JP2007106966A - Super-hydrophilic substrate and method for producing the same - Google Patents

Abstract

[PROBLEMS] To easily produce a superhydrophilic substrate, particularly a superhydrophilic substrate excellent in transparency and durability.
A hydrophilic substrate comprising a hydrophilic concavo-convex structure member having another fine concavo-convex surface on a substrate having a fine concavo-convex shape.
[Selection figure] None

Description

  The present invention relates to a superhydrophilic substrate and a method for producing the same.

  Many applications are expected by making the surfaces of various members hydrophilic. Specifically, for example, proteins, colloids, bacteria, humic substances, fats and oils used in the fields of food industry, medicine (including medical equipment such as artificial organs and diagnosis), pharmaceutical industry, wastewater treatment, painting, printing, etc. Molded articles with little adsorption of pollutants in the atmosphere, biocompatible molded articles, immobilization carriers that do not denature enzymes, fungus bodies, etc., commercial, agricultural, transportation, household goods, optical instruments, paints, etc. Antifogging films such as antifogging films and antifogging coatings used in the above field, and surface hydrophilic members that can be used for applications such as antistatic use used in the fields of electronic industry and the like.

  Surface characteristics required for hydrophilic members used in each of the above fields include suppression of adsorption of materials such as proteins, fats and oils, humic substances, etc., antifogging properties, ecological compatibility, antistatic properties, etc. Is mentioned. These functions can be realized by high hydrophilicity. For example, in the paint field, these substances are unique especially when used on antifouling paint films and sensor surfaces to which oily substances in rainwater do not adhere. A surface that does not adsorb on the surface is desired. Further, an antifogging surface in which water droplets are in an extended wet state due to strong hydrophilicity is required to have higher optical transparency and smoothness in addition to this hydrophilicity. Further, regarding biocompatibility, in the medical field such as artificial organs, a surface that suppresses thrombus, hemolysis, sensitization, antigen-antibody reaction and the like is required. Furthermore, expression of antistatic ability due to hydrophilicity is regarded as important particularly in the field of electronic industry.

As an example of a surface hydrophilization method for satisfying such a requirement, a method of surface grafting a hydrophilic monomer is known.
As a specific method, a hydrophilic radically polymerizable compound is formed on the surface of a lipophilic substrate mainly composed of a lipophilic resin having a predetermined amount of hydrogen groups bonded to carbon-carbon double bonds and / or tertiary carbons. A method of forming a hydrophilic layer on the surface by applying actinic light and irradiating actinic rays (for example, see Patent Document 1), a photopolymerization initiation layer (consisting of a photopolymerization initiator, a monomer and / or an oligomer) on the substrate surface A method in which a hydrophilic polymer is grafted onto the surface of the lower layer by applying energy in a state where the hydrophilic monomer is in contact with the lower layer to which the coating is applied (see, for example, Patent Document 2). Provided with a polymerization initiating layer in which a polymer having a polymerization initiating ability and a polymer having a crosslinkable group are immobilized by a crosslinking reaction, and a hydrophilic compound having a polymerizable group is directly bonded to the polymerization initiating layer. Form Law (Patent Document 3) it is known.
JP-A-53-17407 Japanese Patent Laid-Open No. 10-53658 JP 2004-123837 A

  However, it is still difficult to develop a sufficiently hydrophilic surface in any of the above methods, and a technique capable of more easily producing a superhydrophilic substrate has been desired. In addition, it is desired to realize a superhydrophilic substrate excellent in transparency and a superhydrophilic substrate excellent in durability.

The above-described problem of the present invention is achieved by a hydrophilic substrate having a hydrophilic concavo-convex structure having another fine concavo-convex surface containing a compound having a hydrophilic group on a substrate having a fine concavo-convex shape. It was found that
That is, the present invention is greatly characterized in that a multi-step uneven shape is achieved by providing a hydrophilic surface uneven structure made of another member on the surface of a substrate having an uneven shape. Thereby, it is possible to easily control the multi-step surface uneven shape, and at the same time, the surface uneven structure can contain a compound having a hydrophilic group, thereby making it possible to more easily form a substrate having a superhydrophilic surface. Obtainable.
In particular, it is preferable that the hydrophilic surface uneven structure is formed by forming a surface unevenness using a polymerization reaction so that the multistage uneven structure can be controlled extremely finely and easily. In order to form the concavo-convex structure, it is necessary to have a compound having a polymerization initiating ability and a polymerizable compound, but these functions are separated into a polymerization initiating layer and a polymerizable surface hydrophilic layer. As a result, the adhesion between the polymerization initiation layer and the substrate can be further improved, and the durability can be improved.

That is, the configuration of the present invention is as follows.
(1) A hydrophilic substrate having a hydrophilic uneven structure member having another fine uneven surface on a substrate having a fine uneven shape.
(2) The hydrophilic substrate according to (1), wherein the hydrophilic concavo-convex structure member has a concavo-convex surface formed using a polymerization reaction.
(3) The hydrophilic concavo-convex structure member includes a polymerization initiating layer containing a compound having a polymerization initiating ability, and a hydrophilic layer in which a compound containing a polymerizable group is directly bonded to the polymerization initiating layer. The hydrophilic substrate as described in (2) above, wherein

(4) The hydrophilic substrate according to any one of (1) to (3) above, wherein at least one fine irregular shape of the substrate is formed by photolithography.
(5) The hydrophilic substrate according to any one of (1) to (3) above, wherein at least one fine irregular shape of the substrate is formed by a coating layer containing fine particles.

