JP6452557B2 - Manufacturing method of surface-modifiable laminates - Google Patents

Description

  The present invention relates to a method for producing a novel laminate capable of surface modification. More specifically, the present invention relates to a base layer and a surface that has been modified to be easily functionalized through chemical modification using various surface modifiers formed on the base layer. The present invention relates to a method for producing a surface-modifiable laminate comprising a photocured film layer.

  Various surface treatment methods are known in order to functionalize the surface of a base material layer made of materials such as various plastics, metals, glass, and cellulose, and the surface of a layer formed on the base material layer. In general, functionalization is performed by directly treating the surface of the base material layer using these surface treatment methods. When the layer is formed on the base material layer, the adhesiveness with the base material layer may be insufficient, and in that case, an underlayer for improving the adhesiveness may be provided.

  Examples of the surface treatment method include dry treatment such as flame treatment, corona treatment, atmospheric pressure plasma treatment, ozone treatment, UV / ozone treatment, and wet treatment of chemical treatment with alkali, acid, peroxide, amines, etc. There are methods. Examples of functionalization by these surface treatment methods include imparting various properties such as hydrophilicity, antistatic properties and antifogging properties, and surface cleaning.

  Moreover, after surface-treating the surface of the base material layer by such a surface treatment method, it is further functionalized by chemical modification (or surface modification) using various surface modifiers. Functionalization of printing, water repellency, oil repellency, electrical conductivity, light shielding, infrared shielding, ultraviolet shielding, heat shielding, antibacterial, antiviral, antigen / antibody reaction reaction fields, etc. is performed.

  As a surface treatment method for modification, when the above-described dry treatment is performed, the dry treatment is free from contamination due to the surface treatment method in the base material layer as compared with the wet treatment, except for appearance defects due to surface alteration. There are advantages such as low sticking and high productivity. However, depending on the material constituting the base material layer, there are problems of deterioration due to aging of the modified surface, poor adhesion of the coating agent to the modified surface due to processing unevenness, and repellency of the coating agent.

  On the other hand, wet processing has problems such as poor appearance due to insufficient cleaning of chemicals and low productivity.

  Furthermore, recently, vacuum ultraviolet (VUV) treatment is performed as a dry treatment method. It is known that VUV treatment has a higher effect of decomposing organic residues and cleaning the surface than ultraviolet (UV) / ozone treatment (Non-Patent Document 1).

  However, Non-Patent Document 1 does not disclose that the surface treated by the VUV treatment is modified so as to be easily functionalized through chemical modification using various surface modifiers.

  Moreover, as one of methods using VUV treatment, a method for producing a gas barrier film is known (Patent Document 1). In this production method, when producing a gas barrier film having a gas barrier layer and a protective layer formed on the gas barrier layer on at least one surface side of the substrate, the organic silicon compound forming the protective layer is treated with VUV treatment. Thus, the organosilicon compound is converted to silica.

  Although there is a description in Patent Document 1 that a layer containing an organosilicon compound is converted to silica by subjecting the layer containing an organosilicon compound to VUV treatment, chemicals using various surface modifiers on the surface by VUV treatment are disclosed. It is not disclosed that it can be easily functionalized via modification.

JP2013-52561A

USHIO ELECTRIC OPTICAL TECHNOLOGY "LIGHT EDGE" No.36 <Special Issue No.1> Issued in March 2012 VUV Cleaning and Modification Technology in Nanoimprint

  The present invention is a novel laminate that can be chemically modified, and more specifically, easily functionalized through chemical modification using a base material layer and various surface modifiers formed on the base material layer. An object of the present invention is to provide a surface-modifiable laminate comprising a photocured film layer having a surface modified as described above.

  The inventors apply a photocurable composition containing a polymerizable monomer, a silicon compound, and a photopolymerization initiator on one surface of the base material layer to form a coating film. A photocured film layer is formed by irradiating light to cure the photocurable composition, and the photocured film layer is irradiated with vacuum ultraviolet light containing light having a wavelength of 183 nm or less. The present inventors have found that a laminate having a modified surface capable of surface modification can be produced by modifying the surface of the layer so as to be easily functionalized through chemical modification using various surface modifiers. Invented.

  According to the present invention, a photocurable composition containing a polymerizable monomer, a silicon compound, and a photopolymerization initiator is used, and after applying on the base material layer, the light is irradiated and cured, thereby the light. A cured film layer is formed, and the photocured film layer is irradiated with vacuum ultraviolet light containing light having a wavelength of 183 nm or less to modify the surface of the photocured film layer, thereby modifying the base material layer and the modified material layer. Even if no undercoat layer is provided between the photocured film layer and the surface, the deterioration due to aging of the surface treatment, which is a problem in dry treatment, poor adhesion due to treatment unevenness, repellency of the coating agent, dry treatment, In addition, the effect of being able to produce a surface-modifiable laminate having excellent appearance defects and productivity, which are problems in wet processing, is achieved.

  When the photocured film layer is required to have a desired uneven pattern according to the use of the surface-modifiable laminate according to the present invention, the photocurable composition of the present invention is particularly suitable for imprinting. It is suitable for (including nanoimprint), and can transfer the pattern from the mold well in accordance with the imprint method. Moreover, since the photocurable composition has good adhesion to the base material layer, It is not necessary to provide a formation.

  The present invention relates to a photocurable film layer having a base material layer and a surface formed on the base material layer so as to be easily functionalized by chemical modification using various surface modifiers. And a photocurable composition containing a polymerizable monomer, a silicon compound and a photopolymerization initiator on one surface of the base material layer. A coating film is formed by applying an object, and the coating film is irradiated with light to cure the photocurable composition to form a photocured film layer, and the photocured film layer has a wavelength of 183 nm or less. Irradiating vacuum ultraviolet light containing light to modify the surface of the photocured film layer so as to be easily functionalized through chemical modification using various surface modifiers The present invention relates to a method for producing a modifiable laminate.

  The photocurable composition used in the present invention will be described.

  The photocurable composition comprises a polymerizable monomer, a silicon compound, and a photopolymerization initiator. In the present invention, a known polymerizable monomer can be used without any limitation, but it is also important that the adhesiveness with a base material layer such as a resin film, and further excellent productivity, From the viewpoint of adhesion to a substrate layer such as the above, and productivity, a photocurable polymerizable monomer is preferable. In general, as the photopolymerizable monomer of the photocurable composition, a monomer containing a polymerizable monomer having a (meth) acryl group is preferably used. The term “(meth) acrylic group” used in the present invention means an acrylic group or a methacrylic group. The “polymerizable monomer having a (meth) acrylic group” does not include a (meth) acrylic group-containing alkoxysilane represented by the general formula (3) which is a silicon compound described later and a hydrolyzate thereof. To do.

  Hereinafter, the polymerizable monomer having a (meth) acryl group will be described.

Polymerizable monomer having a (meth) acryl group (polymerizable monomer)
In the present invention, the polymerizable monomer having a (meth) acryl group (hereinafter also simply referred to as “polymerizable monomer”) is not particularly limited, and is a known polymerizable used for photopolymerization. Monomers can be used. Examples of the polymerizable monomer include polymerizable monomers having a (meth) acryl group and containing no silicon atom in the molecule. These polymerizable monomers may be monofunctional polymerizable monomers having one (meth) acryl group in one molecule, or have two or more (meth) acryl groups in one molecule. A polyfunctional polymerizable monomer may be used. Furthermore, these monofunctional polymerizable monomers and polyfunctional polymerizable monomers can also be used in combination.

  If the example of a polymerizable monomer is illustrated concretely, as a monofunctional polymerizable monomer which has one (meth) acryl group in 1 molecule, methyl (meth) acrylate (The term "(meta ) "Acrylate" means acrylate or methacrylate), ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, isodecyl (meth) acrylate, isoamyl (meth) acrylate, isomyristyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, long chain alkyl (Meth) acrylate, n-butyl Xylethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, dicyclopentenyl (meta) ) Acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, hydroxy Ethyl (meth) acrylamide, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethylene glyco Modified (meth) acrylate, ethoxyethylene glycol modified (meth) acrylate, propoxyethylene glycol modified (meth) acrylate, methoxypropylene glycol modified (meth) acrylate, ethoxypropylene glycol modified (meth) acrylate, propoxypropylene glycol modified (meth) Acrylate, isobornyl (meth) acrylate, adamantane (meth) acrylate derivative, aliphatic acrylate such as acryloylmorpholine; benzyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethylene glycol modified (meth) Acrylate, phenoxypropylene glycol modified (meth) acrylate, hydroxyphenoxyethyl (meta ) Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, hydrophenoxyethylene glycol modified (meth) acrylate, hydroxyphenoxypropylene glycol modified (meth) acrylate, alkylphenol ethylene glycol modified (meth) acrylate, alkylphenol propylene glycol modified (Meth) acrylate, (meth) acrylate having an aromatic ring such as a monomer having an o-phenylphenol group in the molecule, and the like.

  As a polyfunctional polymerizable monomer (bifunctional polymerizable monomer) having two (meth) acryl groups in one molecule, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Polyolefin glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, dioxane glycol di (meth) acrylate , Tricyclodecane dimethanol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (Meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, butyl Aliphatic di (meth) acrylates such as ethylpropanediol di (meth) acrylate and 3-methyl-1,5-pentanediol di (meth) acrylate; ethoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A Examples include di (meth) acrylate having an aromatic ring such as di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, and di (meth) acrylate having a fluorene structure.

  Further, in the polyfunctional polymerizable monomer, as the polymerizable monomer having three or more (meth) acryl groups in one molecule, ethoxylated glycerin tri (meth) acrylate, trimethylolpropane tri (meta) ) Acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Examples include ethoxylated pentaerythritol tetra (meth) acrylate and dipentaerythritol polyacrylate.

  Moreover, the said polymerizable monomer may be individual and may be used in combination of multiple types.

Next, the silicon compound will be described.
Silicon Compound The photocurable composition used in the present invention contains a silicon compound in addition to the polymerizable monomer described above. According to the present invention, since a silicon compound is present in the photocurable composition, the VUV treatment provides a preferable modification for surface modification on the surface of the photocured film layer.

  Among silicon compounds, a silicon compound having a siloxane bond is more preferable. As the silicon compound having such a siloxane bond, any known compound can be used, but alkoxysilanes or hydrolysates of alkoxysilanes are preferably used, and alkoxysilanes or alkoxysilanes are preferably used. As the hydrolyzate of silanes, for example, the following compounds can be used.

