitrogen stream.

  After refluxing, 60 g of PGMEA was added, a distillation column was set, ethanol and water were removed, and a PGMEA solution was obtained.

  To this polymer, 15 g of PGMEA, 25 g of toluene and 4.60 g (0.058 mol) of pyridine were added and mixed, and 5.73 g (0.053 mol) of TMCS was added dropwise over 5 minutes while stirring. After stirring for 3 hours at room temperature, 10 g of water was added to the resulting reaction solution and stirred, and 20 g of acetonitrile and extraction were repeated three times to wash the polymer. Using a vacuum pump, the solvent was removed under reduced pressure to obtain polymer 7 as a silica particle-containing condensation reaction product.

  10% by mass of tricyclodecane dimethanol diacrylate and 0.5% by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine as a photopolymerization initiator were added to the obtained polymer 7 (89.3% by mass). Oxide, 0.2 wt% ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] was added and stirred with a web rotor until dissolved at ambient temperature, Photosensitive resin (P-9) was prepared.

[Comparative Example 1]
99.3% by mass of tricyclodecane dimethanol diacrylate, 0.5% by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide as a photopolymerization initiator, 0.2% by mass of ethylenebis (oxy Ethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] was added and stirred with a web rotor until dissolved at room temperature to prepare a photosensitive resin (P-10).

<Production of single layer resin stamper>
The obtained photosensitive resin (P-1) is dropped with a dropper on the central part of the Ni matrix, and a non-alkali glass surface-treated with a release agent composed of a fluorine compound is further placed on the photosensitive resin. The photosensitive resin that was fixed and dropped was placed under anaerobic conditions where oxygen curing inhibition could be ignored. Then, ultraviolet rays were irradiated from the non-alkali glass surface with a light intensity of 3000 mJ / cm ² using a metal halide lamp (CV-110Q-G, manufactured by Fusion UV Systems Japan Co., Ltd., main wavelength: about 380 nm). After the ultraviolet irradiation, it was peeled off from the matrix and the alkali-free glass to obtain a single layer resin stamper.

  For the photosensitive silicone resin compositions (P-2) to (P-10), single-layer resin stampers were produced in the same manner as described above.

[Preparation of cured film]
The obtained photosensitive resin (P-1) was treated with a dropper at the center on an alkali-free glass (thickness 0.7 mm, length and width 5 cm × 5 cm, manufactured by Corning) surface-treated with a release agent composed of a fluorine compound. It was dripped. At this time, two polycarbonate films (thickness 1 mm, length and width 0.5 cm × 5 cm) were laid on both sides of the alkali-free glass, and surface treatment was performed with a release agent composed of another fluorine compound on the photosensitive resin. An alkali-free glass was placed and fixed, and the dropped photosensitive resin was sandwiched between two sheets of alkali-free glass so that the oxygen curing inhibition was negligible. Then, from one alkali-free glass surface, a metal halide lamp (CV-110Q-G manufactured by Fusion UV Systems Japan Co., Ltd., main wavelength of about 380 nm) was irradiated with ultraviolet light at a light intensity of 3000 mJ / cm ² , and the film thickness was 1 mm. A cured molded product was produced and designated as a cured molded product 1-1.

  Regarding the photosensitive silicone resin compositions (P-2) to (P-10), cured molded products were prepared in the same manner as described above, and cured molded products 2-1 to 10-1 were obtained, respectively.

  In addition, the cured molded products 6-1 to 9-1 were heated at 150 ° C. for 1 hour to obtain cured molded products 6-2 to 9-2, respectively.

  Cured molded products 1-1 to cured molded products 10-1 and cured products prepared using the photosensitive silicone resin compositions (P-1) to (P-10) fabricated in Examples 1 to 9 and Comparative Example 1. Table 1 below shows the results of measurement and evaluation of the samples 6-2 to 9-2 according to the following (1) light resistance test and (2) pencil hardness measurement.

  As is clear from Table 1, Comparative Example 1 does not contain a silicon-containing compound, so that the deterioration in the light resistance test is severe.