(6) Forming a hydrophilic concavo-convex structure member having a fine concavo-convex surface by forming a hydrophilic layer having polymerization initiating ability and polymerization ability on a substrate having a fine concavo-convex shape and exposing it like an image. The method for producing a hydrophilic substrate as described in (1) or (2) above, wherein
(7) A hydrophilic concavo-convex structure member having a fine concavo-convex surface by forming a layer having a polymerization initiating ability and a hydrophilic layer having a polymerization ability on a substrate having a fine concavo-convex shape, and exposing it like an image. The method for producing a hydrophilic substrate according to any one of (1) to (3), wherein the hydrophilic substrate is formed.

  According to the present invention, a superhydrophilic substrate can be easily produced. Furthermore, it is possible to provide a superhydrophilic substrate having excellent transparency and durability.

<Board>
The substrate of the present invention has a fine uneven shape.
The substrate is not particularly limited as long as the uneven shape can be formed on the substrate, and any substrate made of an inorganic substance or an organic substance such as a polymer can be used. As a substrate made of an inorganic substance, a glass plate, a silicon plate, an aluminum plate, a stainless steel plate, a metal plate such as gold, silver, zinc, or copper, and a metal oxide such as ITO, tin oxide, alumina, or titanium oxide A substrate or the like provided on the surface can also be used.
Polymer substrates include polyethylene, polypropylene, polystyrene, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polycarbonate, polyvinyl acetal, polyurethane, epoxy resin, polyester A substrate made of resin, acrylic resin, or polyimide resin can be used.
In the case where the hydrophilic concavo-convex structure member provided on the substrate has a reactive group (for example, a polymerization initiator), these polymer substrates are subjected to corona treatment in order to improve the binding property with the reactive group. It may be one in which a functional group such as a hydroxyl group or a carboxyl group is introduced to the surface by plasma treatment or the like.

(Pattern formation / means on the substrate)
Any of various conventionally known methods can be used as a method for forming a fine uneven shape on the substrate.
For example, it can be formed by physical machining or grinding, or vacuum deposition, lithography, ion beam processing, plasma processing, etc., which are used for integrated circuit manufacturing, and can also be formed by laser processing or printing technology. can do. A method of dissolving or corroding a solid surface by electrolysis, chemical reaction, microbial reaction, etc., which is naturally generated by controlling external factors such as temperature and temperature gradient, chemical concentration and concentration gradient, and electromagnetic field, electrolysis A method of depositing a substance on the surface of a solid by diffusion-controlled aggregation, a method of attaching a fine particle aggregate to the surface of a solid, mixing two kinds of incompatible substances with each other, and proceeding phase separation, so that the two phases are involved with each other Use a method in which only one of the substances is eluted when a phase separation pattern is formed, or a method in which the crystal phase is controlled by temperature, such as alkyl ketene dimer or dialkyl ketone, to form multi-step irregularities naturally. There are methods. In particular, those that are naturally multi-stepped when solidified at room temperature can be used as water-repellent paints.
In particular, a photolithography method is one of the methods for forming surface irregularities. It is widely used in semiconductor manufacturing, and irregularities of about 1 μm to 100 μm can be created easily and inexpensively.
A fine particle-containing liquid coating method is also used as a method for forming surface irregularities. It can be prepared by dispersing fine particles such as silica, zirconium and titanium oxide having a diameter of 0.01 to 100 μm in a coating solution and coating the substrate by spin coating, casting or the like.

  Furthermore, the substrate itself may be a so-called multi-step uneven structure surface in which the uneven structure A having a large period is formed by machining, and an uneven structure having a smaller period is formed by a method such as corrosion. Various combinations of the above methods may be used to form a multi-step uneven structure surface, or a metal mold or epoxy resin may be used to create a mold from a multi-step uneven surface that already exists in nature, such as the lotus leaf surface. However, it can also be formed by using the mold itself or a replica of the surface of the multi-level uneven structure created from the mold.

  The shape of the fine uneven shape of the substrate, specifically, the shape of the convex part or concave part, the width of the convex part or concave part, the height of the convex part, the depth of the concave part, and further, between the convex parts or between the concave parts The distance and the like are not particularly limited, and can be appropriately set so that desired hydrophilicity is finally obtained. The shape of the convex portion may be, for example, a quadrangle, a triangle, an irregular shape, or the like. In general, the height of the convex portion is preferably in the range of 0.05 to 100 μm. The distance between the convex portions is usually preferably in the range of 0.05 to 1000 μm, more preferably in the range of 0.5 to 100 μm.

<Hydrophilic concavo-convex structure member>
The hydrophilic concavo-convex structure member of the present invention is provided by another means as another structure on the substrate having the fine concavo-convex shape. Thereby, since a hydrophilic surface member can be provided independently, it is easy to control the expression of hydrophilicity, and in particular, a fine surface uneven shape can be easily controlled. The concavo-convex shape of the hydrophilic structural member is preferably finer than the concavo-convex shape on the substrate surface, and preferably has a period in the range of 1/50 to 1/2 of the concavo-convex period on the substrate surface.