Alkoxysilanes or hydrolysates of alkoxysilanes As alkoxysilanes, in addition to a general alkoxysilane in which one or more alkoxy groups are bonded to a silicon atom, a group other than an alkoxy group may be a phenyl group. , Alkoxysilane having an aromatic ring such as naphthyl group, biphenyl group, alkoxysilane having a functional group such as (meth) acryl group, epoxy group, thiol group, hydroxyl group, carboxyl group, phosphonium group, sulfonyl group, fluorine, chlorine, etc. It may be an alkoxysilane having a halogen element, or a mixture thereof.

  The hydrolyzate of alkoxysilanes is a product of hydrolysis of a part or all of the alkoxy groups of the above alkoxysilanes, a polycondensate of alkoxysilane, and a hydrolysis of part or all of the alkoxy groups of the polycondensate. Means products and various mixtures thereof.

  The better the dispersibility between the hydrolyzate of alkoxysilanes and the polymerizable monomer, the easier the pattern transfer. In order to improve the dispersibility, depending on the functional group of the polymerizable monomer, for example, when the polymerizable monomer is a polymerizable monomer having a (meth) acryl group, alkoxysilane is used. It is preferable to use a hydrolyzate of an alkoxysilane having a (meth) acrylic group as a hydrolyzate of the class, and when the polymerizable monomer has an epoxy group, an alkoxysilane containing an epoxy group The hydrolyzate is preferred.

  General alkoxysilanes that are alkoxysilanes, (meth) acryl group-containing alkoxysilanes, and alkoxysilanes having a halogen element will be described.

（式中、Ｒ¹は、同種又は異種の炭素数１〜４のアルキル基であり、ｎは１〜１０の整数である）で示されるアルコキシシランを好ましく用いることができる。 Among general alkoxysilanes or hydrolyzate alkoxysilanes thereof , general alkoxysilanes include those represented by the general formula (1)

An alkoxysilane represented by the formula (wherein R ¹ is the same or different alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 10) can be preferably used.

  Among the above alkoxysilanes, when n exceeds 1 or a hydrolyzate thereof, the resulting photocurable composition can be obtained at a relatively lower pressure when pattern transfer is performed from a mold by an imprint method. This is advantageous for pattern transfer. Moreover, the adhesiveness to a base material can be improved by using the said alkoxysilane or its hydrolyzate.

In the general formula (1), R ¹ which is an alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, and a ter-butyl group. Of these, a methyl group and an ethyl group are preferable.

  Specific examples of these alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and polycondensates thereof. Of these, tetramethoxysilane, tetraethoxysilane, and polycondensates thereof are preferred because they are alcohols that can be easily removed after forming a coating film, and because of reactivity, in particular, the value of n or n Is preferably tetramethoxysilane having a mean value of 3 to 7, or a polycondensate of tetraethoxysilane.

（式中、Ｒ²は、水素原子又はメチル基であり；Ｒ³は、炭素数１〜１０のアルキレン基、炭素数３〜１０のシクロアルキレン基又は炭素数３〜１０のポリメチレン基であり；Ｒ⁴は、炭素数１〜４のアルキル基、炭素数３〜４のシクロアルキル基又は炭素数６〜１２のアリール基であり；Ｒ⁵は、炭素数１〜４のアルキル基又は炭素数３〜４のシクロアルキル基であり；ｌは１〜３の整数であり、ｍは０〜２の整数であり、ｋは１〜３の整数であり、ｌ＋ｍ＋ｋは４であり；Ｒ²、Ｒ³、Ｒ⁴およびＲ⁵がそれぞれ複数存在する場合には、その複数のＲ²、Ｒ³、Ｒ⁴およびＲ⁵は、同種又は異種の基であってよい）で示される（メタ）アクリル基含有アルコキシシランを好ましく用いることができる。 The (meth) acrylic group-containing alkoxysilane or a hydrolyzate thereof (meth) acrylic group-containing alkoxysilane has the general formula (2)

Wherein R ² is a hydrogen atom or a methyl group; R ³ is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a polymethylene group having 3 to 10 carbon atoms; R ⁴ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R ⁵ is an alkyl group having 1 to 4 carbon atoms or 3 carbon atoms. L is an integer of 1 to 3, m is an integer of 0 to 2, k is an integer of 1 to 3, and l + m + k is 4; R ² , R ³ , R ⁴ and R ⁵ each having a plurality thereof, the plurality of R ² , R ³ , R ⁴ and R ⁵ may be the same or different groups). Alkoxysilane can be preferably used.

  When a polymerizable monomer having a (meth) acrylic group is used as the polymerizable monomer, a photocurable composition with good dispersibility can be obtained by using the above (meth) acrylic group-containing alkoxysilane or a hydrolyzate thereof. A product is obtained, purification by filtration is easy, productivity is good, and this is preferable. Further, when the photocurable composition contains this (meth) acrylic group-containing alkoxysilane or a hydrolyzate thereof, the inorganic component and the organic component are relatively homogeneous in the fine structure of the cured film obtained by photocuring. (The inorganic component does not become a dispersed state that is extremely aggregated). As a result, it is estimated that a uniform photocured film layer can be formed.

In the general formula (2), R ² is a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferable because the photocuring speed when curing the photocurable composition is high.

R ³ is an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms. Specifically, examples of the alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, propylene group, isopropylene group, cyclopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, cyclohexane. Butylene group, cyclopropylmethylene group, 2,2-dimethylpropylene group, 2-methylbutylene group, 2-methyl-2-butylene group, 3-methylbutylene group, 3-methyl-2-butylene group, pentylene group, 2 -Pentylene group, 3-pentylene group, 2,3-dimethyl-2-butylene group, 3,3-dimethylbutylene group, 3,3-dimethyl-2-butylene group, 2-ethylbutylene group, hexylene group, 2- Hexylene group, 3-hexylene group, 2-methylpentylene group, 2-methyl-2-pentylene group, 2-methyl-3-pentylene group, 3-methylpentylene group, 3-methyl-2-pentylene group, 3-methyl-3-pentylene group, 4-methylpentylene group, 4-methyl-2-pentylene group, 2,2-dimethyl-3-pentylene Group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl-2-pentylene group, 3-ethyl-3-pentylene group, heptylene group, 2-heptylene Group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3-hexylene group, 5-methylhexylene group, 5-methyl-2-hexylene group, 2-ethylhexylene group, 6- Methyl-2-heptylene group, 4-methyl-3-heptylene group, octylene group, 2-octylene group, 3-octylene group, 2-propylpentylene group, 2,4,4-trimethylpentylene group, Methylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, and the like. Especially, as a C1-C10 alkylene group, a methylene group, ethylene group, a propylene group, an isopropylene group, a butylene group, a trimethylene group, and a tetramethylene group are preferable. Examples of the cycloalkylene group having 3 to 10 carbon atoms include a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.

R ⁴ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Specifically, examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group; Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, and a cyclopropylmethyl group; examples of the aryl group having 6 to 12 carbon atoms include benzene derivatives such as a phenyl group and a benzyl group, a 1-naphthyl group, a 2-naphthyl group, and o- Naphthalene derivatives such as a methyl naphthyl group can be mentioned, and among them, a methyl group and an ethyl group are preferable.

R ⁵ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms. Specifically, examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group; Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, and a cyclopropylmethyl group. Specifically, R ⁵ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group.

  l is an integer of 0-2, m is an integer of 0-2, k is an integer of 1-3, and l + m + k is 4.

  Specific examples of such (meth) acrylic group-containing alkoxysilanes include trimethoxysilylmethylene (meth) acrylate, trimethoxysilyldimethylene (meth) acrylate, trimethoxysilyltrimethylene (meth) acrylate, triethoxy Silylmethylene (meth) acrylate, triethoxysilyldimethylene (meth) acrylate, triethoxysilyltrimethylene (meth) acrylate, tripropoxysilylmethylene (meth) acrylate, tripropoxysilylethylene (meth) acrylate, tripropoxysilyl trimethylene (Meth) acrylate, tributoxysilylmethylene (meth) acrylate, tributoxysilyldimethylene (meth) acrylate, tributoxysilyltrimethylene (meth) acrylate Triisopropoxysilylmethylene (meth) acrylate, triisopropoxysilyldimethylene (meth) acrylate, triisopropoxysilyltrimethylene (meth) acrylate, dimethoxymethylsilylmethylene (meth) acrylate, dimethoxymethylsilyldimethylene (meta) ) Acrylate, dimethoxymethylsilyltrimethylene (meth) acrylate, diethoxymethylsilylmethylene (meth) acrylate, diethoxymethylsilyldimethylene (meth) acrylate, diethoxymethylsilyltrimethylene (meth) acrylate, dimethoxyethylsilylmethylene ( (Meth) acrylate, dimethoxyethylsilyldimethylene (meth) acrylate, dimethoxyethylsilyltrimethylene (meth) acrylate, diet Siethylsilylmethylene (meth) acrylate, diethoxyethylsilyldimethylene (meth) acrylate, diethoxyethylsilyltrimethylene (meth) acrylate, methoxydimethylsilylmethylene (meth) acrylate, methoxydimethylsilyldimethylene (meth) acrylate, Methoxydimethylsilyltrimethylene (meth) acrylate, ethoxydimethylsilylmethylene (meth) acrylate, ethoxydimethylsilyldimethylene (meth) acrylate, ethoxydimethylsilyltrimethylene (meth) acrylate, methoxydiethylsilylmethylene (meth) acrylate, methoxydiethyl Silyldimethylene (meth) acrylate, methoxydiethylsilyltrimethylene (meth) acrylate, ethoxydiethylsilylmeth Examples include lene (meth) acrylate, ethoxydiethylsilyldimethylene (meth) acrylate, and ethoxydiethylsilyltrimethylene (meth) acrylate. Of these, trimethoxysilyltrimethylene (meth) acrylate and triethoxysilyltrimethylene (meth) acrylate are preferable.

（式中、Ｒ⁶およびＲ⁸は、それぞれ、炭素数１〜１０のアルキル基又は炭素数３〜１０のシクロアルキル基であり；Ｒ⁷は、含フッ素アルキル基、含フッ素シクロアルキル基又は含フッ素アルコキシエーテル基であり；ａは１〜３の整数であり、ｂは０〜２の整数であり、ただし、ａ＋ｂ＝１〜３であり；Ｒ⁶、Ｒ⁷およびＲ⁸がそれぞれ複数存在する場合には、その複数のＲ⁶、Ｒ⁷およびＲ⁸は、それぞれ同一であっても、異なる基であってもよい）で示されるフッ素化シラン化合物を好ましく用いることができる。このフッ素化シラン化合物又はその加水分解物を使用することにより、基材と光硬化膜層との密着性、およびパターンを形成することが要求される際の金型とパターンが形成された光硬化膜層との間の離型性を向上させることができる。 As the alkoxysilane having a halogen element or its hydrolyzate halogen element, the general formula (3)

Wherein R ⁶ and R ⁸ are each an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms; R ⁷ is a fluorine-containing alkyl group, fluorine-containing cycloalkyl group or A fluorine alkoxy ether group; a is an integer of 1 to 3, b is an integer of 0 to 2, provided that a + b = 1 to 3; and a plurality of R ⁶ , R ⁷ and R ⁸ are present. In some cases, a plurality of R ⁶ , R ⁷ and R ⁸ may be the same or different groups). By using this fluorinated silane compound or a hydrolyzate thereof, the adhesion between the substrate and the photocured film layer, and the photocuring in which a mold and a pattern are formed when it is required to form a pattern. The releasability between the film layers can be improved.

