JP2010057690A - Goggle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a goggle which is excellent in antifogging property, durability, visibility and weatherability. <P>SOLUTION: In the goggle which has a hydrophilic layer containing hydrophilic polymer on the base material of acrylic plastic or polycarbonate system plastic, the hydrophilic polymer has at least one hydrophilic group and hydrolyzable alkoxysilyl group, thickness of the hydrophilic layer is 50-1,000 nm, the waterdrop contact angle on the hydrophilic layer surface at 20°C is 15° or less and the light transmittance is 85% or more. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to goggles, motorcycle helmet goggles, goggles used for snow sports such as skiing and snowboarding, underwater goggles used for swimming and diving, safety goggles for preventing scattering of chemicals and foreign substances, etc. About.

  Lightweight is required for motorcycle helmet goggles, goggles used for snow sports such as skiing and snowboarding, underwater goggles used for swimming and diving, and safety goggles to prevent scattering of chemicals and foreign substances. A highly transparent resin such as an acrylic resin or a polycarbonate resin is used. Such resinous goggles have a problem of hindering visibility because the surface of the resin may condense depending on the environment of use and fogging may occur. As methods for suppressing the occurrence of such fogging, methods as described in Patent Documents 1 to 7 below have been known.

Patent Document 1 is characterized by containing at least a hydrolyzable silane compound having a sulfonic acid group and / or a precursor group thereof and / or a partial hydrolyzate thereof in a dissolved state in a hydrophilic organic solvent. A coating liquid for imparting hydrophilicity to a substrate surface is disclosed.
Patent Document 2 discloses an underwater goggles having anti-fogging properties characterized in that a water film can be held on the inner surface of the underwater goggles in an atmosphere of 10 to 100 ° C. and 100% RH. It is disclosed. However, the techniques described in Patent Documents 1 and 2 have a drawback that the hydrophilic coating layer is peeled off by repeatedly rubbing with a cloth or the like.
Patent Document 3 contains an inorganic alkoxide and at least one polymer having an OH group formed by hydrolysis and polycondensation of the alkoxide; a polyalkylene oxide; a catalyst; and a water-containing organic solvent. An antifogging coating composition is disclosed. However, the technique described in Patent Document 3 has a drawback that the hydrophilicity is insufficient and the desired antifogging property cannot be obtained.
In Patent Document 4, a polycarbonate resin is used as a base material, a non-water-absorbing barrier layer is provided as a first layer on at least one surface of the base material, and a water-absorbing type antifogging is provided as a second layer on the first layer. A polycarbonate resin molded body characterized in that a layer is formed is disclosed. However, in the technique described in Patent Document 4, it is necessary to increase the thickness of the hydrophilic layer because the hydrophilic layer is water-absorbing and fogging occurs when the water absorption reaches saturation. If the hydrophilic layer is thickened, the visibility of goggles may decrease. In addition, since it is a UV curable water-absorbing layer, a special processing machine such as a UV irradiation device is required, and there is a disadvantage in terms of cost.
Patent Document 5 discloses a water droplet diffusing agent that diffuses water droplets on the surface of a polycarbonate resin containing an acrylic silicone copolymer, perfluoroalkylcarboxylic acid, and polyvinyl alcohol. However, in the technique described in Patent Document 5, the hydrophilic layer may be dissolved by condensed water, and the anti-fogging sustainability during repeated use is insufficient.
Patent Document 6 includes a goggle frame and a goggle lens that is detachably fitted in a groove formed in an inner periphery of the goggle frame, and a plurality of air holes are provided on the upper part of the goggle lens. In the goggles, there is disclosed a goggle characterized in that the right and left side vent holes are made larger than the central side vent hole. Patent Document 7 discloses a helmet that is attached to the head and protects the head. A power generation means for generating electricity with sunlight, a power storage means for storing the power generated by the power generation means, and a cooling means for cooling the inside of the helmet with a current supplied from the power storage means. A helmet is disclosed. However, the techniques described in Patent Documents 6 and 7 are not a method of coating a layer having antifogging properties, but are provided with a ventilation hole or a cooling device in a helmet or the like, and it is sufficient that the ventilation hole is provided. There are drawbacks that anti-fogging properties cannot be obtained, and that the cooling device takes time to exhibit the anti-fogging effect.
JP 2002-60692 A JP 2002-78821 A JP-A-8-231944 JP 2007-210138 A JP 2000-230171 A JP 2001-231810 A JP-A-10-212616

  An object of this invention is to provide the goggles which have the outstanding hydrophilic property, the transmittance | permeability, anti-fogging property, durability, and temperature cycling property.

The present invention is as follows.
[1]
A goggle having a hydrophilic layer containing a hydrophilic polymer on a base of an acrylic resin or a polycarbonate resin, wherein the hydrophilic polymer has at least one hydrophilic group and a hydrolyzable alkoxysilyl group. A goggle having a hydrophilic layer thickness of 50 nm to 1000 nm, a water droplet contact angle at 20 ° C. of the hydrophilic layer surface of 15 ° or less, and a light transmittance of 85% or more.
[2]
The goggles according to [1], wherein the goggle includes an intermediate layer including a compound having a hydrolyzable alkoxysilyl group and having a thickness of 10 to 100 nm between the base material and the hydrophilic layer.
[3]
The hydrophilic polymer is represented by the following hydrophilic polymers (I), (II-1) and (II-2) having a structure represented by the following general formulas (I-1) and (I-2) The hydrophilic polymer (II) containing a structure or the hydrophilic polymer (III) containing a structure represented by the general formulas (III-1) and (III-2) [1] or The goggles according to [2].

In general formulas (I-1) and (I-2), R ^{101 to} R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 to 3, and L ¹⁰¹ and L ¹⁰² each independently represent a single bond or a polyvalent organic linking group. x and y represent a composition ratio, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ¹⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.

In general formulas (II-1) and (II-2), R ^{201 to} R ²⁰⁵ each independently represents a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to 3, and L ²⁰¹ and L ²⁰² each independently represent a single bond or a polyvalent organic linking group. A ²⁰¹ is _{-OH, -OR a, -COR a,} -CO 2 R e, -CON (R a) (R b), - N (R a) (R b), - NHCOR d, -NHCO 2 R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.

In formulas (III-1) and ^(III-2), each represent R 301 ^{to R 311} independently represent a hydrogen atom or a hydrocarbon group. r represents an integer of 1 to 3, and L ^{301 to} L ³⁰³ each independently represent a single bond or a polyvalent organic linking group. x and y represent a composition ratio, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ³⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , -OCON (R _a ) (R _b ), -NHCON (R _a ) (R _b ), -SO ₃ R _e , -OSO ₃ R _e , -SO ₂ R _d , -NHSO ₂ R _d , -SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.
[4]
Goggles according to any one of the at least one (1) to (3), wherein the hydrophilic group is selected from -CONH _2, -COOH and -OH.
[5]
The hydrolyzable alkoxysilyl group, a _{-Si (OCH 3) n, -Si} (OC 2 H 5) n and _{-Si (OC 3 H 7) n} ( n represents an integer of 2-3) The goggles according to any one of [1] to [4], which have at least one selected alkoxysilyl group.