  From the viewpoint of controlling the surface uneven shape, it is particularly preferable to form the fine uneven shape by a chemical method utilizing a polymerization reaction. Specifically, a pattern can be formed by exposing the polymerizable compound imagewise in the presence of a polymerization initiator to easily form a fine concavo-convex shape. In that case, since a hydrophilic group can be introduce | transduced in the form of a surface graft by polymerizing the polymeric compound which has a hydrophilic group on the base-material surface, hydrophilicity is expressed more and is preferable.

The polymerizable compound and the polymerization initiator may be contained in the same layer, or may be contained separately in two or more layers. In particular, by separating a polymerization initiator layer containing a polymerization initiator from the hydrophilic polymerizable layer and providing it between the substrate and the polymerizable layer, adhesion to the substrate can be improved and obtained. Since durability of a hydrophilic base material can be improved, it is preferable.
In the case of providing a polymerization initiating layer, the use of a polymerizable compound having a polymerization initiating ability or a polymer having a polymerization initiating ability as a compound having a polymerization initiating ability to be contained in the layer is effective for strengthening the polymerization initiating layer. preferable. In the case of using a polymerizable compound having a polymerization initiating ability, adhesion to the substrate can be further improved by providing a layer containing the compound on the substrate and polymerizing the compound on the substrate. In the case of using a polymer having a polymerization initiating ability, it is possible to further improve the adhesion to the substrate by further adding a crosslinkable group to the polymer and causing a crosslinking reaction on the substrate. In either case, the adhesiveness between the two can be further strengthened by introducing a functional group that reacts with the compound into the surface of the substrate by corona treatment or plasma treatment.

[Initiator]
(Functional group capable of initiating polymerization)
As a copolymerization component having a polymerization initiating group constituting a polymerization initiating polymer, or a polymerizable compound having a polymerization initiating ability (monomer component), a radical, anion, or It preferably comprises a polymerizable group capable of cationic polymerization. That is, this copolymer component has a structure in which both a polymerizable group capable of polymerization and a functional group capable of initiating polymerization exist in the molecule.
The structure having the ability to initiate polymerization includes (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f) Examples thereof include ketoxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) active ester compounds, (j) compounds having a carbon halogen bond, and (k) pyridinium compounds. Specific examples of the above (a) to (k) are given below, but the present invention is not limited to these.

(A) Aromatic ketones In the present invention, (a) aromatic ketones preferable as a structure having a polymerization initiating ability include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” P. Fouassier, J. et al. F. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in Rabek (1993), p77-117. For example, the following compounds are mentioned.

Among these, particularly preferred examples of (a) aromatic ketones are listed below.
The α-thiobenzophenone compound described in JP-B-47-6416 and the benzoin ether compound described in JP-B-47-3981 include, for example, the following compounds.

  Examples of the α-substituted benzoin compounds described in JP-B-47-22326 include the following compounds.

  Examples thereof include benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, for example, the following compounds.

  Examples of the benzoin ethers described in JP-B-60-26403 and JP-A-62-181345 include the following compounds.

  Examples of the α-aminobenzophenones described in JP-B-1-34242, US Pat. No. 4,318,791, and European Patent 0284561A1, such as the following compounds.

  P-Di (dimethylaminobenzoyl) benzene described in JP-A-2-211452, for example, the following compounds may be mentioned.

  Examples of the thio-substituted aromatic ketone described in JP-A-61-194062 include the following compounds.

  The acylphosphine sulfide described in JP-B-2-9597, for example, the following compounds may be mentioned.

  Examples of the acylphosphine described in JP-B-2-9596 include the following compounds.

  Further, thioxanthones described in JP-B-63-61950, coumarins described in JP-B-59-42864, and the like can also be mentioned.

(B) Onium Salt Compound In the present invention, examples of the preferable (b) onium salt compound as a structure having polymerization initiating ability include compounds represented by the following general formulas (1) to (3).

In General Formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a carbon atom having 12 or less carbon atoms. An aryloxy group is mentioned. (Z ² ) ⁻ represents a counter ion selected from the group consisting of halogen ion, perchlorate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, and sulfonate ion, preferably perchloric acid Ions, hexafluorophosphate ions, and aryl sulfonate ions.

In General Formula (2), Ar ³ represents an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms. (Z ³ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

In the general formula (3), R ²³ , R ²⁴ and R ²⁵ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. (Z ⁴ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

  Specific examples of the (b) onium salt compound that can be suitably used in the present invention include paragraph numbers [0030] to [0033] of JP-A No. 2001-133969 and paragraph numbers of JP-A No. 2001-305734. Examples include [0048] to [0052] and those described in paragraph numbers [0015] to [0046] of JP-A-2001-343742.

(C) Organic peroxide In the present invention, (c) the organic peroxide preferable as the structure having a polymerization initiating ability includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) -3,3. , 5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroper Oxide, para Methane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide , Dicumyl peroxide, bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-xanoyl peroxide, succinic peroxide Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl Peroxy carbonate , Di (3-methyl-3-methoxybutyl) peroxydicarbonate, t-butylperoxyacetate, t-butylperoxypivalate, t-butylperoxyneodecanoate, t-butylperoxyoctanoate , T-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, tertiary carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) Benzophenone, 3,3 ′, 4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3 ′ , 4,4′-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (cumylpa Oxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylperoxy) Dihydrogen diphthalate) and the like.