In the general formula (3), R ⁶ and R ⁸ are an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group. Butyl group, sec-butyl group, isobutyl group, and ter-butyl group. Specifically, R ⁶ is more preferably a methyl group, an ethyl group, or a propyl group.

（式中、ｘは１以上の整数であり、ｙは２以上の整数である）で表されるアルコキシエーテル基において１又は２以上の水素原子をフッ素原子に置換したものが好ましい。一般式（４）において、ｘは１〜６、ｙは５〜５０が好ましい。 R ⁷ is a fluorine-containing alkyl group, a fluorine-containing cycloalkyl group or a fluorine-containing alkoxy ether group. Here, the fluorine-containing alkyl group means one obtained by substituting one or more hydrogen atoms of an alkyl group with a fluorine atom, and other fluorine-containing cycloalkyl groups or fluorine-containing alkoxy ether groups are also cycloalkyl groups. Means an alkoxy ether group in which one or more hydrogen atoms are substituted with fluorine atoms. The fluorine-containing alkyl group and the fluorine-containing alkoxy group preferably have 1 to 10 carbon atoms, and the fluorine-containing cycloalkyl group preferably has 3 to 10 carbon atoms. Further, the fluorine-containing alkoxy ether group in the present invention has the general formula (4)

In the alkoxy ether group represented by the formula (wherein x is an integer of 1 or more and y is an integer of 2 or more), one in which one or more hydrogen atoms are substituted with fluorine atoms is preferable. In the general formula (4), x is preferably 1 to 6, and y is preferably 5 to 50.

Specific examples of these fluorinated silane compounds are (heptadecafluoro-1,1,2,2-tetrahydrodecyl) -triethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl). -Trimethoxysilane, nonafluorohexyltriethoxysilane, nonafluorohexyltrimethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) -triethoxysilane, (tridecafluoro-1,1,2) , 2-tetrahydrooctyl) -trimethoxysilane, pentafluoro-1,1,2,2-tetrahydropentyltriethoxysilane, pentafluoro-1,1,2,2-tetrahydropentyltrimethoxysilane, (3,3, 3-trifluoropropyl) dimethylethoxysilane, (3,3,3-trifluoropropyl) dimethyl Methoxysilane, (3,3,3-trifluoropropyl) methyldiethoxysilane, (3,3,3-trifluoropropyl) methyldimethoxysilane, (3,3,3-trifluoropropyl) triethoxysilane, ( 3,3,3-trifluoropropyl) trimethoxysilane, perfluoropropyltriethoxysilane, perfluoropropyltrimethoxysilane, 5,5,6,6,7,7,8,8,9,9,10, 10,10-tridecafluoro-2- (tridecafluorohexyl) decyltriethoxysilane, 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro -2- (Tridecafluorohexyl) decyltrimethoxysilane, perfluorododecyl-1H, 1H, 2H, 2H-triethoxysilane, perfluorododecyl-1H, 1H, 2H, 2H-trimeth Sisilane, perfluorotetradecyl-1H, 1H, 2H, 2H-triethoxysilane, perfluorotetradecyl-1H, 1H, 2H, 2H-trimethoxysilane, 3- (perfluorocyclohexyloxy) propyltrimethoxysilane, etc. Examples of the fluorinated silane compound having a fluorine-containing alkoxy ether group of the above general formula (4) include, for example, OPTOOL HD-1100TH manufactured by Daikin Industries, Ltd. Among these, the interaction between molecules is relatively weak and the molecular arrangement structure is disturbed, which is considered advantageous for surface releasability, and the ease of hydrolysis of the alkoxy group consisting of —OR ^{6 in the} general formula (3). (Tridecafluoro-1,1,2,2-tetrahydrooctyl) -trimethoxysilane and (3,3,3-trifluoropropyl) trimethoxysilane are preferable.

  In the photocurable composition used in the present invention, for example, when the polymerizable monomer contains a polymerizable monomer having a (meth) acryl group, the silicon compound is represented by the general formula (2). Preferred is a hydrolyzed (meth) acrylic group-containing alkoxysilane, a general alkoxysilane represented by the general formula (1), and a (meth) acrylic group-containing general formula (2). What hydrolyzed the fluorinated silane compound of alkoxysilane and the alkoxysilane which has the halogen element represented by the said General formula (3) is more preferable, Furthermore, the mixture containing the metal alkoxide mentioned later other than these alkoxysilanes A product obtained by hydrolyzing is preferable.

  In this invention, the preferable compounding quantity of the hydrolyzate of said alkoxysilane is, for example, when a photocurable composition contains the polymerizable monomer which has a (meth) acryl group as a polymerizable monomer. The hydrolyzate of (meth) acrylic group-containing alkoxysilane obtained by hydrolyzing 3 parts by mass to 300 parts by mass with respect to 100 parts by mass of the polymerizable monomer having a (meth) acrylic group, Furthermore, in addition to the (meth) acryl group-containing alkoxysilane, in the case of containing the general alkoxysilane, it is preferable to blend a hydrolyzate obtained by hydrolyzing 10 mass parts to 250 mass parts of a general alkoxysilane, When the fluorinated silane compound is contained in addition to the previous composition, 0.001 to 4 parts by mass of the fluorinated silane compound, In addition to orchids, when a metal alkoxide described below is included, it is preferable to blend a hydrolyzate obtained by hydrolyzing 1 to 100 parts by weight of a metal alkoxide.

（式中、Ｍは、ジルコニウム又はチタニウムであり；Ｒ⁹は、同種又は異種の炭素数１〜１０のアルキル基である）で示される金属アルコキシドの加水分解物を含むことができる。 In the present invention, the photocurable composition further includes a general formula (5) which is a metal alkoxide excluding alkoxylanes.

(Wherein, M is zirconium or titanium; and R ⁹ is the same or different alkyl group having 1 to 10 carbon atoms).

R ⁹ is more preferably an alkyl group having 2 to 4 carbon atoms from the viewpoint of an appropriate hydrolysis rate. Specifically, R ⁹ is preferably an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, or a ter-butyl group.

  Examples of suitable metal alkoxides include tetramethyltitanium alkoxide, tetraethyltitanium alkoxide, tetraisopropyltitanium alkoxide, tetrapropyltitanium alkoxide, tetraisobutyltitanium alkoxide, tetrabutyltitanium alkoxide, tetrasec-butyltitanium alkoxide, tetrater-butyltitanium. Alkoxide, tetrapentyl zirconium alkoxide, tetraheptyl titanium alkoxide, tetrahexyl titanium alkoxide, tetraheptyl titanium alkoxide, tetraoctyl titanium alkoxide, tetranonyl titanium alkoxide, tetradecyl titanium alkoxide, tetramethyl zirconium alkoxide, tetraethyl Luconium alkoxide, tetraisopropyl zirconium alkoxide, tetrapropyl zirconium alkoxide, tetraisobutyl zirconium alkoxide, tetrabutyl zirconium alkoxide, tetra sec-butyl zirconium alkoxide, tetra ter-butyl zirconium alkoxide, tetrapentyl zirconium alkoxide, tetrahexyl zirconium alkoxide, tetraheptyl Zirconium alkoxide, tetraoctyl zirconium alkoxide, tetranonyl zirconium alkoxide, and tetradecyl zirconium alkoxide are exemplified. Among these, tetraethyl zirconium alkoxide, tetraisopropyl zirconium alkoxide, tetrapropyl zirconium alkoxide, tetraisobutyl zirconium alkoxide, and tetrabutyl zirconium alkoxide are preferable.

  In addition to the hydrolyzate of alkoxysilanes, the photocurable composition used in the present invention includes a hydrolyzate of zirconium alkoxide or titanium alkoxide, a polycondensate of zirconium alkoxide or titanium alkoxide, and an alkoxy group of the polycondensate. A part or all of the hydrolyzate, and a reaction product of zirconium alkoxide or titanium alkoxide and alkoxysilane (polycondensate of zirconium alkoxide or titanium alkoxide and alkoxysilane, part of alkoxy group of the polycondensate) For the preparation thereof, the photocurable composition may contain water, a hydrolysis catalyst, and the like. In addition, in order to improve the storage stability of the prepared photocurable composition, water used in preparing the photocurable composition, hydrolysis catalyst, etc. are vacuum-dried in any step of the preparation. It may be removed by distillation, heating or the like. At that time, if the solvent is removed at the same time, a necessary amount of the solvent may be appropriately added after removing water, the hydrolysis catalyst, and the like.

  The photocurable composition is a polymerizable monomer containing a (meth) acrylic group, a silicon compound having a siloxane bond (general alkoxysilane and (meth) acrylic group-containing alkoxysilane, and, if necessary, further When a hydrolyzate (including alkoxysilane having a halogen element) and a partial condensate thereof are included, dispersibility is improved, and therefore, a more preferable modification is made with respect to the surface modification of the laminate of the present invention.

  The photocurable composition preferably further contains a hydrolyzate of zirconium alkoxide or titanium alkoxide, or a reaction product of zirconium alkoxide or titanium alkoxide and alkoxysilanes.

  The photocurable composition is a polymerizable monomer containing a (meth) acryl group, a hydrolyzate of a silicon compound having a siloxane bond and a partial condensate thereof, a hydrolyzate of zirconium alkoxide or titanium alkoxide, or a zirconium alkoxide or When the reaction product of titanium alkoxide and alkoxysilane is included, the dispersibility is further improved, and therefore, a more preferable modification is made with respect to the surface modification of the laminate of the present invention.

Next, the photopolymerization initiator will be described.
Photopolymerization initiator In the present invention, the photopolymerization initiator is not particularly limited, and any photopolymerization initiator can be used as long as it can photopolymerize a polymerizable monomer.