ADVANTAGE OF THE INVENTION According to this invention, the goggles which have the outstanding hydrophilic property, the transmittance | permeability, anti-fogging property, durability, and temperature cycling property are provided.
The goggles of the present invention have a hydrophilic layer containing a hydrophilic polymer having at least one hydrophilic group and a hydrolyzable alkoxysilyl group, so that the goggles have high hydrophilicity and exhibit excellent antifogging properties. Can do. Since the hydrophilic composition of the present application is excellent in leveling, the unevenness of the substrate can be filled with a thin hydrophilic layer, so that there is an effect of obtaining high hydrophilicity without impairing the visibility of goggles.
In addition, since the hydrophilic layer contains a polymer, it is easy to follow changes in thermal expansion, thermal contraction, etc. of the acrylic resin or polycarbonate resin that is the base material, and is difficult to cause cracks on the base material surface due to temperature changes. Cycle performance can be improved.
Furthermore, even if the hydrophilic layer is a thin film having a thickness of 50 nm to 1000 nm, it exhibits excellent antifogging properties, hydrophilicity, durability, and temperature cycle resistance, and therefore has goggles with high light transmittance and excellent transparency. It became possible to do.

The present invention is described in detail below.
The goggles of the present invention are goggles having a hydrophilic layer containing a hydrophilic polymer on a base of an acrylic resin or a polycarbonate resin, and the hydrophilic polymer contains at least one hydrophilic group and hydrolyzable. It has an alkoxysilyl group, the thickness of the hydrophilic layer is 50 nm to 1000 nm, the water droplet contact angle at 20 ° C. of the surface of the hydrophilic layer is 15 ° or less, and the light transmittance is 85% or more.

In addition to the hydrophilic layer, the goggles of the present invention may have an intermediate layer and an undercoat layer described in detail later.
The hydrophilic layer can be formed by applying a hydrophilic composition on at least one surface of an acrylic resin or polycarbonate resin substrate and drying it.
Preferably, a hydrophilic composition containing a hydrophilic polymer having at least one hydrophilic group and hydrolyzable alkoxysilyl group in the molecule is applied to at least one surface of an acrylic resin or polycarbonate resin substrate. It can be formed by drying.

  The hydrophilic composition is a coating (hydrophilic film, hydrophilic layer) formed by hydrolysis and polycondensation of an alkoxide (also referred to as metal alkoxide) of an element selected from Si, Ti, Zr, and Al. Or a hydrophilic layer), and the hydrophilic layer having such a crosslinked structure is obtained by using a metal alkoxide compound, a hydrophilic polymer, and an appropriate catalyst described in detail later. It can be formed as appropriate.

In the present invention, the cross-linked structure formed by hydrolysis and condensation polymerization of the metal alkoxide is hereinafter appropriately referred to as a sol-gel cross-linked structure. Such a hydrophilic layer includes, for example, (A) a polymer compound represented by the following general formula (I) having a hydrolyzable alkoxysilyl group at the terminal, or the hydrolyzable alkoxysilyl group of the backbone polymer. Hydrophilic composition containing a polymer compound represented by the following general formula (II) as a side chain, (B) a hydrolyzable metal alkoxide compound, and a metal complex catalyst that causes the hydrolysis and polycondensation It can be easily formed by preparing a product, applying it and drying it.
Below, each component contained in the hydrophilic composition for forming the hydrophilic layer which is this preferable aspect is demonstrated.

[Hydrophilic polymer]
The hydrophilic polymer used in the present invention has at least one hydrophilic group and hydrolyzable alkoxysilyl group (sometimes simply referred to as an alkoxysilyl group) in the molecule.

The main chain structure of the hydrophilic polymer is not particularly limited. Preferred main chain structures include acrylic resin, methacrylic resin, polyvinyl acetal resin, polyurethane resin, polyurea resin, polyimide resin, polyamide resin, epoxy resin, polystyrene resin, novolac type phenol resin, polyester resin, synthetic rubber, natural rubber, etc. An acrylic resin and a methacrylic resin are particularly preferable. The hydrophilic polymer may be a copolymer, and the copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer.
In addition, since the hydrophilic layer contains a polymer, the acrylic resin or polycarbonate resin that is the base material of the goggles of the present invention can easily follow the change of thermal expansion and contraction, and the coating film cracks due to temperature change. Less prone to defects.

The alkoxysilyl group is a group that reacts with water to generate silanol (Si—OH), and is preferably represented by the following general formula (a).
Formula (a): —Si (R ¹⁰² ) _a (OR ¹⁰¹ ) _3-a
In general formula (a), R ¹⁰¹ is a hydrogen atom or an alkyl group, R ¹⁰² is a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group, an aryl group and an aralkyl group, and a is an integer of 0 to 2. . When a plurality of R ¹⁰¹ or R ¹⁰² are present, they may be the same as or different from each other.

When R ¹⁰¹ represents an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹⁰² represents an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and when R ¹⁰¹ represents an aryl group, it has 6 carbon atoms. An aryl group having ˜25 is preferred, and an aralkyl group having 7 to 12 carbon atoms is preferred when it represents an aralkyl group.

The alkoxysilyl group is preferably an alkoxysilyl group bonded to a carbon atom.
There may be a case where one or a plurality of alkoxysilyl groups are present at the terminal of the polymer main chain or a case where one or a plurality of alkoxysilyl groups are present in the side chain. When two or more alkoxysilyl groups are contained, the two or more alkoxysilyl groups may be the same as or different from each other.
Hydrolyzable alkoxysilyl group in the present _{invention, -Si (OCH 3) n,} -Si (OC 2 H 5) n and _{-Si (OC 3 H 7) n} ( where n is an integer of 2-3 It is preferably at least one alkoxysilyl group selected from This is because it is easy to hydrolyze and has high crosslinkability, so that a hydrophilic layer excellent in antifogging properties and excellent in durability can be formed.

  The alkoxysilyl group can form a chemical bond by reacting with a hydrolysis or polycondensate of an alkoxide (also referred to as a metal alkoxide) containing an element selected from Si, Ti, Zr, and Al described later. Moreover, alkoxysilyl groups may form a chemical bond. The hydrophilic polymer is preferably water-soluble, and preferably becomes water-insoluble by reacting with a hydrolysis or polycondensate of a metal alkoxide. The chemical bond in this case includes a covalent bond, an ionic bond, a coordination bond, and a hydrogen bond in the same manner as usual. The chemical bond is preferably a covalent bond.

The hydrophilic group is preferably a carboxyl group, an alkali metal salt of a carboxyl group, a sulfonic acid group, an alkali metal salt of a sulfonic acid group, a hydroxyl group, an amide group, a carbamoyl group, a sulfonamide group, a sulfamoyl group or the like. Can be mentioned. More preferably, it is at least one selected from —CONH ₂ , —COOH and a hydroxy group. It is advantageous in that it is easily available, and is preferable because an excellent hydrophilic layer having high hydrophilicity can be formed.