  Among these, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3, 3 ′, 4,4′-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 Peroxyesters such as '-tetra- (cumylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate A system is preferably used.

(D) Thio compound In the present invention, examples of the preferable (d) thio compound as a structure having polymerization initiating ability include compounds having a structure represented by the following general formula (4).

(In the general formula (4), R ²⁶ represents an alkyl group, an aryl group or a substituted aryl group, R ²⁷ represents a hydrogen atom or an alkyl group, and R ²⁶ and R ²⁷ are bonded to each other to form oxygen, sulfur, And a group of nonmetallic atoms necessary to form a 5- to 7-membered ring that may contain a heteroatom selected from nitrogen atoms.
As an alkyl group in the said General formula (4), a C1-C4 thing is preferable. The aryl group is preferably one having 6 to 10 carbon atoms such as phenyl or naphthyl, and the substituted aryl group may be a halogen atom such as a chlorine atom or a methyl group as described above. Those substituted with an alkoxy group such as an alkyl group, a methoxy group, and an ethoxy group are included. R ²⁷ is preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the thio compound represented by the general formula (4) include the following compounds.

(E) Hexaarylbiimidazole compound In the present invention, preferred (e) hexaarylbiimidazole compounds as a structure having a polymerization initiating ability include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, For example, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5 '-Tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4, 4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimi Sol, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

(F) Ketooxime ester compound In the present invention, preferable (f) ketoxime ester compound as a structure having a polymerization initiating ability includes 3-benzoyloxyiminobutane-2-one and 3-acetoxyiminobutane-2-one. 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1- ON, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

(G) Borate Compound In the present invention, examples of the preferable (g) borate compound as a structure having a polymerization initiating ability include compounds represented by the following general formula (5).

(In the general formula (5), R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may be the same or different from each other, and each is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Represents an alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group, and R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are bonded to form a cyclic structure. Provided that at least one of R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ is a substituted or unsubstituted alkyl group (Z ⁵ ) ⁺ is an alkali metal cation or a quaternary ammonium cation. Is shown.)
Specific examples of the compound represented by the general formula (5) are described in US Pat. Nos. 3,567,453 and 4,343,891, European Patents 109,772 and 109,773. Compounds and those shown below are mentioned.

(H) Azinium Compound In the present invention, preferable (h) azinium salt compounds as a structure having a polymerization initiating ability include JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, Listed are compounds having an N—O bond described in JP-A-63-143537 and JP-B-46-42363.

(I) Active ester compound In the present invention, (i) an active ester compound preferable as a structure having a polymerization initiating ability includes an imide sulfonate compound described in JP-B-62-2223, JP-B-63-14340, JP-A-59- And active sulfonates described in No. 174831.

(J) Compound having a carbon halogen bond In the present invention, preferred compounds having a carbon halogen bond as a structure having a polymerization initiating ability include those represented by the following general formulas (6) to (12). .

The compound represented by the said General formula (6).
(In General Formula (6), X ² represents a halogen atom, and Y ¹ represents —C (X ² ) ₃ , —NH ₂ , —NHR ³⁸ , —NR ³⁸ , —OR ³⁸ , where R ³⁸ represents An alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group, and R ³⁷ represents —C (X ² ) ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and a substituted alkenyl group.

The compound represented by the said General formula (7).
(In the general formula (7), R ³⁹ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group or a cyano group. X ³ is a halogen atom, and n is an integer of 1 to ^3. )

The compound represented by the said General formula (8).
(In the general formula (8), R ⁴⁰ is an aryl group or a substituted aryl group, R ⁴¹ is a group or halogen shown below, and Z ⁶ is —C (═O) — or —C (═S ) — Or —SO ₂ —, X ³ is a halogen atom, and m is 1 or 2.)

(In the formula, R ⁴² and R ⁴³ are an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, and R ⁴⁴ is the same as R ³⁸ in the general formula (6). )

The compound represented by the said General formula (9).
(In the general formula (9), R ⁴⁵ is an optionally substituted aryl group or heterocyclic group, R ⁴⁶ is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms, and p is 1, 2, or 3.)

A carbonylmethylene heterocyclic compound having a trihalogenomethyl group represented by the general formula (10).
(In the general formula (10), L ⁷ is a hydrogen atom or a substituent of the formula: CO— (R ⁴⁷ ) _q (C (X ⁴ ) ₃ ) _r , Q ² is a sulfur, selenium or oxygen atom, dialkylmethylene. A group, an alkene-1,2-ylene group, a 1,2-phenylene group or an N—R group, and M ⁴ is a substituted or unsubstituted alkylene group or alkenylene group, or a 1,2-arylene group. R ⁴⁸ is an alkyl group, an aralkyl group or an alkoxyalkyl group, R ⁴⁷ is a carbocyclic or heterocyclic divalent aromatic group, X ⁴ is a chlorine, bromine or iodine atom, q = 0 and r = 1, or q = 1 and r = 1 or 2.)