  Specific examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 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-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4 Acetophenone derivatives such as methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2 2,6-Dichlorobenzoyldiphenylphosphine oxide, 2,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, bis- (2,6-dichlorobenzoyl) phenylphosphine Oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide Bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4- Trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis- (2,5,6- Acylphosphine oxide derivatives such as trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazo O-acyloxime derivatives such as -3-yl]-, 1- (o-acetyloxime); diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, Α-diketones such as 4,4′-oxybenzyl, camphorquinone, 9,10-phenanthrenequinone, and acenaphthenequinone; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin propyl ether; 2,4- Thioxanthone derivatives such as diethoxythioxanthone, 2-chlorothioxanthone, methylthioxanthone; benzophenone derivatives such as benzophenone, p, p′-dimethylaminobenzophenone, p, p′-methoxybenzophenone; bis (η5-2, 4-cyclopentadiene-1- Le) - bis (2,6-difluoro-3-(1H-pyrrol-1-yl) - phenyl) titanocene derivatives such as titanium is preferably used.

  These photopolymerization initiators are used alone or in combination of two or more.

  When α-diketone is used, it is preferably used in combination with a tertiary amine compound. Tertiary amine compounds that can be used in combination with α-diketone include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline. N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N- Dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranic acid methyl Ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p Dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tri Butylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate N, N-diethylaminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol, and the like. In particular, it is preferable to use an acetophenone derivative, an acylphosphine oxide derivative, an o-acyloxime derivative, or an α-diketone.

  In this invention, it is preferable that the usage-amount of the said photoinitiator is 1-10 mass parts with respect to 100 mass parts of said polymerizable monomers.

Other Additive Components Other components can be added to the photocurable composition as long as the effects of the present invention are not impaired.

  Specifically, a surfactant, a polymerization inhibitor, a reactive diluent and the like can be blended. The surfactant is blended from the viewpoint of the uniformity of the coating film, and the polymerization inhibitor is blended for stabilization so that a polymerization reaction does not occur during storage.

  When the surfactant is blended, it is blended at a ratio of 0.0001 to 0.1 parts by mass, preferably 0.0005 to 0.01 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Can do.

  As the surfactant, a fluorine-containing surfactant, a silicone-containing surfactant, and an aliphatic surfactant can be used. Among these, when the photocurable composition is applied onto a substrate, an aliphatic surfactant is used because it does not cause “repelling” and is easily applied regardless of the material of the substrate. More preferably it is used. Examples of surfactants include metal salts of higher alcohol sulfates such as sodium decyl sulfate and sodium lauryl sulfate, aliphatic carboxylic acid metal salts such as sodium laurate, sodium stearate and sodium oleate, lauryl alcohol and ethylene oxide. Anionic activity such as metal salts of higher alkyl ether sulfates such as sodium lauryl ether sulfate esterified with adducts with sodium, sulfosuccinic diesters such as sodium sulfosuccinate, phosphate esters of higher alcohol ethylene oxide adducts, etc. Agents; Cationic surfactants such as alkylamine salts such as dodecylammonium chloride and quaternary ammonium salts such as trimethyldodecylammonium bromide; such as dodecyldimethylamine oxide Zwitterionic surfactants such as alkyl dimethyl betaines such as alkyl dimethyl amine oxides, alkyl carboxy betaines such as dodecyl carboxy betaine, alkyl sulfo betaines such as dodecyl sulfo betaine, and amide amino acid salts such as lauramido propyl amine oxide; polyoxyethylene lauryl ether, etc. Polyoxyethylene alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene distyrenated phenyl ethers, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene lauryl phenyl ether, polyoxyethylene tribenzylphenyl ethers, Fatty acid polyoxyethylene esters such as fatty acid polyoxyethylene lauryl ester, polio such as polyoxyethylene sorbitan lauryl ester It can be mentioned non-ionic surfactants such as polyoxyethylene sorbitan esters.

  Surfactants can be used not only independently but also in combination of a plurality of types as required.

  When blending a polymerization inhibitor, 0.01 to 1.0 part by weight, preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the polymerizable monomer. Can do.

  Examples of the polymerization inhibitor include known ones. For example, the most typical ones include hydroquinone monomethyl ether, hydroquinone, butylhydroxytoluene and the like.

  Examples of the reactive diluent include known ones such as N-vinylpyrrolidone.

  The addition amount of the reactive diluent is not particularly limited, but when forming a photocured film layer having a pattern, it is appropriately selected within a range that does not affect the transfer of the pattern from the mold. It is suitably selected from the range of 1 to 50 parts by mass with respect to 100 parts by mass of the mass. Among these, it is preferable that it is 5-30 mass parts, when low viscosity of the composition for photocurable imprint, the mechanical strength of a pattern, etc. are considered.

  In addition, spherical fine particles such as a piper branch polymer can be added as another additive component. In this case, it is preferable to blend a spherical hyperbranched polymer having a diameter of 1 to 10 nm and a molecular weight of 10,000 to 100,000. It is preferable that a compounding quantity is a quantity of 0.1-10 mass parts with respect to 100 mass parts of polymerizable monomers.

Preparation Method of Photocurable Composition The photocurable composition used in the present invention is used by being applied on a substrate in one aspect. In this case, the photocurable composition is diluted with a solvent. Can also be used. Moreover, a solvent can also be mix | blended for the objective of stabilizing a photocurable composition, or the other objective. As the solvent to be used, any solvent that can dissolve the photocurable composition can be used without any limitation. For example, acetonitrile, tetrahydrofuran, toluene, chloroform, acetic acid ethyl ester, methyl ethyl ketone, dimethylformamide, cyclohexanone, ethylene glycol, Propylene glycol, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethylene glycol monoethyl ether acetate, ethyl lactate, ethyl-3-ethoxypropionate, butyl acetate, 2-heptanone, methyl Examples include isobutyl ketone, acetylacetone, diacetone alcohol, polyethylene glycol, water, and alcohols.

  When using a solvent, the amount used is not particularly limited and is appropriately selected according to the thickness of the target coating film.

  The photocurable composition used in the present invention is prepared by mixing a polymerizable monomer, a silicon compound, a photopolymerization initiator, and other additive components blended as necessary. The order of addition of these components is not particularly limited.

Formation of Photocured Film Layer Next, a method for forming a photocured film layer using this photocurable composition will be described.
A photocurable composition is apply | coated on a base material according to a well-known method, and forms a coating film. The substrate is not particularly limited, and a plate, sheet, or film can be used. Specifically, silicon wafer, quartz, glass, sapphire, various metal materials, ceramics such as alumina, aluminum nitride, silicon carbide, silicon nitride, polyethylene terephthalate, polypropylene, polycarbonate, triacetyl cellulose, polystyrene, cycloolefin resin, etc. A sheet or film made of any known thermoplastic resin can be used. In addition, in order to improve the adhesiveness with the photocuring film layer formed from the photocurable composition used by this invention to the base-material surface, it can also surface-treat. However, it is not necessary to provide an underlayer for improving adhesion. Examples of the surface treatment include known methods such as flame treatment, corona discharge treatment in the atmosphere or nitrogen gas, atmospheric pressure plasma treatment, blast treatment, honing treatment, and UV ozone treatment.

  As a method for applying the photocurable composition on the substrate, a spin coating method, a dipping method, a dispensing method, an ink jet method, a roll coating method, a reverse roll coating method, a gravure coating method, a spray coating method, a kiss coating method, There are known methods such as a die coating method, a slit coating method, a rod coating method, a bar coating method, a gravure coating method combined with a chamber doctor, a curtain coating method, and a roll-to-roll method. The thickness of the coating film is not particularly limited, and is usually 0.1 to 10 μm, and a coating film having a thickness of 0.01 to 0.1 μm can be suitably formed.

  In order to apply thinly, it is also possible to dilute the photocurable composition with an organic solvent, and in that case, a drying step may be appropriately incorporated depending on the boiling point and volatility of the organic solvent to be used. it can.

  Thereafter, the coating film is photocured. The coating film is irradiated with light to cure the coating film and to integrate the photocured film layer with the substrate. Although the light to irradiate depends on the type of light source and photoinitiator used, it generally includes light having a wavelength of 500 nm or less, and the light irradiation time is selected from the range of 0.1 to 300 seconds. Although it depends on the thickness of the coating film, etc., it is usually 1 to 60 seconds.

  The atmosphere during photopolymerization can be polymerized even in the air, but in order to promote the photopolymerization reaction, photopolymerization in an atmosphere with little oxygen inhibition is preferred. For example, a nitrogen gas atmosphere, an inert gas atmosphere, a fluorine gas atmosphere, a vacuum atmosphere, or the like is preferable.

  The photocurable composition may further contain a radical polymerization initiator. When an unpolymerized product is present after photocuring, the photocurable composition may be further thermally cured by heating. The temperature range in the case of thermosetting is 60 ° C to 200 ° C, preferably 70 ° C to 180 ° C, and more preferably 80 ° C to 160 ° C.

  The photocured film layer may be required to have a pattern. It is known that various functions can be achieved by forming an uneven pattern on the surface. For example, the moth-eye technology (with fine protrusion processing) demonstrates functions such as antireflection and water repellency, and the pillar structure performs functions such as light confinement, light extraction, and photonic crystal, and has a hole structure. In such a case, functions such as quantum dots, photonic crystals, and metamaterials are exhibited. In the needle structure, functions such as antibacterial and antiviral functions are exhibited. In a lattice and L (line) / S (space) structure, microchannels are exhibited. In the dot structure, characteristics such as quantum dots, photonic crystals, and metamaterials are exhibited.

  As the concavo-convex pattern forming method, optical imprint (including nano-imprint), photolithography, electron beam drawing, and the like can be used.

  For example, according to the photoimprint method, a pattern having a desired pattern formation surface is used to transfer a pattern to the photocured film layer.

  As described above, the photocurable composition is applied onto the base material layer to form a coating film, and the formed coating film is brought into contact with the pattern forming surface of the mold, and the coating film is brought into contact therewith. On the other hand, light is irradiated through the base material layer or the mold to cure the coating film. After photocuring, by separating the mold from the cured coating film, it is possible to form a photocured film layer to which the pattern has been transferred.

  A mold having a pattern forming surface can be cured with a transparent material such as quartz or sapphire or thermoplastic so that the coated film material to which the pattern is transferred can be cured by light irradiation and a cured coating film can be formed. It is preferably formed of a resin. If the mold having the pattern forming surface is a silicon wafer or a material with poor transparency such as Ni, the material of the base material layer must be light transmissive, such as quartz, sapphire, A thermoplastic resin is preferred.

  The photocurable composition used in the present invention can transfer a pattern at a relatively low pressure when pressing a mold. The pressure at this time is not particularly limited, but is in the range of 0.01 MPa to 3 MPa. As a matter of course, the pattern can be transferred even at a pressure higher than the upper limit of the pressure.