  These groups may be present at any position in the polymer. A polymer structure in which a plurality of polymers are bonded directly from a polymer main chain or via a linking group, or bonded to a polymer side chain or a graft side chain, is preferred.

  A linking group is preferably interposed between the repeating unit containing a hydrophilic group and the alkoxysilyl group, or between the repeating unit containing a hydrophilic group and the main chain.

  The hydrophilic polymer is represented by the hydrophilic polymer (I) having the structures represented by the following general formulas (I-1) and (I-2), and the general formulas (II-1) and (II-2). It is preferably either the hydrophilic polymer (II) containing a structure or the hydrophilic polymer (III) containing a structure represented by the general formulas (III-1) and (III-2).

[Hydrophilic polymer (I) having a structure represented by general formulas (I-1) and (I-2)]

In general formulas (I-1) and (I-2), R ^{101 to} R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 to 3, and L ¹⁰¹ and L ¹⁰² each represents a single bond or a polyvalent organic linking group. x and y represent a composition ratio, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ¹⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.

In the formula (I-1) and ^{(I-2), R 101} ~R 108 each independently represent a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. R ^{101 to} R ¹⁰⁸ are preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoints of effects and availability.

  These hydrocarbon groups may further have a substituent. When the alkyl group has a substituent, the substituted alkyl group is constituted by a bond between a substituent and an alkylene group, and a monovalent nonmetallic atomic group excluding hydrogen is used as the substituent. Preferred examples include halogen atoms (-F, -Br, -Cl, -I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, amino groups, N-alkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, ア ル キ ル -alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-reelcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-aryl Acylamino group, ureido group, N ′ Alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N -Arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureate group, N', N'-dialkyl- N-arylureido group, N′-aryl-Ν-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl- N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N -Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group,

Aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfur group Sulfamoyl group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group phosphono group _(-PO 3 _{H 2} ) And conjugated base groups thereof (hereinafter referred to as phosphonate groups), dialkyl phosphono groups (—PO ₃ (alkyl) ₂ ), diaryl phosphono groups (—PO ₃ (aryl) ₂ ), alkylaryl phosphono groups (— PO ₃ (alkyl) (aryl)), monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H) (Aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphonooxy group (-OPO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonophenyl group), dialkyl phosphonooxy group _(-OPO 3 _(alkyl) 2), diaryl phosphonooxy group _(-OPO 3 _(aryl) 2), An alkylarylphosphonooxy group (—OPO (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and a conjugated base group thereof (hereinafter referred to as an alkylphosphonatooxy group), mono Arylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonateoxy group), morpholino group, cyano group, nitro group, aryl group, alkenyl group, alkynyl group It is done.

In these substituents, specific examples of the alkyl group include those alkyl groups similarly mentioned in R ¹ to R ^8, specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, Xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl, benzoyloxyphenyl, methylthiophenyl , Phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamo Butylphenyl group include a phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, a phosphonophenyl phenyl group. Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1-butenyl, A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups.

  Among these substituents, more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkyls. Amino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfamoy Group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphonate group Group, phosphonooxy group, phosphonatooxy group, aryl group, and alkenyl group.

  On the other hand, the alkylene group in the substituted alkyl group is preferably a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Preferably, it is a straight chain having 1 to 12 carbon atoms, more preferably a straight chain having 1 to 8 carbon atoms, more preferably a branched structure having 3 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms, and More preferable examples include cyclic alkylene groups having 5 to 10 carbon atoms, and further preferably 5 to 8 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a hydroxymethyl group, a methoxymethyl group, and a methoxyethoxy group. Ethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonyl group Group, allyloxycarbonyl butyl group,

  Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoyl Methyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (Phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, Torilho Phonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

  Of these, a hydroxymethyl group is preferred from the viewpoint of hydrophilicity.

L ^{101 to} L ¹⁰² represent a single bond or an organic linking group. Here, the single bond means that the polymer main chain and X are directly bonded without a linking chain.
When L ^{101 to} L ¹⁰² represent an organic linking group, L ^{101 to} L ¹⁰² represent a polyvalent linking group composed of a nonmetallic atom, 0 to 60 carbon atoms, and 0 to 10 nitrogen atoms. It consists of atoms, 0 to 50 oxygen atoms, 0 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. Specifically, it is preferably selected from -N <, an aliphatic group, an aromatic group, a heterocyclic group, and combinations thereof, -O-, -S-, -CO-, -NH-, or A combination containing -O- or -S- or -CO- or -NH- is preferably a divalent linking group.
More specific examples of the linking group include the following structural units or those formed by combining them.

In General Formula (I-1), L ¹⁰¹ represents a single bond or one structure selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. A linking group having the above is preferable.
L ¹⁰² is selected from the group consisting of —CH ₂ CH ₂ CH ₂ S—, —CH ₂ S—, —CONHCH (CH ₃ ) CH ₂ —, —CONH—, —CO—, —CO ₂ — and —CH ₂ —. A linking group having one or more selected structures is preferred.

In the general formula (I-2), A ¹⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ). , —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , -NHSO ₂ R _d , -SO ₂ N (R _a ) (R _b ), -N (R _a ) (R _b ) (R _c ), -N (R _a ) (R _b ) (R _c ) ( _{R g), - PO 3 (} R e) (R f), - OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having 1 to 8 carbon atoms), and R _d is a linear, branched or cyclic group. R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 8), an alkali metal, R 1 represents an alkaline earth metal or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. In addition, —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₂ N (R _a ) (R _b ), -N (R _a ) (R _b ) (R _c ), -N (R _a ) (R _b ) (R _c ) (R _g ), -PO ₃ (R _e ) R _{a to} R _g may be bonded to each other to form a ring with _{respect to} (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ), The formed ring may be a heterocycle containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom. R _{a to} R _g may further have a substituent, and the substituent that can be introduced here is the same as the substituent that can be introduced when R ^{1 to} R ⁸ are alkyl groups. Can be listed.

Specific examples of the linear, branched or cyclic alkyl group in R _{a to} R _f include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and an isopropyl group. , Isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
In addition, in R _{a to} R _g , preferable examples of the alkali metal include lithium, sodium, and potassium, the alkaline earth metal includes barium, and the onium includes ammonium, iodonium, sulfonium, and the like.
Examples of the halogen ion include fluorine ion, chlorine ion, bromine ion, inorganic anion includes nitrate anion, sulfate anion, tetrafluoroborate anion, hexafluorophosphate anion, etc., organic anion includes methanesulfonate anion, Preferred examples include trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, p-toluenesulfonic acid anion, and the like.