4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivative represented by the general formula (11).
(In General Formula (11), X ⁵ is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, and R ⁴⁹ is a hydrogen atom or a CH _{3 -t} X ⁵ _t group. And R ⁵⁰ is an s-valent unsaturated organic group which may be substituted)

A 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative represented by the general formula (12).
(In General Formula (12), X ⁶ is a halogen atom, v is an integer of 1 to 3, u is an integer of 1 to 4, and R ⁵¹ is a hydrogen atom or a CH _{3 -v} X ⁶ _v group. And R ⁵² is an u-valent unsaturated organic group which may be substituted.)

  Specific examples of such a compound having a carbon-halogen bond include, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), for example, 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2 -(2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6 -Bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6- Scan (trichloromethyl) -S- triazine. In addition, compounds described in British Patent 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine, etc. And compounds described in JP-A No. 53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphtho) 1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloro Til-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine), 2- (acenaphtho-5-yl) -4,6- Examples include compounds described in German Patent No. 3333724, such as bis-trichloromethyl-S-triazine, and the like.

  F.F. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2, 4,6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine, etc. be able to. Furthermore, for example, the following compounds described in JP-A-62-258241 can be exemplified.

  Furthermore, for example, the following compounds described in JP-A-5-281728 can be exemplified.

  Alternatively, M.M. P. Hutt, E .; F. Elslager and L. M.M. The following compounds that can be easily synthesized by those skilled in the art according to the synthesis method described in “Journalof Heterocyclic Chemistry”, Volume 7 (No. 3) by Herbel, page 511 et seq. (1970) Examples of the group include the following compounds.

(K) Pyridium compounds In the present invention, examples of the (k) pyridium compounds that are preferable as a structure having a polymerization initiating ability include compounds represented by the following general formula (13).

(In general formula (13), R ⁵ preferably represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, or a substituted alkynyl group, and R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom, a halogen atom or a monovalent organic residue, and at least one of the following general formulas ( 14) In addition, R ⁵ and R ⁶ , R ⁵ and R ¹⁰ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ are included. And may be bonded to each other to form a ring, and X represents a counter anion, and m represents an integer of 1 to 4.)

(In the general formula (14), R ¹² and R ¹³ are each independently a hydrogen atom, halogen atom, alkyl group, substituted alkyl group, aryl group, substituted aryl group, alkenyl group, substituted alkenyl group, alkynyl group or substituted alkynyl. R ¹¹ represents a hydrogen atom, alkyl group, substituted alkyl group, aryl group, substituted aryl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, hydroxyl group, substituted oxy group, mercapto group, substituted thio Represents a group, an amino group, or a substituted amino group, and R ¹² and R ¹³ , R ¹¹ and R ¹² , R ¹¹ and R ¹³ may be bonded to each other to form a ring, and L includes a heteroatom 2 Represents a valent linking group.)

  Although the preferable specific example of a compound represented by General formula (13) below is shown, this invention is not limited to these.

  Among these structures having polymerization initiating ability, aromatic ketones and triazines having the following structure are preferably pendant to the polymerizable group.

  Moreover, as for the structure which has such a polymerization initiating ability, only 1 type may be pendant to the polymeric group, and 2 or more types may be pendant.

  Examples of the polymerizable group pendant with such a structure having a polymerization initiating ability include a polymerizable group capable of undergoing radical, anionic, and cationic polymerization such as an acryl group, a methacryl group, an acrylamide group, a methacrylamide group, and a vinyl group. Among these, an acrylic group and a methacryl group are particularly preferable because of ease of synthesis.

  Specific examples of the copolymer component having a functional group having a polymerization initiating ability in the present invention include monomers having the following structures.

(Light irradiation)
In the process, the active energy ray used for the exposure for causing the graft polymerization reaction is not particularly limited as long as the photopolymerization start site remaining on the substrate surface can absorb the energy and generate an active site. Specifically, UV and visible light having a wavelength of 200 to 800 nm, preferably 300 to 600 nm are desirable.
Examples of the exposure light source include a high-pressure mercury lamp, a low-pressure mercury lamp, a halogen lamp, a xenon lamp, an excimer laser, a dye laser, a YAG laser, and sunlight. The exposure energy is preferably about 10 mJ / m ^{3 to} 10,000 J / m ³ .

(Reaction solvent)
In the present invention, the graft polymerization reaction may be carried out without a solvent, that is, without using a solvent alone, or in various solvents. Examples of solvents that can be used in the polymerization reaction include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole, and dimethoxybenzene; halogenated hydrocarbons such as methylene chloride, chloroform, and chlorobenzene. Solvents; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, t-butyl alcohol; nitriles such as acetonitrile, propionitrile, benzonitrile System solvents; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate; and water. These can be used individually or in mixture of 2 or more types. In general, the graft polymerization reaction using a solvent is performed by adding a monomer in a solvent, adding a catalyst as necessary, and then immersing a substrate on which an initiator is fixed in the solvent and reacting for a predetermined time. This is done. The solvent-free graft polymerization reaction is generally performed at room temperature or in a heated state up to 100 ° C.

<Creation of hydrophilic surface>
In the present invention, it is preferable to contain a compound having a hydrophilic group in order to impart hydrophilicity to the surface uneven structure member. Here, when a polymerization reaction is used for imparting an uneven shape to the structural member, it is preferable that the compound having a hydrophilic group further has a polymerizable group.
Hereinafter, the case where the compound having a hydrophilic group also has a polymerizable group (monomer) will be described in detail.