Formation of the modified surface in the photocured film layer Subsequently, for the laminate comprising the base material layer and the photocured film layer obtained by the above method, the photocured film layer uses various surface modifiers. Surface modification is performed so as to have a modified surface that is functionalized by chemical modification. According to the present invention, the surface modification of the photocured film layer is performed by VUV treatment in which the surface of the photocured film layer is irradiated with vacuum ultraviolet light (VUV) containing light having a wavelength of 183 nm or less.

  The vacuum ultraviolet light only needs to include light having a wavelength of 183 nm or less, but preferably includes light having a wavelength of 180 nm or less, and a vacuum having a spectral distribution centered on one of the wavelengths of 126 nm, 146 nm, and 172 nm. More preferably, it has ultraviolet light. In the vacuum ultraviolet light including light having a wavelength of 183 nm or less, light having a wavelength of 183 nm or less is preferably 20% or more, more preferably 30% or more in terms of integrated relative intensity.

  The atmosphere irradiated with vacuum ultraviolet light is preferably a sealed space in which the oxygen concentration can be adjusted because the oxygen concentration can be easily controlled. The oxygen concentration in the space irradiated with vacuum ultraviolet light is preferably adjusted from the range of 0.1 to 100,000 ppm in order to enhance the effect of hydrophilizing the photocured film surface. Can do. If the oxygen concentration is too low, the surface modification effect by photoexcited oxygen is diminished, and surface functional groups generated by vacuum ultraviolet light treatment are not sufficiently generated, and chemical modification may not be sufficiently performed. If it is too high, the vacuum ultraviolet light is absorbed by oxygen, the reaction between the vacuum ultraviolet light and oxygen takes precedence, a large amount of ozone is generated, and surface functional groups may not be sufficiently generated on the modified surface. is there. Moreover, the irradiation time required to achieve the surface modification of the present invention becomes long, which is not preferable from the viewpoint of productivity. More preferably, it can select from the range of 1-50,000 ppm, More preferably, it can select from the range of 10-30,000 ppm.

  In order to control the oxygen concentration in the space irradiated with vacuum ultraviolet light within the range of 0.1 to 100,000 ppm, purging with nitrogen gas, argon gas, or the like, or evacuation, and the pressure is set to the above preferred oxygen concentration The method of controlling within the range is mentioned. The oxygen concentration in the space irradiated with vacuum ultraviolet light is the oxygen concentration in the local space between the light source that irradiates vacuum ultraviolet light and the surface of the photocured film. A laminated body including a light source that irradiates vacuum ultraviolet light and a base material layer and a photocured film layer may be installed in the sealed space, and the oxygen concentration in the sealed space may be controlled. Alternatively, irradiation with vacuum ultraviolet light can be performed in an open space. In this case, nitrogen gas may simply flow through the space between the light source that irradiates vacuum ultraviolet light and the surface of the photocured film. If so, the oxygen concentration may be controlled locally.

  Regardless of the control of oxygen concentration, even under normal pressure air, depending on the irradiation intensity (radiation intensity) of vacuum ultraviolet light by shortening the distance between the light source that irradiates vacuum ultraviolet light and the photocured film layer, It is possible to overcome the effect of vacuum ultraviolet light being absorbed by oxygen in the air. In that case, it is preferable to keep the distance between the light source for irradiating vacuum ultraviolet light and the photocured film layer at 5 mm or less. When the distance exceeds 5 mm, it is necessary to increase the irradiation intensity. However, a vacuum ultraviolet lamp having a large irradiation intensity is expensive, and when the irradiation intensity increases, the reaction between oxygen in the atmosphere and vacuum ultraviolet light occurs. Preferentially, a large amount of ozone is generated, and a sufficient effect is not achieved. The distance between the light source and the photocured film layer is more preferably 1 to 3 mm.

  A known light source for irradiating vacuum ultraviolet light is used without any limitation, and a dielectric barrier discharge excimer lamp, excimer lamp, excimer laser, or the like can be usually used. In the above-mentioned integrated relative intensity, in the case of a 172 nm excimer lamp, the spectral distribution shows a single peak pattern with 172 nm as the top, and the integrated relative intensity at a wavelength of 183 nm or less is usually 80% or more.

In the formation of the modified surface of the photocured film layer of the present invention, the irradiation intensity of vacuum ultraviolet light and the laminate irradiated from the light source are adjusted so that the light exposure amount is 0.01 J / cm ^{2 to} 100 J / cm ^2. It is preferable to appropriately adjust the distance and the irradiation time.

  As described above, the surface of the photocured film layer in the laminate may be a flat surface or have an uneven pattern. When the surface of the photocured film layer is flat, the entire surface of the plane may be irradiated with VUV, and the entire surface of the plane may be modified, or VUV may be irradiated through a photomask, etc. It is also possible to obtain a surface modified surface obtained by modifying the surface corresponding to the mask pattern. In addition, any surface modified surface can then be surface modified with a surface modifier. The concavo-convex pattern can be formed by the above-described method, and the entire surface of the concavo-convex pattern can be irradiated with VUV to obtain a surface modified surface.

It is considered that the chemical bond breakage and the oxidative decomposition reaction of the organic substance by excited oxygen atoms proceed with the energy of light by VUV treatment to the photocured film made of the photocurable composition. In particular, the silicon compound finely dispersed in the photocured film is formed by breaking Si—O—Si bond of Si—O—Si or Si—O— (CH ₂ ) _n CH ₃ (n is an integer of 0 or more). Examples thereof include generation of Si—OH by breaking the O—C bond. In addition, in the course of the oxidative decomposition reaction of the photocured film, a change to a carboxyl group, a carbonyl group, an aldehyde group, a ketone group, or the like, or a radical reaction caused by an oxygen radical is also assumed. In the present invention, the surface of the photocured film is hydrophilized by these chemical changes, and surface modification with a surface modifier can be easily performed.

In particular, Si—OH is generated by breaking the Si—O—Si bond of Si—O—Si or breaking the O—C bond of Si—O— (CH ₂ ) _n CH ₃ (n is an integer of 0 or more). The effect (hydrophilization) of modifying the surface of the photocured film can be maintained for a long time. In a composition that does not contain a silicon compound, even if VUV treatment is performed, the effect of surface modification (hydrophilization) may be insufficient, decomposition reactions may be given priority, and pattern shape changes may occur. .

  The surface-modifiable laminate according to the present invention is easily functionalized on the modified surface through chemical modification with various surface modifiers.

  The surface modifier preferably used includes a compound having a functional group capable of reacting with a hydroxyl group. Examples of the compound having a functional group capable of reacting with a hydroxyl group include a compound having only a functional group capable of reacting with a hydroxyl group, a functional group capable of reacting with a hydroxyl group, a carboxyl group, an imino group, an epoxy group, an amino group, (meta ) A compound having a functional group such as an acryl group or a thiol group. Examples of the compound having a functional group capable of reacting with a hydroxyl group include a compound having a carboxyl group, a compound having an alkoxysilyl group, a compound having a silanol group, a compound having an epoxy group, a compound having an isocyanate group, and a compound having an acid anhydride Etc. Among these, a compound having an alkoxysilyl group is preferably used because of simple reaction conditions. The other surface modifier may be a compound capable of covalent bond, hydrogen bond, ionic bond, radical reaction, adsorption, coordination, etc. on the modified surface. For example, halides, metals, metal complexes, metal ions, carbon, saccharides, celluloses and the like can be mentioned.

  As the compound having an alkoxysilyl group, in addition to the compound having an alkoxysilyl group, at least one group selected from an alkoxysilyl group, a carboxyl group, an imino group, an epoxy group, an amino group, a (meth) acryl group, and a thiol group A compound having a repeating unit having an alkoxysilyl group, a repeating unit having an alkoxysilyl group, a carboxyl group, an imino group, an epoxy group, an amino group, a (meth) acryl group, and a thiol group Examples thereof include a copolymer containing a repeating unit having at least one. Among them, in addition to the alkoxysilyl group, a compound having at least one of a carboxyl group, an imide group, an epoxy group, an amino group, a (meth) acryl group, and a thiol group is easy to obtain materials and easy to react. From the point of view, it can be preferably used. For example, a carboxyl group becomes a reaction field such as a compound having a hydroxyl group, an amino group, or the like, or a compound, protein or antibody having an amino group and a carboxyl group when activated with N-hydroxysuccinimide. Reaction groups such as immobilization of compounds having amino group, hydroxyl group, thiol group, phenol group, immobilization using amino group of DNA, immobilization of antibody by reacting with amino group or imidazole group of antibody For example, an amino group becomes a reaction field with a fluorescent substance that reacts with an amino group, an aldehyde group, a protein, etc., for example, a (meth) acryl group becomes a reaction field for radical polymerization, for example, a thiol group has Reaction with fluorescent substances that react with thiol groups, disulfide bonds, bonds with gold, coupling with maleimide groups, etc. The 応場.

  Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

(Adhesion evaluation with substrate)
Place the 15 mm wide cellophane tape 405 (manufactured by Nichiban Co., Ltd.) on the surface of the photocured film, press the finger on the cellophane tape and reciprocate it three times, and then adhere it with the finger pressure. The adhesion between the photocured film and the substrate was visually evaluated according to the following criteria.
The cured film was not removed at all: 5
Exfoliation area less than 10%: 4
Exfoliation area of 10% or more and less than 50%: 3
Exfoliation area 50% or more and less than 100%: 2
With peeling area of 100% (full peeling): 1

(Appearance after photocuring film surface modification)
The photocured film surface obtained by modifying the surface of the photocured film was visually evaluated according to the following criteria.
Those that have no appearance defects due to the modification treatment: ◎
Unevenness in the range of less than 10% due to the modification treatment: ○
Unevenness in the range of 10% or more due to reforming treatment: △
All whitened by the modification treatment: ×

(Contact angle evaluation)
As an evaluation of the modification treatment of the photocured film surface, the contact angle with water was measured. The measurement is performed using a contact angle measuring device DM-700 (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle between the modified cured film surface and water is measured, and an average value of 10 measured values is obtained. The contact angle was used. The surface modification (chemical modification) was carried out by reacting a compound having a functional group capable of reacting with a hydroxyl group before the modification treatment on the surface of the photocured film, immediately after the modification treatment and after standing for 2 days at room temperature. ) At each time point.