The A ^101, _{specifically, -NHCOCH 3, -CONH 2, -CON} (CH 3) 2, -COOH, -SO 3 - NMe 4 +, -SO 3 - K +, - (CH 2 CH 2 O) _n H, morpholyl group and the like are preferable. More _{preferably, -NHCOCH 3, -CONH 2, -CON} (CH 3) 2, -SO 3 - K +, - (CH 2 CH 2 O) n H, is. In the above, n preferably represents an integer of 1 to 100.

  p represents an integer of 1 to 3, preferably 2 to 3, and more preferably 3.

  In the hydrophilic polymer including the structures represented by the general formulas (I-1) and (I-2), x and y are the structures represented by the general formula (I-1) in the (A) specific hydrophilic polymer. The composition ratio of the unit and the structural unit represented by the general formula (I-2) is represented. x is 0 <x <100, and y is 0 <y <100. x is preferably in the range of 1 <x <90, and more preferably in the range of 1 <x <50. y is preferably in the range of 10 <y <99, and more preferably in the range of 50 <y <99.

  The copolymerization ratio of the hydrophilic polymer (I) including the structures represented by the general formulas (I-1) and (I-2) is such that the amount of the general formula (I-2) having a hydrophilic group is within the above range. Can be set arbitrarily. Preferably, the molar ratio (y) of the structural unit of the general formula (I-2) and the molar ratio (x) of the structural unit of the general formula (I-1) having a hydrolyzable silyl group amount are y / x = The range of 30/70 to 99/1 is preferable, y / x = 40/60 to 98/2 is more preferable, and y / x = 50/50 to 97/3 is most preferable. If y / x is 30/70 or more, the hydrophilicity is not insufficient. On the other hand, if y / x = 99/1 or less, the hydrolyzable silyl group amount is sufficient and sufficient curing is obtained. The film strength is also sufficient.

  The mass average molecular weight of the polymer containing the structures represented by the general formulas (I-1) and (I-2) is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, 1,000 to 200,000 is most preferred.

   Specific examples of the hydrophilic polymer including the structures represented by the general formulas (I-1) and (I-2) are shown below together with their mass average molecular weights (MW). It is not limited to. In addition, the polymer of the specific example shown below means that each structural unit described is a random copolymer or a block copolymer contained in the described molar ratio.

Each compound for synthesizing the hydrophilic polymer including the structures represented by the general formulas (I-1) and (I-2) is commercially available, and can be easily synthesized.
Any conventionally known method can be used as the radical polymerization method for synthesizing the hydrophilic polymer containing the structures represented by the general formulas (I-1) and (I-2).
Specifically, general radical polymerization methods include, for example, New Polymer Experiments 3 (1996, Kyoritsu Shuppan), Polymer Synthesis and Reaction 1 (Polymer Society of Japan, 1992, Kyoritsu Shuppan), New Experiment Chemistry Lecture 19 (1978, Maruzen), Polymer Chemistry (I) (Edited by The Chemical Society of Japan, 1996, Maruzen), Synthetic Polymer Chemistry (Materials Engineering Lecture, 1995, Tokyo Denki University Press) These can be applied.

[Hydrophilic polymer (II) including structures represented by general formulas (II-1) and (II-2)]

In general formulas (II-1) and (II-2), R ^{201 to} R ²⁰⁵ each independently represent a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to ^{3, L 201} and ^{L 202} each represents a single bond or a polyvalent organic linking group. A ²⁰¹ is _{-OH, -OR a, -COR a,} -CO 2 R e, -CON (R a) (R b), - N (R a) (R b), - NHCOR d, -NHCO 2 R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.

  The hydrophilic polymer (II) including the structures represented by the general formulas (II-1) and (II-2) has a structural unit represented by the above general formula (II-2), and has a polymer chain. It preferably has a partial structure represented by the above general formula (II-1) at the terminal thereof.

In the general formulas (II-1) and (II-2), R ^{201 to} R ²⁰⁵ each independently represents a hydrogen atom or a hydrocarbon group, and hydrocarbons in the case where R ^{201 to} R ²⁰⁵ represent a hydrocarbon group. Examples of the group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable. Specifically, there may be mentioned the same ones as mentioned in R ¹⁰¹ to R ¹⁰⁸ in the general formula (I-1) and (I-2).
L ²⁰¹ and L ²⁰² each independently represents a single bond or a polyvalent organic linking group. Here, the single bond means that the main chain of the polymer is directly bonded to the A ²⁰¹ and Si atoms without a connecting chain. When L ²⁰¹ and L ²⁰² represent a polyvalent organic linking group, specific examples and preferred examples thereof may be the same as those described for L ¹⁰¹ in the general formula (I-1).
A ²⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Specific examples and preferred examples of A ²⁰¹ include the same examples as those described for A ¹⁰¹ in formula (I-2).
q represents an integer of 1 to 3. Preferably it is 2-3, More preferably, it is 3.

L ²⁰¹ and L ²⁰² are —CH ₂ CH ₂ CH ₂ S—, —CH ₂ S—, —CONHCH (CH ₃ ) CH ₂ —, —CONH—, —CO—, —CO ₂ — and —CH ₂ —. A linking group having at least one structure selected from the group consisting of

  The hydrophilic polymer containing the structure represented by the general formulas (II-1) and (II-2) is, for example, a chain transfer agent (described in the radical polymerization handbook (NTS, Mikiji Tsunoike, Go Endo)). And Iniferter (described in Macromolecules 1986, 19, p287- (Otsu)) can be synthesized by radical polymerization of a hydrophilic monomer (eg, potassium salt of acrylamide, acrylic acid, 3-sulfopropyl methacrylate). Examples of chain transfer agents include 3-mercaptopropionic acid, 2-aminoethanethiol hydrochloride, 3-mercaptopropanol, 2-hydroxyethyl disulfide, 3-mercaptopropyltrimethoxysilane. Alternatively, a hydrophilic monomer (eg, acrylamide) may be radically polymerized using a radical polymerization initiator having a reactive group without using a chain transfer agent.

  The hydrophilic polymer including the structures represented by the general formulas (II-1) and (II-2) is represented by the following general formula (i) and a radically polymerizable monomer represented by the following general formula (i). In the radical polymerization, it can be synthesized by radical polymerization using a silane coupling agent having chain transfer ability. Since the silane coupling agent (ii) has chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the end of the polymer main chain in radical polymerization.

In the above formula (i) and ^{(ii), R 201 ~R 205} , L 201, L 202, A 201, q is the same as defined in the general formula (II-1). These compounds are commercially available and can also be easily synthesized. The radically polymerizable monomer represented by the general formula (i) has a hydrophilic group ^A201 , and this monomer becomes one structural unit in the hydrophilic polymer.

  In the hydrophilic polymer (II) including the structures represented by the general formulas (II-1) and (II-2), the number of moles of the structural unit of the general formula (II-1) having a hydrolyzable silyl group amount. On the other hand, the number of moles of the structural unit of the general formula (II-2) is preferably in the range of 1000 to 10 times, more preferably 500 to 20 times, and most preferably 200 to 30 times. If it is 30 times or more, the hydrophilicity is not insufficient. On the other hand, if it is 200 times or less, the amount of hydrolyzable silyl groups is sufficient, sufficient curing is obtained, and the film strength is also sufficient.