(1) Light resistance test 1.6 W / cm < ² > using the high-pressure mercury lamp (Ushio Electric Co., Ltd. SPOTCURE SP-7, main wavelength about 365 nm) for the produced hardened | cured molding 1-1 to 10-1. For 100 hours. The transmittance of the cured molded product 1-1 to 10-1 was measured with UV3101PC manufactured by Shimadzu Corporation at a slit width of 5.0 nm before and after UV irradiation. Evaluation criteria for light resistance are ○, 70% or more when the transmittance at 400 nm wavelength after ultraviolet irradiation is 90% or more when the transmittance at 400 nm wavelength of the cured molded product before ultraviolet irradiation is 100%. Those with Δ, less than 70%, or those that cannot be measured due to material destruction were marked with ×.

(2) Pencil hardness measurement Regarding the produced cured molded products 1-1 to 10-1 and cured molded products 6-2 to 9-2, Clemens type scratch hardness tester (manufactured by Tester Sangyo Co., Ltd., HA-301-E). The pencil hardness was measured with a test speed of 2.5 mm / s and a load of 500 g. The evaluation criteria for pencil hardness were ◎ for pencil hardness of 5H or more, ◯ for 2H or more, Δ for H or more, and × for less than H.

  The single-layer resin stamper of the present invention includes, for example, optical lenses for cellular phones in the field of optical materials, light emitting diodes (LEDs), plastic lenses for automotive applications, replica materials, optical sheets for backlights such as liquid crystal displays, illumination, various sensors, To form patterns by optical imprinting as a single-layer resin stamper for manufacturing various plastic lens materials used in printers, copiers, etc., or in various fields such as electronics, photonics, magnetic devices, biology, opt Can be suitably used.

Claims (7)

Silica particles;
A silicon-containing compound ; and
A compound having no silicon and having a photopolymerizable functional group;
A method for producing a resin stamper having a pattern forming portion formed by irradiating a single layer made of a photosensitive resin containing ultraviolet light with ultraviolet light to cure the photosensitive resin ,
Pencil hardness of RESIN stamper Ri der more H,
The pattern forming portion is a single layer, and
The silicon-containing compound has the following general formula (1):
R ¹ _n1 SiX ¹ _4-n1 (1)
{In the formula, R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms which may contain nitrogen, sulfur, oxygen or fluorine, and X ¹ is a hydroxyl group, a halogen atom, or 1 to 6 carbon atoms. A group selected from the group consisting of an alkoxy group and an acetoxy group having 1 to 6 carbon atoms, n1 is an integer of 0 to 3, and when n1 is 2 or 3, a plurality of R ¹ are the same as each other Or when n1 is 0, 1 or 2, the plurality of X ¹ may be the same as or different from each other. }
A polysiloxane compound comprising a hydrolysis-condensation product of at least one silane compound represented by: or a mixture of the silane compound and the polysiloxane compound.
A method for producing the resin stamper. The silica particles, the chemically bonded by a portion Si-O-Si bonds polysiloxane compound and / or the silane compound, method for producing a dendritic fat stamper of claim 1. The silica particles, the chemically bonded by a portion Si-O-Si bonds polysiloxane compound, method for producing a dendritic fat stamper according to claim 2. The polysiloxane compound and / or the silane compound having a photopolymerizable functional group, the manufacturing method of the tree butter stamper of claim 1. The polysiloxane compound having a photopolymerizable functional group, the manufacturing method of the tree butter stamper according to claim 4. The following steps:
A filling step of filling the matrix having the pattern with the photosensitive resin;
A laminating step of superimposing a matrix having a substrate or a pattern on a single layer made of the photosensitive resin;
Curing step of curing the photosensitive resin by irradiating ultraviolet light, as well as peeling step of peeling the single-layer consisting of the cured photosensitive resin from the mother mold and / or the substrate, according to claim 1 to 5 method for producing a dendritic fat stamper according to any one of. The manufacturing method of the resin stamper of Claim 6 which further includes the heating process of heating the single layer which consists of the said hardening photosensitive resin after the said peeling process.