[Example 1]
(Preparation of photocurable composition)
As a (meth) acryl group-containing alkoxysilane, trimethoxysilyl trimethylene acrylate (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103) 3.0 g, as a general alkoxysilane, ethyl silicate 40 (manufactured by Colcoat Co., Ltd.) An average pentamer of tetraethoxysilane) 6.8 g and ethanol 13.6 g, with stirring, ethanol 3.6 g / water 1.6 g / 2N HCl 0.1 g 2N HCl / ethanol mixture An aqueous solution is gradually added dropwise and stirred at room temperature for 1 hour to mix a hydrolyzate of (meth) acrylic group-containing alkoxysilane and a mixture of general alkoxysilane hydrolysates or a reaction product. A liquid was obtained.
As a polymerizable monomer, 2.5 g of polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-200), ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A) -BPE-10) 7.5 g, phenoxypolyethylene glycol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester AMP-10G) 5.0 g, ethoxylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) NK ester A-LEN-10) 5.0 g and tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-DCP) 5.0 g were used.
As a photopolymerization initiator, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (manufactured by BASF Japan Ltd., IRGACURE ( (Registered trademark) 379 EG) 1.0 g was used.
As a polymerization inhibitor, hydroquinone monomethyl ether 0.0375 g and butylhydroxytoluene 0.005 g were used.
The polymerizable monomer, photopolymerization initiator, and polymerization inhibitor were uniformly mixed, and 2.0 g of the mixture was collected. To 2.0 g of the mixture, 7.0 g of a mixture of a hydrolyzate of (meth) acrylic group-containing alkoxysilane obtained above and a general hydrolyzate of alkoxysilane or a reaction product of a silicon compound 7.0 g Was added and stirred at room temperature for 15 minutes to obtain a photocurable composition.

(Preparation of photocured film)
On a φ4 inch silicon wafer (P-type, single mirror surface, no oxide film), 2 ml of the photocurable composition obtained above is dropped, spin-coated at 3000 rpm for 30 seconds, and dried at 120 ° C. for 2 minutes. Thus, a silicon wafer coated with a coating film of the photocurable composition was obtained. The silicon wafer coated with the above coating film can be purged with nitrogen gas. The top plate is put into a container made of a quartz plate so that the above coating film becomes the top surface and sealed, and then purged with nitrogen. Then, light was irradiated at a UV exposure amount of 1 J / cm ² from the coated film surface side with an LED having an emission wavelength of 365 nm through a quartz plate to obtain a laminate in which a photocured film was laminated on a silicon wafer.

The adhesion of the laminate comprising the obtained photocured film and the silicon wafer was evaluated by the above method, and the results are shown in Table 1.

(Photocuring film modification process)
Silicon wafer having the photocured film obtained above in a chamber equipped with a dielectric barrier discharge excimer lamp (center wavelength: 172 nm, half width: 14 nm, irradiance: 10 mW / cm ² , integrated relative intensity of 90% or less of 183 nm) The laminate made of is set so that the photocured film side is irradiated with light at a distance of 3 mm from the lamp, evacuated from the atmospheric pressure, and with an excimer lamp at a vacuum degree of 100 Pa (oxygen concentration 200 ppm) for 2 minutes. Irradiated with vacuum ultraviolet light.
Thus, the laminated body which consists of a silicon wafer which modified the surface was obtained.

By the above method, the appearance after the modification treatment and the contact angle with the water of the photocured film surface of the laminate comprising the obtained silicon wafer were measured. Table 2 shows the measurement results of the appearance and contact angle (before modification, immediately after modification, and after 2 days) after the modification treatment.

(Surface modification of laminate)
3- (2-aminoethylaminopropyl) trimethoxysilane (Shin-Etsu Chemical Co., Ltd.) was used as a surface modifier on the photocured film surface of the laminate comprising the silicon wafer obtained by modifying the surface obtained above. Manufactured by LS2480) 0.1 g and 2 ml of a mixed solution of 1-methoxy-2-propanol 100 g as a solvent, spin-coated at 2000 rpm for 20 seconds, and dried at 120 ° C. for 2 minutes. A silicon wafer coated with the coating film was obtained. The silicon wafer coated with the coating film was placed in an oven maintained at 70 ° C. for 1 hour, and the surface modifier was reacted on the photocured film surface of the laminate.
Thereafter, the laminate obtained by reacting the surface modifier on the surface of the photocured film was immersed in isopropyl alcohol in a glass container, subjected to ultrasonic treatment at 45 Hz for 2 minutes, and did not react on the surface of the photocured film. Excess surface modifier was removed by rinsing. After drying the surface of the photocured film, using an infrared spectrophotometer (Perkin Elmer, Fourier Transform Infrared Spectrophotometer Spectrum One, one reflection ATR, 16 integrations, Resolution 4 cm ^-1 ) Infrared spectroscopy surface reflection (FT-IR ATR) analysis of the cured film surface was performed, and it was confirmed that there was an absorption peak peculiar to an amino group. Thus, a surface-modified laminate was obtained.

The contact angle of the surface-modified surface of the obtained surface-modified laminate with water was measured by the above method. The measurement results are shown in Table 3.

[Example 2]
(Method for producing photocurable composition)
As an alkoxysilane having a halogen element, 0.28 g of a solution obtained by diluting (3,3,3-trifluoropropyl) trimethoxysilane with ethanol to a solid content of 1%, While stirring, a mixture of 3.0 g of methoxysilyltrimethylene acrylate (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103) and 13.6 g of ethanol was mixed with ethanol 1.6 g / water 0.3 g / 2N-HCl 0. 1 g of 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise and stirred at room temperature for 1 hour to obtain a mixture or reaction product of a hydrolyzate of alkoxysilane having a halogen element and (meth) acrylic group-containing alkoxysilane. Obtained. The obtained reaction product was further mixed with 6.8 g of ethyl silicate 40 (an average pentamer of tetraethoxysilane manufactured by Colcoat Co., Ltd.) as a general alkoxysilane and 85% by mass of zirconium butoxide as a zirconium alkoxide. 1.7 g of 1-butanol solution of (tetrabutylzirconium alkoxide) is mixed, and with stirring, 2.6 g of ethanol / 0.7 g of water / 2 g of 0.1N HCl and 2 g of 2N HCl / ethanol mixed aqueous solution are mixed. The solution was gradually added dropwise at room temperature. Furthermore, an ethanol aqueous solution of ethanol 1.0 g / water 0.4 g was gradually added dropwise and stirred at room temperature for 1 hour. In this manner, a mixed liquid of a general alkoxysilane, an alkoxysilane having a halogen element, a (meth) acryl group-containing alkoxysilane and a hydrolyzate or reaction product of a zirconium alkoxide was obtained.
To the mixture of polymerizable monomer, photopolymerization initiator and polymerization inhibitor prepared in Example 1, 2.0 g of the general alkoxysilane obtained above, alkoxysilane having a halogen element, (meth) acrylic A photocurable composition was obtained by adding 7.0 g of a mixed solution of a silicon compound comprising a hydrolyzate or reaction product of a group-containing alkoxysilane and zirconium alkoxide and stirring at room temperature for 15 minutes.

(Preparation of photocured film)
Except for using the obtained photocurable composition, a laminate was produced in the same manner as in Example 1, and the adhesion of the obtained laminate comprising the photocured film and the silicon wafer was determined. Evaluation was performed by the above method, and the results are shown in Table 1 above.

(Photocuring film modification process)
A laminate comprising a silicon wafer having a photocured film obtained in a chamber equipped with a dielectric barrier discharge excimer lamp (center wavelength: 172 nm, half width: 14 nm, irradiance: 10 mW / cm ² , cumulative relative intensity of 90% or less of 183 nm) The body was set so that the photocured film side was irradiated with light at a distance of 3 mm from the lamp, evacuated from atmospheric pressure, and irradiated with vacuum ultraviolet light at a vacuum degree of 100 Pa (oxygen concentration 200 ppm) for 2 minutes, The same operation as in Example 1 was performed to obtain a laminate composed of a silicon wafer whose surface was modified.

  By the above method, the appearance after the modification treatment and the contact angle with the water of the photocured film surface of the laminate comprising the obtained silicon wafer were measured. Table 2 shows the measurement results of the appearance and contact angle (before modification, immediately after modification, and after 2 days) after the modification treatment.

(Surface modification of laminate)
3- (2-aminoethylaminopropyl) trimethoxysilane (Shin-Etsu Chemical Co., Ltd.) was used as a surface modifier on the photocured film surface of the laminate comprising the silicon wafer obtained by modifying the surface obtained above. Manufactured by LS2480) 0.1 g and 2 ml of a mixed solution of 1-methoxy-2-propanol 100 g as a solvent, spin-coated at 2000 rpm for 20 seconds, and dried at 120 ° C. for 2 minutes. A silicon wafer coated with the coating film was obtained. The silicon wafer coated with the coating film was placed in an oven maintained at 70 ° C. for 1 hour, and the surface modifier was reacted on the photocured film surface of the laminate.
Thereafter, the laminate obtained by reacting the surface modifier on the surface of the photocured film was immersed in isopropyl alcohol in a glass container, subjected to ultrasonic treatment at 45 Hz for 2 minutes, and did not react on the surface of the photocured film. Excess surface modifier was removed by rinsing. After drying the surface of the photocured film, infrared spectroscopic surface reflection (FT-IR ATR) analysis of the photocured film surface was performed, and it was confirmed that there was an absorption peak peculiar to the amino group. Thus, a surface-modified laminate was obtained.

  The contact angle of the surface-modified surface of the obtained surface-modified laminate with water was measured by the above method. The measurement results are shown in Table 3.

[Example 3]
In the modification of the photocured film, a chamber equipped with a dielectric barrier discharge excimer lamp (center wavelength: 172 nm, half width: 14 nm, irradiance: 10 mW / cm ² , cumulative relative intensity of 90% or less of 183 nm) The obtained laminate made of a silicon wafer having a photocured film was set so that the photocured film side was irradiated with light at a distance of 3 mm from the lamp, evacuated from atmospheric pressure, and a vacuum degree of 1 kPa (oxygen) Except for irradiating the vacuum ultraviolet light at a concentration of 2,000 ppm for 2 minutes, the same operation as in Example 2 was performed to obtain a laminate composed of a silicon wafer whose surface was modified.

  By the above method, the appearance after the modification treatment and the contact angle with the water of the photocured film surface of the laminate comprising the obtained silicon wafer were measured. Table 2 shows the measurement results of the appearance and contact angle (before modification, immediately after modification, and after 2 days) after the modification treatment.

(Surface modification of laminate)
In the same manner as in Example 2, a surface modifier was reacted on the photocured film surface of the laminate composed of the silicon wafer obtained by modifying the surface obtained above.
Thereafter, the laminate obtained by reacting the surface modifier on the surface of the photocured film was immersed in isopropyl alcohol in a glass container, subjected to ultrasonic treatment at 45 Hz for 2 minutes, and did not react on the surface of the photocured film. Excess surface modifier was removed by rinsing. After drying the surface of the photocured film, infrared spectroscopic surface reflection (FT-IR ATR) analysis of the photocured film surface was performed, and it was confirmed that there was an absorption peak peculiar to the amino group. Thus, a surface-modified laminate was obtained.