   The weight average molecular weight of the hydrophilic polymer (II) including the structures represented by the general formulas (II-1) and (II-2) is preferably 1,000 to 1,000,000, and 1,000 to 500,000. 000 is more preferable, and 1,000 to 200,000 is most preferable.

  Specific examples of the hydrophilic polymer (II) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto.

[Hydrophilic polymer (III) including structures represented by general formulas (III-1) and (III-2)]
The hydrophilic polymer (III) includes structures represented by the following general formulas (III-1) and (III-2). The hydrophilic polymer (III) is preferably a hydrophilic graft polymer obtained by introducing a side chain having a hydrophilic group into a trunk polymer having a reactive group.

In general formulas (III-1) and (III-2), R ^{301 to} R ³¹¹ each independently represents a hydrogen atom or a hydrocarbon group. r represents an integer of 1 to 3, and L ^{301 to} L ³⁰³ each represents a single bond or a polyvalent organic linking group. x and y represent a composition ratio, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ³⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , -OCON (R _a ) (R _b ), -NHCON (R _a ) (R _b ), -SO ₃ R _e , -OSO ₃ R _e , -SO ₂ R _d , -NHSO ₂ R _d , -SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.

In the general formulas (III-1) and (III-2), R ^{301 to} R ³¹¹ each independently represents a hydrogen atom or a hydrocarbon group, and hydrocarbons in the case where R ^{301 to} R ³¹¹ represent a hydrocarbon group. Examples of the group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable. Specifically, the same as those mentioned for R ^{101 to} R ¹⁰⁸ in the general formulas (I-1) and (I-2) can be given, and preferred ranges are also the same.
L ³⁰¹ , L ³⁰² and L ³⁰³ each independently represents a single bond or a polyvalent organic linking group. Here, the single bond means that the main chain of the polymer and A ³⁰¹ , the side chain, and the Si atom are directly bonded without a connecting chain. When L ³⁰¹ , L ³⁰² and L ³⁰³ represent a polyvalent organic linking group, specific examples and preferred examples are the same as those described for L ¹⁰¹ in the general formula (I-1). Can do.
A ³⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , -OCON (R _a ) (R _b ), -NHCON (R _a ) (R _b ), -SO ₃ R _e , -OSO ₃ R _e , -SO ₂ R _d , -NHSO ₂ R _d , -SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Specific examples and preferred examples of A ²⁰¹ include the same examples as those described for A ¹⁰¹ in formula (I-2).
r represents an integer of 1 to 3. Preferably it is 2-3, More preferably, it is 3.

  This hydrophilic graft polymer can be prepared using a method generally known as a method for synthesizing a graft polymer. Specifically, a general method for synthesizing a graft polymer is described in “Graft Polymerization and its Application” by Fumio Ide, published in 1977, “Polymer Publications”, “New Polymer Experimental 2” Reaction ", edited by Polymer Society, Kyoritsu Shuppan Co., Ltd. 1995, and these can be applied.

  As a synthesis method of the graft polymer, basically, 1. 1. Polymerize the branch monomer from the trunk polymer. 2. Link the branch polymer to the trunk polymer. It can be divided into three methods of copolymerizing a branch polymer with a trunk polymer (macromer method). Any of these three methods can be used to produce the hydrophilic graft polymer used in the present invention, but “3. Macromer method” is particularly excellent from the viewpoint of production suitability and control of the membrane structure. ing.

  The synthesis of graft polymer using a macromonomer is described in the aforementioned “New Polymer Experiments 2, Polymer Synthesis / Reaction” edited by Polymer Society of Japan, Kyoritsu Publishing Co., Ltd. 1995. It is also described in detail in Yamashita Yu et al., “Macromonomer Chemistry and Industry”, IPC, 1989. The graft polymer used in the present invention is obtained by first copolymerizing a hydrophilic macromonomer (corresponding to a precursor of a hydrophilic polymer side chain) synthesized by the above method and a monomer having a reactive group. Can be synthesized.

  Particularly useful among the hydrophilic macromonomers are macromonomers derived from carboxyl group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylstyrene sulfonic acid, and salts thereof Sulfonic acid macromonomer derived from the monomer of amide, amide macromonomer such as acrylamide and methacrylamide, amide macromonomer derived from N-vinylcarboxylic amide monomer such as N-vinylacetamide and N-vinylformamide, Macromonomers derived from hydroxyl-containing monomers such as hydroxyethyl methacrylate, hydroxyethyl acrylate, glycerol monomethacrylate, methoxyethyl acrylate, methoxypolyethylene glycol acrylic Over bets, a macromonomer derived from alkoxy group or ethylene oxide group-containing monomers such as polyethylene glycol acrylate. 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 macromonomers, the useful polymer has a mass average molecular weight (hereinafter simply referred to as molecular weight) in the range of 400 to 100,000, preferably 1000 to 50,000, and particularly preferably 1500 to 20,000. . If the molecular weight is 400 or more, effective hydrophilicity is obtained, and if it is 100,000 or less, the polymerizability with the copolymerization monomer forming the main chain tends to be high, both of which are preferable.

  In the hydrophilic polymer (III) including the structures represented by the general formulas (III-1) and (III-2), x is preferably in the range of 1 <x <90, and in the range of 1 <x <50. More preferably. y is preferably in the range of 10 <y <99, and more preferably in the range of 50 <y <99.

  The copolymerization ratio of the hydrophilic polymer (III) can be arbitrarily set so that the amount of the general formula (III-2) having a hydrophilic group is within the above range. Preferably, the molar ratio (y) of the structural unit of the general formula (III-2) and the molar ratio (x) of the structural unit of the general formula (III-1) having a hydrolyzable silyl group amount are y / x = The range of 30/70 to 99/1 is preferable, y / x = 40/60 to 98/2 is more preferable, and y / x = 50/50 to 97/3 is most preferable. If y / x is 30/70 or more, the hydrophilicity is not insufficient. On the other hand, if y / x = 99/1 or less, the hydrolyzable silyl group amount is sufficient and sufficient curing is obtained. The film strength is also sufficient.

  The hydrophilic polymer (III) preferably has a mass average molecular weight of 1,000,000 or less, and has a molecular weight of 1,000 to 1,000,000, more preferably 20,000 to 100,000. When the molecular weight is 1,000,000 or less, there is a problem in handling properties, such as the ability to form a uniform coating film without lowering the solubility in a solvent when preparing a coating solution for forming a hydrophilic coating film, without lowering the solubility in the solvent. This is preferable.

  Specific examples of the hydrophilic polymer (III) including the structures represented by the general formulas (III-1) and (III-2) are shown below together with their mass average molecular weights (MW). The invention is not limited to these examples. In addition, the polymer of the specific example shown below means that each structural unit described is a random copolymer or a block copolymer contained in the described molar ratio.