  Examples of hydrophilic monomers include (meth) acrylic acid or alkali metal salts and amine salts thereof, itaconic acid or alkali metal salts and amine salts thereof, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol ( (Meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or its hydrohalide, 3-vinylpropionic acid or its alkali metal salt and amine salt, vinylsulfonic acid or its alkali metal salt and amine salt, 2-sulfoethyl Cals such as (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate Hexyl group, a sulfonic acid group, phosphoric acid group, an amino group or a salt thereof, hydroxyl group and a monomer having a hydrophilic group such as an amide group and an ether group. Examples of the radically polymerizable group-containing hydrophilic polymer constituting the hydrophilic layer include a hydrophilic homopolymer or copolymer obtained by using at least one selected from these hydrophilic monomers.

  The radical polymerizable group-containing hydrophilic polymer is obtained by copolymerizing (a) a method in which a hydrophilic monomer and a monomer having an ethylene addition polymerizable unsaturated group are copolymerized, and (b) a monomer having a hydrophilic monomer and a double bond precursor. It can be synthesized by a method of polymerizing and then introducing a double bond by treatment with a base or the like, (c) a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group, Among these, from the viewpoint of synthesis suitability, a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group is preferable.

When the radically polymerizable group-containing hydrophilic polymer is synthesized by the method (a), examples of the monomer having an ethylene addition polymerizable unsaturated group that is copolymerized with the hydrophilic monomer include an allyl group-containing monomer. Examples include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.
Further, when the radical polymerizable group-containing hydrophilic polymer is synthesized by the method (b), a monomer having a double bond precursor that is copolymerized with a hydrophilic monomer is 2- (3-chloro-1-oxopropoxy). ) Ethyl methacrylate.

  Further, when the radical polymerizable group-containing hydrophilic polymer is synthesized by the method (c), a reaction between a carboxyl group, an amino group or a salt thereof in the hydrophilic polymer and a functional group such as a hydroxyl group and an epoxy group is performed. Monomers having an addition-polymerizable unsaturated group used for introducing unsaturated groups using (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl eutel, 2-isocyanatoethyl (meth) acrylate Etc.

  In addition, the radical polymerizable group-containing hydrophilic polymer contained in the upper layer may be a hydrophilic macromonomer. The method for producing the macromonomer used in the present invention is described in, for example, Chapter 2 of “Macromonomer Chemistry and Industry” (editor, Yuya Yamashita) published on September 20, 1999 by the IP Publishing Bureau. Various production methods have been proposed for “synthesis”.

  Particularly useful hydrophilic macromonomers used in the present invention include macromonomers derived from carboxyl group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid, vinyl styrene sulfone. Sulfonic acid macromonomer derived from monomer of acid and its salt, (meth) acrylamide, N-vinylacetamide, N-vinylformamide, amide macromonomer derived from N-vinylcarboxylic amide monomer, hydroxyethyl Macromonomers derived from hydroxyl group-containing monomers such as methacrylic acid, hydroxyethyl acrylate, glycerol monomethacrylate, methoxyethyl acrylate, methoxypolyethylene glycol acrylate, polyethylene glycol Call acrylate macromonomers derived from alkoxy group or ethylene oxide group-containing monomers such as. A monomer having a polyethylene glycol chain or a polypropylene glycol chain can also be usefully used as the macromonomer of the present invention.

  Among these hydrophilic macromonomers, useful ones have a molecular weight in the range of 250 to 100,000, and a particularly preferable range is 400 to 30,000.

In addition, in forming the upper layer, a hydrophilic monomer may be further added in addition to the radical polymerizable group-containing hydrophilic polymer. By adding a hydrophilic monomer, the hydrophilic graft chain is further bonded to the side chain polymerizable group of the radical polymerizable group-containing hydrophilic polymer (graft chain) bonded to the polymerization initiating layer, thereby forming a branched structure. The graft chain is formed. As a result, both the formation density and the mobility of the hydrophilic graft having high motility are dramatically improved, so that further higher hydrophilicity is expressed.
The amount of the hydrophilic monomer added is preferably 0 to 60% by weight based on the total solid content of the upper layer. If it is 60% by weight or more, the applicability is poor and uniform application is not possible.

(Other hydrophilic monomers)
When forming the upper layer, hydrophilic monomers useful for use in combination with a radically polymerizable group-containing hydrophilic polymer include monomers having a positive charge such as ammonium and phosphonium, sulfonic acid groups, carboxyl groups, phosphorus Examples thereof include monomers having a negative charge or an acidic group that can be dissociated into a negative charge, such as an acid group and a phosphonic acid group. Other examples include a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, and a cyano group. A hydrophilic monomer having a nonionic group such as a group can also be used.