  The contact angle of the surface-modified surface of the obtained surface-modified laminate with water was measured by the above method. The measurement results are shown in Table 3.

[Example 4]
In the modification of the photocured film, a chamber equipped with a dielectric barrier discharge excimer lamp (center wavelength: 172 nm, half width: 14 nm, irradiance: 10 mW / cm ² , cumulative relative intensity of 90% or less of 183 nm) The obtained laminate made of a silicon wafer having a photocured film was set so that the photocured film side was irradiated with light at a distance of 3 mm from the lamp, evacuated from atmospheric pressure, and the degree of vacuum was 13 kPa (oxygen) Except for irradiation with vacuum ultraviolet light at a concentration of 27,000 ppm for 2 minutes, the same operation as in Example 2 was performed to obtain a laminate composed of a silicon wafer whose surface was modified.

  By the above method, the appearance after the modification treatment and the contact angle with the water of the photocured film surface of the laminate comprising the obtained silicon wafer were measured. Table 2 shows the measurement results of the appearance and contact angle (before modification, immediately after modification, and after 2 days) after the modification treatment.

(Surface modification of laminate)
In the same manner as in Example 2, a surface modifier was reacted on the photocured film surface of the laminate composed of the silicon wafer obtained by modifying the surface obtained above.
Thereafter, the laminate obtained by reacting the surface modifier on the surface of the photocured film was immersed in isopropyl alcohol in a glass container, subjected to ultrasonic treatment at 45 Hz for 2 minutes, and did not react on the surface of the photocured film. Excess surface modifier was removed by rinsing. After drying the surface of the photocured film, infrared spectroscopic surface reflection (FT-IR ATR) analysis of the photocured film surface was performed, and it was confirmed that there was an absorption peak peculiar to the amino group. Thus, a surface-modified laminate was obtained.

  The contact angle of the surface-modified surface of the obtained surface-modified laminate with water was measured by the above method. The measurement results are shown in Table 3.

[Example 5]
In the modification process of the photocured film, a chamber equipped with a dielectric barrier discharge excimer lamp (center wavelength 172 nm, half width 14 nm, irradiance 10 mW / cm ² , integrated relative intensity 90% or less of 183 nm) The obtained laminate made of a silicon wafer having a photocured film was set so that the photocured film side was irradiated with light at a distance of 3 mm from the lamp, and nitrogen gas containing 1200 ppm of oxygen gas was placed in the chamber. While continuously supplying, a laminated body made of a silicon wafer having a surface modified was obtained by performing the same operation as in Example 2 except that irradiation with vacuum ultraviolet light was performed for 20 minutes.

  By the above method, the appearance after the modification treatment and the contact angle with the water of the photocured film surface of the laminate comprising the obtained silicon wafer were measured. Table 2 shows the measurement results of the appearance and contact angle (before modification, immediately after modification, and after 2 days) after the modification treatment.

(Surface modification of laminate)
In the same manner as in Example 2, a surface modifier was reacted on the photocured film surface of the laminate composed of the silicon wafer obtained by modifying the surface obtained above.
Thereafter, the laminate obtained by reacting the surface modifier on the surface of the photocured film was immersed in isopropyl alcohol in a glass container, subjected to ultrasonic treatment at 45 Hz for 2 minutes, and did not react on the surface of the photocured film. Excess surface modifier was removed by rinsing. After drying the surface of the photocured film, infrared spectroscopic surface reflection (FT-IR ATR) analysis of the photocured film surface was performed, and it was confirmed that there was an absorption peak peculiar to the amino group. Thus, a surface-modified laminate was obtained.

  The contact angle of the surface-modified surface of the obtained surface-modified laminate with water was measured by the above method. The measurement results are shown in Table 3.

[Example 6]
The same operation as in Example 4 was performed to obtain a laminate composed of a silicon wafer whose surface was modified. By the above method, the appearance after the modification treatment and the contact angle with the water of the photocured film surface of the laminate comprising the obtained silicon wafer were measured. Table 2 shows the measurement results of the appearance and contact angle (before modification, immediately after modification, and after 2 days) after the modification treatment.

(Surface modification of laminate)
On the photocured film surface of the laminate composed of the silicon wafer obtained by modifying the surface obtained above,
As a surface modifier, 0.1 ml of 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., LS3150) and 2 ml of a mixed solution consisting of 100 g of 1-methoxy-2-propanol as a solvent were dropped, 2000 rpm, 20 The film was spin-coated for 2 seconds and dried at 120 ° C. for 2 minutes to obtain a silicon wafer coated with the coating film of the surface modifier. The silicon wafer coated with the coating film was placed in an oven maintained at 70 ° C. for 1 hour, and the surface modifier was reacted on the photocured film surface of the laminate.
Thereafter, the laminate obtained by reacting the surface modifier on the surface of the photocured film was immersed in isopropyl alcohol in a glass container, subjected to ultrasonic treatment at 45 Hz for 2 minutes, and did not react on the surface of the photocured film. Excess surface modifier was removed by rinsing. After drying the surface of the photocured film, infrared spectroscopic surface reflection (FT-IR ATR) analysis of the photocured film surface was performed, and it was confirmed that there was an absorption peak peculiar to the amino group. Thus, a surface-modified laminate was obtained.

  The contact angle of the surface-modified surface of the obtained surface-modified laminate with water was measured by the above method. The measurement results are shown in Table 3.

[Example 7]
The same operation as in Example 4 was performed to obtain a laminate composed of a silicon wafer whose surface was modified. By the above method, the appearance after the modification treatment and the contact angle with the water of the photocured film surface of the laminate comprising the obtained silicon wafer were measured. Table 2 shows the measurement results of the appearance and contact angle (before modification, immediately after modification, and after 2 days) after the modification treatment.

(Surface modification of laminate)
As a surface modifier, (3-mercaptopropyl) trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-) is used as a surface modifier on the surface of the photocured film of the laminate comprising the silicon wafer obtained by modifying the surface obtained above. 803) 2 g of a mixed solution consisting of 1 g of 1 g and 100 g of 1-methoxy-2-propanol as a solvent is dropped, spin-coated at 2000 rpm for 20 seconds, and dried at 120 ° C. for 2 minutes to coat the surface modifier coating film A silicon wafer was obtained. The silicon wafer coated with the coating film was placed in an oven maintained at 70 ° C. for 1 hour, and the surface modifier was reacted on the photocured film surface of the laminate.
Thereafter, the laminate obtained by reacting the surface modifier on the surface of the photocured film was immersed in isopropyl alcohol in a glass container, subjected to ultrasonic treatment at 45 Hz for 2 minutes, and did not react on the surface of the photocured film. Excess surface modifier was removed by rinsing. After drying the surface of the photocured film, infrared spectroscopic surface reflection (FT-IR ATR) analysis of the surface of the photocured film was performed, and it was confirmed that there was an absorption peak peculiar to the thiol group. Thus, a surface-modified laminate was obtained.

  The contact angle of the surface-modified surface of the obtained surface-modified laminate with water was measured by the above method. The measurement results are shown in Table 3.

[Example 8]
(Preparation of photocured film with uneven pattern by imprint method)
A diameter of 230 nm, which was subjected to mold release treatment with a fluorine-containing silane coupling agent (Optool HD-1100TH, manufactured by Daikin Industries, Ltd.) and rinsed with a rinsing liquid (Optool HD-TH, manufactured by Daikin Industries, Ltd.). The photocurable composition obtained in Example 2 was spin-coated at 3000 rpm for 30 seconds on a φ2 inch silicon mold on which a pillar pattern having a height of 500 nm, a pitch of 460 nm, and a triangular arrangement was formed. Then, it was dried at 120 ° C. for 2 minutes to obtain a silicon mold coated with the coating film of the photocurable composition. Silicon mold coated with the above-mentioned coating film and a biaxially stretched polyethylene terephthalate (PET) film with a thickness of 125 μm cut to 10 cm × 10 cm (manufactured by Toyobo Co., Ltd., double-sided easy-adhesion treated PET film, Cosmo Shine A-4300: base material) was set in a nanoimprint apparatus (manufactured by SCIVAX Co., Ltd., X-300), evacuated to 300 Pa, and then a silicon mold coated with the coating film and a PET film. The resulting substrate was brought into contact, a pressure of 2.0 MPa was applied, and light was irradiated from an LED 365 nm light source for 60 seconds to perform UV nanoimprinting. Thereafter, the PET film was peeled off from the silicon mold to obtain a laminate having a photocured film layer having a concavo-convex pattern formed on the surface.

As a result of observing the pattern surface of the laminate obtained above with an AFM (manufactured by Shimadzu Corporation, Nano Search Microscope SFT-3500, Super Sharp SI Probe SSS-NCHR-10), the silicon mold used was It was confirmed that a hole pattern having a diameter of 230 nm, a depth of 500 nm, and a pitch of 460 nm corresponding to the pattern was formed.
The adhesion between the photocured film (pattern surface) and the PET film (base material) of the obtained laminate was evaluated by the above method, and the results are shown in Table 1 above. The photocured film (pattern surface) of the obtained laminate has a two-dimensional photonic crystal structure in which the refractive index changes periodically.

(Photocuring film modification process)
The laminate obtained above was placed in a chamber equipped with a dielectric barrier discharge excimer lamp (center wavelength 172 nm, half width 14 nm, irradiance 10 mW / cm ² , cumulative relative intensity 90% or less 183 nm) and the distance from the lamp At 3 mm, the photocured film (pattern surface) was set to be irradiated with light, evacuated from atmospheric pressure, and irradiated with vacuum ultraviolet light with an excimer lamp at a vacuum degree of 100 Pa (oxygen concentration 200 ppm) for 2 minutes.
By the above method, the appearance after the modification treatment and the contact angle with water of the photocured film surface of the obtained laminate were measured. Table 2 shows the measurement results of the appearance and contact angle (before modification, immediately after modification, and after 2 days) after the modification treatment. The obtained laminate has a lower contact angle immediately after modification and after 2 days than the laminate of the comparative example in which the hole pattern is formed on the surface but the hole pattern is not formed. It was found that the surface was sufficiently modified.

(Surface modification of laminate)
3- (2-aminoethylaminopropyl) trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., LS2480) is used as a surface modifier on the photocured film surface of the laminate obtained by modifying the surface obtained above. 4 ml of a mixed solution consisting of 0.1 g and 100 g of 1-methoxy-2-propanol was added dropwise as a solvent, spin-coated at 2000 rpm for 20 seconds, and dried at 120 ° C. for 2 minutes to coat the coating film of the surface modifier. A laminated body was obtained. The laminate coated with the coating film was placed in an oven kept at 70 ° C. for 1 hour, and a surface modifier was reacted on the photocured film surface of the laminate.
Thereafter, the laminate obtained by reacting the surface modifier on the surface of the photocured film was immersed in isopropyl alcohol in a glass container, subjected to ultrasonic treatment at 45 Hz for 2 minutes, and did not react on the surface of the photocured film. Excess surface modifier was removed by rinsing. After drying the surface of the photocured film, infrared spectroscopic surface reflection (FT-IR ATR) analysis of the photocured film surface was performed, and it was confirmed that there was an absorption peak peculiar to the amino group. Thus, a surface-modified laminate was obtained.