  The hydrophilic polymer (I), (II) or (III) may be a copolymer with another monomer. Examples of other monomers used include acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide, etc. These known monomers are also included. By copolymerizing such monomers, various physical properties such as film forming property, film strength, hydrophilicity, hydrophobicity, solubility, reactivity, and stability can be improved.

  Specific examples of acrylic esters include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, Dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chloro Benzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphene Chill acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenyl carbonyloxy) ethyl acrylate.

  Specific examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chloro Benzyl methacrylate, hydroxybenzyl methacrylate, hydroxy E phenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenyl carbonyloxy) ethyl methacrylate.

  Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, and N-tolylacrylamide. N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-phenylacrylamide , N-hydroxyethyl-N-methylacrylamide and the like.

  Specific examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, N-hydroxyethylmethacrylamide, N -Phenylmethacrylamide, N-tolylmethacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide, N , N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like.
Specific examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

  The ratio of these other monomers used for the synthesis of the copolymer needs to be an amount sufficient for improving various physical properties, but the function as a hydrophilic film is sufficient, and the specific hydrophilic polymer (I ), In order to obtain the advantage of adding the specific hydrophilic polymer (II) and / or the specific hydrophilic polymer (III), it is preferable that the ratio is not too large. Accordingly, the preferred total proportion of the other monomers in the specific hydrophilic polymer (I), the specific hydrophilic polymer (II) and / or the specific hydrophilic polymer (III) is preferably 80% by mass or less, more preferably It is 50 mass% or less.

  The copolymerization ratio of the hydrophilic polymer (I), (II) or (III) can be measured by preparing a calibration curve with a nuclear magnetic resonance apparatus (NMR) or a standard substance and measuring with an infrared spectrophotometer. it can.

In the hydrophilic composition in the present invention, the hydrophilic polymers (I), (II) or (III) may be used alone or in combination of two or more.
The hydrophilic polymer (I), (II) or (III) is preferably used in an amount of 20 to 99.5% by mass based on the total solid content of the hydrophilic composition from the viewpoint of curability and hydrophilicity. More preferably, ˜99.5% by mass is used.

  The above-mentioned hydrophilic polymer forms a crosslinked film in a state where it is mixed with a hydrolysis and polycondensate of metal alkoxide. The hydrophilic polymer, which is an organic component, is involved in the film strength and film flexibility. In particular, the hydrophilic polymer has a viscosity of 0.1 to 100 mPa · s (5% aqueous solution, measured at 20 ° C.), preferably When it is in the range of 0.5 to 70 mPa · s, more preferably 1 to 50 mPa · s, good film properties are provided.

[Crosslinking agent]
When the hydrophilic composition in the present invention contains a hydrophilic polymer containing the structure represented by the general formula (I), it is preferable to contain a crosslinking agent in order to obtain good curability. When the hydrophilic composition contains a hydrophilic polymer containing the structure represented by the general formula (II) or the general formula (III), good curability can be obtained even when no crosslinking agent is contained. In order to obtain a coating film having very excellent film strength, a crosslinking agent may be contained.
As the crosslinking agent, an alkoxide compound (also referred to as a metal alkoxide) containing an element selected from Si, Ti, Zr, and Al is particularly preferable. A metal alkoxide is a hydrolyzable polymerizable compound having a functional group capable of being hydrolyzed and polycondensed in its structure and serving as a cross-linking agent, and has a cross-linked structure by polycondensation between metal alkoxides. A strong cross-linked film is formed and further chemically bonded to the hydrophilic polymer. The metal alkoxide can be represented by general formula (V-1) or general formula (V-2), in which R ²⁰ represents a hydrogen atom, an alkyl group or an aryl group, and R ²¹ represents an alkyl group or an aryl group. Z represents Si, Ti or Zr, and m represents an integer of 0-2. The carbon number when R ²⁰ and R ²¹ represent an alkyl group is preferably 1 to 4. The alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, and a mercapto group. This compound is a low molecular compound and preferably has a molecular weight of 2000 or less.

_{^{(R 20) m -Z- (OR}} 21) 4-m (V-1)
Al- (OR ²² ) ₃ (V-2)

Specific examples of the hydrolyzable compound represented by the general formula (V-1) or the general formula (V-2) are shown below, but the present invention is not limited thereto.
When Z is Si, that is, the hydrolyzable compound containing silicon includes, for example, trimethoxysilane, tetramethoxysilane, tetraethoxylane, tetrapropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, γ- Examples include chloropropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and the like. Among these, particularly preferred are trimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane and the like.

When Z is Ti, i.e., including titanium, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl Examples include trimethoxy titanate, methyl triethoxy titanate, ethyl triethoxy titanate, diethyl diethoxy titanate, phenyl trimethoxy titanate, and phenyl triethoxy titanate. When Z is Zr, that is, the one containing zirconium can include, for example, zirconates corresponding to the compounds exemplified as those containing titanium.
In the case where the central metal is Al, that is, examples of the hydrolyzable compound containing aluminum include, for example, trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, triisopropoxy aluminate and the like. be able to.

  Among the above, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane are particularly preferable.

  When the metal alkoxide compound selected from Si, Ti, Zr, and Al uses a hydrophilic polymer including the structure represented by the general formula (I), 1 to 80% by mass is preferably used, and more preferably 5 to 70% by mass. When using a hydrophilic polymer containing a structure represented by the general formula (II) or general formula (III), it is preferably used in an amount of 0 to 80% by mass based on the total solid content of the hydrophilic composition. More preferably, 0 to 70% by mass is used.

[Curing catalyst]
In the hydrophilic composition of the present invention, by dissolving an alkoxysilyl group-containing hydrophilic polymer and a crosslinking agent such as a metal alkoxide compound in a solvent and stirring well, these components are hydrolyzed, polycondensed, and organic -An inorganic composite sol solution is formed, and this sol solution forms a hydrophilic film having high hydrophilicity and high film strength. In preparing the organic / inorganic composite sol solution, it is preferable to use a curing catalyst in order to promote hydrolysis and polycondensation reaction.
As the curing catalyst, it is preferable to use an acidic catalyst, a basic catalyst, or a metal complex.

  As the curing catalyst, a catalyst that promotes a reaction that causes hydrolysis and polycondensation of the cross-linking agent such as the metal alkoxide compound to cause a bond with the alkoxysilyl group-containing hydrophilic polymer is selected, and the acid or basic compound is used as it is. Or an acid or a compound in which a basic compound is dissolved in a solvent such as water or alcohol (hereinafter collectively referred to as an acidic catalyst and a basic catalyst, respectively) is used. The concentration at which the acid or basic compound is dissolved in the solvent is not particularly limited, and may be appropriately selected depending on the characteristics of the acid or basic compound used, the desired content of the catalyst, and the like. Here, when the concentration of the acid or basic compound constituting the catalyst is high, the hydrolysis and polycondensation rates tend to increase. However, when a basic catalyst with a high concentration is used, a precipitate may be generated in the sol solution. Therefore, when a basic catalyst is used, the concentration is preferably 1 N or less in terms of concentration in an aqueous solution.