In the present invention, specific examples of hydrophilic monomers that are particularly useful in combination with the radical polymerizable group-containing hydrophilic polymer include the following monomers.
For example, (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali metal salt and amine salt, allylamine or its hydrohalide salt, 3-vinylpropionic acid or its alkali metal salt and amine salt Vinyl sulfonic acid or its alkali metal salt and amine salt, vinyl styrene sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethylene (meth) acrylate, 3-sulfopropylene (meth) acrylate or its alkali metal salt and Amine salt, 2-acrylamido-2-methylpropanesulfonic acid or its alkali metal salt and amine salt, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, allylamine or its hydrohalic acid Such as carboxyl group, sulfonic acid group, phosphoric acid, amino group or salts thereof, carboxyl group, sulfonic acid group, phosphoric acid, amino such as 2-trimethylaminoethyl (meth) acrylate or its hydrohalide Groups or their salts can be used. Also, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, N-vinylpyrrolidone, N-vinylacetamide, allylamine or a hydrohalide thereof Also useful are monomers having an amino acid skeleton in the molecule such as polyoxyethylene glycol mono (meth) acrylate, N-methacryloyloxyenalcarbamic acid aspartic acid, monomers having a sugar skeleton in the molecule such as glycoxyethyl methacrylate, and the like. .

(Other monomers)
In the polymer compound having a hydrophilic functional group and a polymerizable unsaturated double bond in the side chain of the present invention, other monomers in addition to the hydrophilic group and the polymerizable unsaturated double bond group are used as constituent elements. It may be polymerized. These monomers are used to increase the solvent solubility of the polymer compound of the present invention. Although it does not specifically limit as a monomer used for such a purpose, Acrylic acid ester, such as (meth) acrylic acid methyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid methoxyethyl ester, is used. be able to.

  The molecular weight of the polymer compound having a hydrophilic functional group and a polymerizable unsaturated double bond in the side chain is in the range of 1,000 to 1,000,000, and particularly preferably in the range of 5,000 to 100,000. By using a specific hydrophilic polymer in this molecular weight range, excellent hydrophilicity is realized, and the solvent is excellent in solubility when being brought into contact with the substrate surface, and the handleability is also improved.

  In the present invention, a hydrophilic concavo-convex structure member having a fine concavo-convex surface is formed by forming a hydrophilic layer having a polymerization initiating ability and a polymerization ability on a substrate having a fine concavo-convex shape, and performing patternwise imagewise exposure. It is preferable to form. The pattern shape in the surface concavo-convex structure member is not particularly limited, and a circular shape, a triangular shape, a quadrangular shape, or other polygons can also be used. A shape that can be formed using a photomask used in normal semiconductor manufacturing is preferable from the viewpoint of workability.

Furthermore, when the layer having polymerization initiating ability and the hydrophilic layer having polymerizing ability are set separately, the following two methods can be used.
(1) A coating liquid containing a polymer having a polymerization initiating ability in a side chain is disposed on a substrate by coating or the like, and formed into a film to obtain a polymerization initiating layer. At that time, when the polymer contains a crosslinkable group, the film can be more firmly formed by advancing the crosslinking reaction.
On the polymerization initiating layer, a hydrophilic compound having a polymerizable group is directly bonded by means called surface graft polymerization to form a hydrophilic layer. In the present invention, in order to form a fine concavo-convex shape, after providing a layer containing a hydrophilic compound having a polymerizable group on the polymerization initiation layer, an active species is added to the polymerization initiation polymer constituting the polymerization initiation layer. The energy for giving the image is given to the image. As a result, the polymerization initiating group in the polymerization initiating layer is activated in an image-like manner, a hydrophilic compound having a polymerizable group is bonded to the active species (graft polymerization), and the monomer remaining on the surface is washed after completion of the polymerization. By removing by this, the hydrophilic uneven | corrugated structural member of this invention can be formed.

(2) A layer containing a polymerization initiator and a compound having a polymerizable unsaturated bond is formed on the substrate, the layer is exposed imagewise to form a cured portion and an uncured portion, and then uncured. The part is removed by development, and a polymerization initiation layer for an image containing an unreacted polymerization initiator is provided. A hydrophilic compound having a polymerizable group is brought into contact with the polymerization initiating layer and irradiated with light, thereby generating a graft polymer on the surface of the polymerization initiating layer, and generating a non-generated region of the hydrophilic graft polymer. As a result, the surface uneven structure member can be formed.

  Examples of the present invention are illustrated below, but the present invention is not limited to these examples.

Example 1
A stripe pattern having a width of 2 μm, a depth of 5 μm, and a line interval of 5 μm was formed on a Si substrate by using photolithography used in semiconductor manufacturing.
A graft polymer layer was formed on the prepared substrate surface by the following “1. Photoradical generator binding step” and “2. Graft polymer formation step”.

1. Photoradical generator binding step After the silicon substrate was washed with acetone, it was exposed to a UV ozone cleaner (NL-UV253, manufactured by Nippon Laser Electronics Co., Ltd.) for 5 minutes. A 1% by weight dehydrated toluene solution of 1-benzoyl-1- (11-trichlorosilylundecyloxy) cyclohexane was applied onto the substrate with a spinner and dried at 100 ° C. for 1 minute. Then, it wash | cleaned in order with toluene, acetone, and a pure water.

2. Graft polymer formation process A thin film of an aqueous solution of 5% by mass HEMA (hydroxyethylmethyl methacrylate) is superimposed on the prepared photoradical generator-bonded silicon substrate and sandwiched between quartz plates. The pattern mask is placed so as to be perpendicular to the line generated by photolithography, exposed to XUV exposure apparatus UVX-02516S1LP01 (high pressure mercury lamp, manufactured by USHIO) for 5 minutes, immersed in acetone for 1 hour, and then washed with acetone. Then, the monomer remaining on the surface was removed and dried.