  The contact angle of the surface-modified surface of the obtained surface-modified laminate with water was measured by the above method. The measurement results are shown in Table 3.

[Comparative Example 1]
In the modification treatment of the photocured film of Example 1, 185 nm or 254 nm instead of the dielectric barrier discharge excimer lamp (center wavelength 172 nm, half-value width 14 nm, irradiance 10 mW / cm ² , relative intensity 90% below 183 nm) A laminate composed of a silicon wafer having a photocured film obtained in Example 1 using a low-pressure mercury lamp (irradiance 10 mW / cm ² , cumulative relative intensity 0% of 183 nm or less) that generates ultraviolet light of From the silicon wafer whose surface was modified by performing the same operation as in Example 1 except that the light cured film side of the laminate was irradiated with light at a distance of 3 mm from the lamp and irradiated for 10 minutes. The resulting laminate was obtained.

  By the above method, the appearance after the modification treatment and the contact angle with the water of the photocured film surface of the laminate comprising the obtained silicon wafer were measured. Table 2 shows the measurement results of the appearance and contact angle (before modification, immediately after modification, and after 2 days) after the modification treatment. The contact angle of the surface of the photocured film of the laminate was changed with time and increased after 2 days.

[Comparative Example 2]
As a polymerizable monomer, 2.5 g of polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-200), ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A) -BPE-10) 7.5 g, phenoxypolyethylene glycol acrylate (Shin Nakamura Chemical Co., Ltd., NK ester AMP-10G) 5.0 g, ethoxylated o-phenylphenol acrylate (Shin Nakamura Chemical Co., Ltd.), NK ester A-LEN-10) 5.0 g and tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-DCP) 5.0 g were used.
As a photopolymerization initiator, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (manufactured by BASF Japan Ltd., IRGACURE ( (Registered trademark) 379 EG) 1.0 g was used.
As a polymerization inhibitor, hydroquinone monomethyl ether 0.0375 g and butylhydroxytoluene 0.005 g were used.
By uniformly mixing the above polymerizable monomer, photopolymerization initiator, and polymerization inhibitor, a photocurable composition containing no silicon compound was obtained.

(Preparation of photocured film)
A laminate obtained by laminating a photocured film on a silicon wafer was obtained in the same manner as in Example 1 except that the photocurable composition containing no silicon compound was used. The adhesion of the obtained laminate comprising the photocured film and the silicon wafer was evaluated by the above method, and the results are shown in Table 1 above.

(Photocuring film modification process)
Furthermore, in the same manner as in Example 1, a laminate including a photocured film layer whose surface was subjected to a modification treatment and a silicon wafer was obtained.
By the above method, the appearance after the modification treatment and the contact angle with the water of the photocured film surface of the laminate comprising the obtained silicon wafer were measured. Table 2 shows the measurement results of the appearance and contact angle (before modification, immediately after modification, and after 2 days) after the modification treatment. The contact angle of the photocured film surface of the laminate was larger than that of Example 1.

(Surface modification of laminate)
3- (2-aminoethylaminopropyl) trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., LS2480) is used as a surface modifier on the photocured film surface of the laminate obtained by modifying the surface obtained above. 2 g of a mixed solution consisting of 0.1 g and 100 g of 1-methoxy-2-propanol was added dropwise as a solvent, spin-coated at 2000 rpm for 20 seconds, and dried at 120 ° C. for 2 minutes to coat the surface modifier coating film A laminated body was obtained. The laminate coated with the coating film was placed in an oven kept at 70 ° C. for 1 hour, and a surface modifier was reacted on the photocured film surface of the laminate.
Thereafter, the laminate obtained by reacting the surface modifier on the surface of the photocured film was immersed in isopropyl alcohol in a glass container, subjected to ultrasonic treatment at 45 Hz for 2 minutes, and did not react on the surface of the photocured film. Excess surface modifier was removed by rinsing. After drying the photocured film surface, infrared spectroscopic surface reflection (FT-IR ATR) analysis of the photocured film surface was performed, but no absorption peak peculiar to an amino group was confirmed.

[Comparative Example 3]
(Known film modification treatment)
In a chamber equipped with a dielectric barrier discharge excimer lamp (center wavelength 172 nm, half width 14 nm, irradiance 10 mW / cm ² , integrated relative intensity 90% or less of 183 nm), a cycloolefin polymer film (manufactured by Nippon Zeon Co., Ltd., ZEONOR) Film ZF-16, thickness 100 μm) is set to be irradiated with light at a distance of 3 mm from the lamp, evacuated from atmospheric pressure, and vacuumed by an excimer lamp at a vacuum degree of 100 Pa (oxygen concentration 200 ppm) for 2 minutes. Irradiated with ultraviolet light.
In this way, a cycloolefin polymer film whose surface was modified was obtained.
By the above method, the appearance after the modification treatment and the contact angle of the obtained cycloolefin polymer film with water were measured. Table 2 shows the measurement results of the appearance and contact angle (before modification, immediately after modification, and after 2 days) after the modification treatment.

(Surface modification of laminate)
To the cycloolefin polymer film obtained by modifying the surface obtained above, as a surface modifier, 0.1 g of 3- (2-aminoethylaminopropyl) trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., LS2480) and As a solvent, 2 ml of a mixed solution consisting of 100 g of 1-methoxy-2-propanol was dropped, spin-coated at 2000 rpm for 20 seconds, dried at 120 ° C. for 2 minutes, and a cycloolefin coated with a surface modifier coating film A polymer film was obtained. The cycloolefin polymer film coated with the coating film was placed in an oven maintained at 70 ° C. for 1 hour, and the surface modifier was reacted on the cycloolefin polymer film surface.
Then, the cycloolefin polymer film obtained by reacting the surface modifier with the cycloolefin polymer film surface is immersed in isopropyl alcohol in a glass container, and subjected to ultrasonic treatment at 45 Hz for 2 minutes. The excess surface modifier that did not react was removed by rinsing. After the cycloolefin polymer film surface was dried, infrared spectroscopic surface reflection (FT-IR ATR) analysis of the cycloolefin polymer film surface was performed, and it was confirmed that there was a slight absorption peak peculiar to amino groups. Thus, a surface-modified laminate was obtained.

  The contact angle of the surface-modified surface of the obtained surface-modified laminate with water was measured by the above method. The measurement results are shown in Table 3.

Claims (14)

A substrate layer and a photocured film layer formed on the substrate layer and having a surface modified so as to be easily functionalized by chemical modification using various surface modifiers A method for producing a surface-modifiable laminate,
On one surface of the base material layer, a polymerizable monomer, a silicon compound, a photopolymerization initiator , a hydrolyzate of zirconium alkoxide or titanium alkoxide, or a reaction product of zirconium alkoxide or titanium alkoxide and alkoxysilanes A photocurable composition containing a coating is applied to form a coating film, and the coating film is irradiated with light to cure the photocurable composition, thereby forming the photocurable film layer. The cured film layer is irradiated with vacuum ultraviolet light containing light having a wavelength of 183 nm or less, and the surface of the photocured film layer is modified to be easily functionalized through chemical modification using various surface modifiers. A process for producing a surface-modifiable laminate, characterized by A substrate layer and a photocured film layer formed on the substrate layer and having a surface modified so as to be easily functionalized by chemical modification using various surface modifiers A method for producing a surface-modifiable laminate,
On one surface of the base material layer, a photocurable composition containing a polymerizable monomer, a silicon compound, and a photopolymerization initiator is applied to form a coating film, and the coating film is irradiated with light. Then, the photocurable film layer is formed by curing the photocurable composition, the photocured film layer has a concavo-convex pattern on the surface, and light having a wavelength of 183 nm or less is applied to the photocurable film layer. Surface modification is possible by irradiating the vacuum ultraviolet light containing and modifying the surface of the photocured film layer so as to be easily functionalized through chemical modification using various surface modifiers To make a simple laminate. The method according to claim 1 or 2 , wherein the silicon compound of the photocurable composition is a silicon compound having a siloxane bond. The process according to claim 3 , wherein the silicon compound having a siloxane bond is an alkoxysilane or a hydrolyzate of an alkoxysilane. 3. The method according to claim 1, wherein the vacuum ultraviolet light containing light having a wavelength of 183 nm or less has light having a wavelength of 183 nm or less having an integrated relative intensity of 20% or more. The process according to claim 1 or 2 , wherein the irradiation with vacuum ultraviolet light is performed in an atmosphere having an oxygen concentration of 0.1 to 100,000 ppm in a sealed space. The process according to claim 1 or 2 , wherein the irradiation with the vacuum ultraviolet light is performed in an open space in an atmosphere in which nitrogen is flowed between the light source for irradiating the vacuum ultraviolet light and the photocured film layer. . The method according to claim 1 or 2 , wherein the distance between the light source for irradiating the vacuum ultraviolet light and the photocured film layer is 5 mm or less. A process according to claim 1 or 2 irradiation of vacuum ultraviolet light, the light exposure amount and performs so that 0.01~100J / cm ^2. The method according to claim 2 , wherein the concavo-convex pattern is formed by an imprint method. The method according to claim 2 , wherein the concavo-convex pattern has a photonic crystal structure. On one surface of the base material layer, a photocurable composition containing a polymerizable monomer, a silicon compound, and a photopolymerization initiator is applied to form a coating film, and the coating film is irradiated with light. Then, a photocured film layer is formed by curing the photocurable composition, and the photocured film layer is irradiated with vacuum ultraviolet light containing light having a wavelength of 183 nm or less so as to irradiate the surface of the photocured film layer. A compound having a functional group capable of reacting with a hydroxyl group on the surface of the modified photocured film layer, modified so as to be easily functionalized through chemical modification using various surface modifiers A method for producing a surface-modified laminate, characterized by reacting and chemically modifying the photocured film layer . The method according to claim 12 , wherein the compound having a functional group capable of reacting with a hydroxyl group is a compound having an alkoxysilyl group. The compound having an alkoxysilyl group is a compound having at least one of a carboxyl group, an imide group, an epoxy group, an amino group, a (meth) acryl group, and a thiol group in addition to the alkoxysilyl group. Item 14. The method according to Item 13 .