The type of the acidic catalyst or the basic catalyst is not particularly limited. However, when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element that hardly remains in the coating film after drying is preferable. Specifically, the acid catalyst is represented by hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid or acetic acid, and its R ³⁰ COOH. is the structural formula substituted carboxylic acid was replaced by an R ³⁰ other element or substituent, and sulfonic acids such as benzenesulfonic acid. Examples of the basic catalyst include an ammoniacal base such as aqueous ammonia, ethylamine and aniline, etc. And amines.

The catalyst is particularly preferably a metal complex.
The metal complex catalyst can promote hydrolysis and polycondensation of a metal alkoxide compound selected from Si, Ti, Zr, and Al, and can cause a bond with a hydrophilic polymer. Particularly preferred metal complex catalysts include metal elements selected from groups 2A, 3B, 4A and 5A of the periodic table and β-diketones, ketoesters, hydroxycarboxylic acids or esters thereof, amino alcohols, and enolic active hydrogen compounds. Metal complexes composed of selected oxo or hydroxy oxygen containing compounds.
Among the constituent metal elements, 2A group elements such as Mg, Ca, Sr and Ba, 3B group elements such as Al and Ga, 4A group elements such as Ti and Zr, and 5A group elements such as V, Nb and Ta are preferable. , Each forming a complex with excellent catalytic effect. Among them, complexes obtained from Zr, Al and Ti are excellent and preferred.

  In the present invention, the oxo- or hydroxy-oxygen-containing compound constituting the ligand of the metal complex is a β diketone such as acetylacetone (2,4-pentanedione) or 2,4-heptanedione, methyl acetoacetate, acetoacetic acid Ketoesters such as ethyl and butyl acetoacetate, lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate and other hydroxycarboxylic acids and esters thereof, 4-hydroxy-4-methyl-2-pentanone , 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-heptanone, ketoalcohols such as 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl- Monoethanolamine, diethanol Amino alcohols such as amine and triethanolamine, methylol melamine, methylol urea, methylol acrylamide, enol active compounds such as malonic acid diethyl ester, methyl group, methylene group or carbonyl carbon of acetylacetone (2,4-pentanedione) The compound which has a substituent is mentioned.

  A preferred ligand is acetylacetone or an acetylacetone derivative. In the present invention, the acetylacetone derivative refers to a compound having a substituent on the methyl group, methylene group or carbonyl carbon of acetylacetone. Substituents for substitution on the methyl group of acetylacetone are all linear or branched alkyl groups having 1 to 3 carbon atoms, acyl groups, hydroxyalkyl groups, carboxyalkyl groups, alkoxy groups, alkoxyalkyl groups, and acetylacetone As a substituent for substituting the methylene group, a carboxyl group, each of which is a linear or branched carboxyalkyl group and hydroxyalkyl group having 1 to 3 carbon atoms, and as a substituent for substituting the carbonyl carbon of acetylacetone, Is an alkyl group of 1 to 3, and in this case, a hydrogen atom is added to the carbonyl oxygen to form a hydroxyl group.

  Specific examples of preferable acetylacetone derivatives include ethylcarbonylacetone, n-propylcarbonylacetone, i-propylcarbonylacetone, diacetylacetone, 1-acetyl-1-propionyl-acetylacetone, hydroxyethylcarbonylacetone, hydroxypropylcarbonylacetone, acetoacetic acid. , Acetopropionic acid, diacetacetic acid, 3,3-diacetpropionic acid, 4,4-diacetbutyric acid, carboxyethylcarbonylacetone, carboxypropylcarbonylacetone, diacetone alcohol. Of these, acetylacetone and diacetylacetone are particularly preferred. The complex of the above acetylacetone derivative and the above metal element is a mononuclear complex in which one to four molecules of the acetylacetone derivative are coordinated per metal element, and the coordinateable bond of the acetylacetone derivative is a coordinateable bond of the acetylacetone derivative. When the number of hands is larger than the total number of hands, ligands commonly used for ordinary complexes such as water molecules, halogen ions, nitro groups, and ammonio groups may coordinate.

  Examples of preferred metal complexes include tris (acetylacetonato) aluminum complex, di (acetylacetonato) aluminum / aco complex, mono (acetylacetonato) aluminum / chloro complex, di (diacetylacetonato) aluminum complex, ethylacetate Acetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), cyclic aluminum oxide isopropylate, tris (acetylacetonato) barium complex, di (acetylacetonato) titanium complex, tris (acetylacetonato) titanium complex, di-i -Propoxy bis (acetylacetonato) titanium complex salt, zirconium tris (ethyl acetoacetate), zirconium tris (benzoic acid) complex salt, etc. are mentioned. These are excellent in stability in aqueous coating solutions and in gelation promotion effect in sol-gel reaction during heat drying, but in particular, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), di ( Acetylacetonato) titanium complex and zirconium tris (ethylacetoacetate) are preferred.

  Although the description of the counter salt of the metal complex described above is omitted in this specification, the type of the counter salt is arbitrary as long as it is a water-soluble salt that maintains the neutrality of the charge as the complex compound, such as nitrate, Salt forms such as halogenates, sulfates, phosphates, etc., that ensure stoichiometric neutrality are used. For the behavior of the metal complex in the silica sol-gel reaction, see J.A. Sol-Gel. Sci. and Tec. There is a detailed description in 16.209 (1999). The following scheme is estimated as the reaction mechanism. That is, in the coating solution, the metal complex has a coordinated structure and is stable, and in the dehydration condensation reaction that starts in the heat drying process after coating, it is considered that crosslinking is promoted by a mechanism similar to an acid catalyst. In any case, the use of this metal complex has led to satisfying the improvement of coating solution aging stability and film surface quality, and high hydrophilicity and high durability.

In addition to the above metal complex catalyst, the acidic catalyst and the basic catalyst may be used in combination.
The above metal complex catalyst can be easily obtained as a commercial product, and can also be obtained by a known synthesis method, for example, reaction of each metal chloride with an alcohol.

  The catalyst is preferably used in an amount of 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total solid content of the hydrophilic composition.

[Surfactant]
A surfactant may be added to the hydrophilic composition.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826.
The addition amount of the surfactant is appropriately selected according to the purpose, but is preferably 0.001 to 10% by mass, and 0.01 to 5% by mass with respect to the total solid content of the hydrophilic composition. More preferably.

[Other ingredients]
The various additives that can be used in the hydrophilic composition used in the present invention as necessary are described below.

(Antimicrobial agent)
In order to impart antibacterial, antifungal and antialgal properties to the goggles of the present invention, the hydrophilic composition can contain an antibacterial agent. In the formation of the hydrophilic layer, it is preferable to contain a hydrophilic or water-soluble antibacterial agent in the hydrophilic composition. By including a hydrophilic and water-soluble antibacterial agent, goggles excellent in antibacterial, antifungal and antialgal properties can be obtained without impairing surface hydrophilicity.
As the antibacterial agent, it is preferable to add a compound that does not decrease the hydrophilicity of goggles, and examples of such an antibacterial agent include inorganic antibacterial agents and water-soluble organic antibacterial agents. As the antibacterial agent, those exhibiting a bactericidal effect against fungi existing around us, such as bacteria represented by Staphylococcus aureus and Escherichia coli, and fungi such as fungi and yeast are used.