  The contact angle of the substrate surface obtained as described above was measured (Data Physics, OCA20). The contact angle was less than 15 °. Further, after a durability test that was left outdoors for 2 weeks, the contact angle was measured again and found to be less than 15 °.

Example 2
In Example 1, instead of forming a stripe pattern having a width of 2 μm, a depth of 5 μm, and a line interval of 5 μm using photolithography, a stripe pattern of width 2 μm, a depth of 10 μm, and a line interval of 5 μm was formed using photolithography. Except for the above, a substrate was prepared in the same manner as in Example 1. The contact angle of the obtained substrate surface was less than 15 °. Further, after the durability test, the contact angle was measured again and found to be less than 15 °.

Example 3
In Example 1, a substrate was prepared in the same manner as in Example 1 except that a stripe pattern mask having a width of 5 μm and a line interval of 15 μm was used instead of a stripe pattern mask having a width of 5 μm and a line interval of 10 μm. . The contact angle of the obtained substrate surface was less than 15 °. Further, after the durability test, the contact angle was measured again and found to be less than 15 °.

Comparative Example 1
A substrate was prepared in the same manner as in Example 1 except that the stripe pattern was not formed using photolithography. The contact angle of the obtained substrate surface was 20 °. Further, after the durability test, the contact angle was measured again and found to be less than 40 °.

Example 4
A suspension obtained by suspending 1% by mass of silica fine particles in a methanol solution of 5% by mass of triethoxysilane was applied to a glass substrate with a film thickness of 1.0 μm by spin coating and dried at 120 ° C. for 1 hour. I let you.
A graft polymer layer was formed on the prepared substrate surface by the following “1. Photoradical generator binding step” and “2. Graft polymer formation step”.

1. Photoradical generator binding step A dehydrated toluene solution of 1% by mass of 1-benzoyl-1- (11-trichlorosilylundecyloxy) cyclohexane was applied on a substrate with a spinner and dried at 100 ° C. for 1 minute. Then, it wash | cleaned in order with toluene, acetone, and a pure water.

2. Graft polymer formation process A thin film of 5 mass% HEMA (hydroxyethylmethylmethacrylate) aqueous solution is superimposed on the prepared photoradical generator binding substrate and sandwiched between quartz plates, on which a stripe of 5 μm width and 10 μm line spacing is formed. After placing a pattern mask and exposing for 5 minutes with an XUV exposure apparatus UVX-02516S1LP01 (high pressure mercury lamp, manufactured by USHIO), dipping in acetone for 1 hour, washing with acetone and pure water to remove monomers remaining on the surface, Dried.

  The contact angle of the substrate surface obtained as described above was measured (Data Physics, OCA20). The contact angle of the substrate surface was less than 15 °. Further, after a durability test that was left outdoors for 2 weeks, the contact angle was measured again and found to be less than 15 °.

Example 5
In Example 4, a substrate was prepared in the same manner as in Example 4 except that the coating was applied by spin coating to a film thickness of 0.8 μm instead of coating by 1.0 μm. The contact angle of the obtained substrate surface was less than 15 °. Further, after the durability test, the contact angle was measured again and found to be less than 15 °.

Example 6
In Example 4, a substrate was prepared in the same manner as in Example 4 except that a stripe pattern mask having a width of 5 μm and a line interval of 15 μm was used instead of a stripe pattern mask having a width of 5 μm and a line interval of 10 μm. . The contact angle of the obtained substrate surface was less than 15 °. Further, after the durability test, the contact angle was measured again and found to be less than 15 °.

Comparative Example 3
A base material was prepared in the same manner as in Example 4 except that coating with a film thickness of 1.0 μm by spin coating was not performed. The contact angle of the obtained substrate surface was 22 °. Further, after the durability test, the contact angle was measured again and found to be 25 °.

Claims (7)

  A hydrophilic substrate having a hydrophilic concavo-convex structure member having another fine concavo-convex surface on a substrate having a fine concavo-convex shape.   The hydrophilic substrate according to claim 1, wherein the hydrophilic concavo-convex structure member has a concavo-convex surface formed using a polymerization reaction.   The hydrophilic uneven structure member comprises a polymerization initiating layer containing a compound having a polymerization initiating ability, and a hydrophilic layer in which a compound containing a polymerizable group is directly bonded to the polymerization initiating layer. The hydrophilic substrate according to claim 2.   The hydrophilic base material in any one of Claims 1-3 whose at least 1 fine uneven | corrugated shape of this board | substrate is formed by photolithography.   The hydrophilic substrate according to any one of claims 1 to 3, wherein at least one fine uneven shape of the substrate is formed by a coating layer containing fine particles.   A hydrophilic concavo-convex structure member having a fine concavo-convex surface is formed by forming a hydrophilic layer having a polymerization initiating ability and a polymerization ability on a substrate having a fine concavo-convex shape and exposing it like an image. The manufacturing method of the hydrophilic base material of Claim 1 or 2.   Forming a hydrophilic concavo-convex structure member having a fine concavo-convex surface by forming a layer having a polymerization initiating ability and a hydrophilic layer having a polymerization ability on a substrate having a fine concavo-convex shape and exposing it like an image The manufacturing method of the hydrophilic base material in any one of Claims 1-3 characterized by these.