Examples of organic antibacterial agents include phenol ether derivatives, imidazole derivatives, sulfone derivatives, N-haloalkylthio compounds, anilide derivatives, pyrrole derivatives, quaternary ammonium salts, pyridines, triazines, benzoisothiazolines, and isothiazolines. It is done.
For example, 1,2-benzisothiazolin-3-one, N-fluorodichloromethylthio-phthalimide, 2,3,5,6-tetrachloroisophthalonitrile, N-trichloromethylthio-4-cyclohexene-1,2-dicarboxyl Imido, copper 8-quinolinate, bis (tributyltin) oxide, 2- (4-thiazolyl) benzimidazole (hereinafter referred to as TBZ), methyl 2-benzimidazole carbamate (hereinafter referred to as BCM), 10,10 '-Oxybisphenoxyarsine (hereinafter referred to as OBPA) 2,3,5,6-tetrachloro-4- (methylsulfone) pyridine, bis (2-pyridylthio-1-oxide) zinc (hereinafter referred to as ZPT) >, N, N-dimethyl-N ′-(fluorodichloromethylthio) -N′-phenylsulfamide <dichloro Luanide>, poly- (hexamethylene biguanide) hydrochloride, dithio-2-2′-bis (benzmethylamide), 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 2-bromo-2 -Nitro-1,3-propanediol, hexahydro-1,3-tris- (2-hydroxyethyl) -S-triazine, p-chloro-m-xylenol, 1,2-benzisothiazolin-3-one, etc. However, it is not limited to these.
These organic antibacterial agents can be appropriately selected and used in consideration of hydrophilicity, water resistance, sublimation property, safety and the like. Among organic antibacterial agents, 2-bromo-2-nitro-1,3-propanediol, TBZ, BCM, OBPA, and ZPT are preferable from the viewpoint of hydrophilicity, antibacterial effect, and cost.

  Examples of inorganic antibacterial agents include mercury, silver, copper, zinc, iron, lead, bismuth and the like in descending order of bactericidal action. For example, the thing which carry | supported metals and metal ions, such as silver, copper, zinc, nickel, on the silicate type | system | group support | carrier, phosphate type | system | group support, an oxide, glass, potassium titanate, an amino acid, etc. is mentioned. For example, zeolite antibacterial, calcium silicate antibacterial, zirconium phosphate antibacterial, calcium phosphate antibacterial, zinc oxide antibacterial, soluble glass antibacterial, silica gel antibacterial, activated carbon antibacterial, titanium oxide Antibacterial agent, titania antibacterial agent, organometallic antibacterial agent, ion exchanger ceramic antibacterial agent, layered phosphate-quaternary ammonium salt antibacterial agent, antibacterial stainless steel, etc. Absent.

Natural antibacterial agents include chitosan, a basic polysaccharide obtained by hydrolyzing chitin contained in crabs and shrimp shells.
In the present invention, Nikko's “trade name Holon Killer Bees Sera” made of aminometal in which a metal is compounded on both sides of an amino acid is preferable.
These are not transpirationable, easily interact with the polymer and crosslinker component of the hydrophilic layer, can be stably molecularly dispersed or solid dispersed, and the antibacterial agent is effectively exposed to the hydrophilic layer surface, And even if it splashes with water, it does not elute, can maintain the effect for a long time, and does not affect the human body. Moreover, it can disperse | distribute stably with respect to a hydrophilic layer and a coating liquid, and deterioration of a hydrophilic layer and a coating liquid does not occur.
Among the antibacterial agents, silver-based inorganic antibacterial agents and water-soluble organic antibacterial agents are most preferable because of their great antibacterial effects. In particular, silver zeolite in which silver is supported on zeolite, which is a silicate carrier, antibacterial agent in which silver is supported on silica gel, 2-bromo-2-nitro-1,3-propanediol, TPN, TBZ, BCM, OBPA ZPT is preferred. Particularly preferred commercially available silver zeolite antibacterial agents include “Zeomic” from Shinagawa Fuel, “Sylwell” from Fuji Silysia Chemical, and “Bactenone” from JEOL. In addition, Toa Gosei's “Novalon” in which silver is supported on an inorganic ion exchanger ceramic, “Atomy Ball” from Catalytic Chemical Industry, and “Suneyeback P” as a triazine antibacterial agent are also preferred.

  The content of the antibacterial agent is generally 0.001 to 10% by mass, preferably 0.005 to 5% by mass, more preferably 0.01 to 3% by mass, and 0.02 to 1.5%. Mass% is particularly preferable, and 0.05 to 1 mass% is most preferable. If the content is 0.001% by mass or more, an effective antibacterial effect can be obtained. Further, if the content is 10% by mass or less, the hydrophilicity is not lowered, the aging is not deteriorated, and the antifouling property and the antifogging property are not adversely affected.

(Inorganic fine particles)
The hydrophilic layer of the present invention may contain inorganic fine particles in order to improve hydrophilicity, prevent cracking of the film, and improve film strength. As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate or a mixture thereof can be preferably mentioned.
The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 0.5 to 3 μm. Within the above range, goggles that are stably dispersed in the hydrophilic layer, sufficiently retain the film strength of the hydrophilic layer, and have high durability and excellent hydrophilicity can be formed.
Among the inorganic fine particles as described above, a colloidal silica dispersion is particularly preferable and can be easily obtained as a commercial product.
The content of the inorganic fine particles is preferably 80% by mass or less, and more preferably 50% by mass or less, based on the total solid content of the hydrophilic layer.

In addition to this, if necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, tackifiers, etc. within a range that does not impair hydrophilicity in order to improve adhesion to the substrate, etc. Can be contained.
As the tackifier, specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, 5-6p (for example, (meth) acrylic acid and an alkyl group having 1 to 20 carbon atoms). An ester with an alcohol having, an ester of (meth) acrylic acid with an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer comprising an ester of (meth) acrylic acid with an aromatic alcohol having 6 to 14 carbon atoms) And a low molecular weight tackifying resin having a polymerizable unsaturated bond.

(UV absorber)
From the viewpoint of improving the weather resistance and durability of the coating film, an ultraviolet absorber can be used.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194843, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492 and 56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Examples thereof include compounds described in No. 24239, compounds that emit ultraviolet light by absorbing ultraviolet rays typified by stilbene and benzoxazole compounds, so-called fluorescent brighteners, and the like.
Although the addition amount of a ultraviolet absorber is suitably selected according to the objective, it is preferable that it is 0.5-15 mass% with respect to the total solid of a hydrophilic composition.

(Antioxidant)
An antioxidant can be added to improve the stability of the hydrophilic composition. Examples of the antioxidant include European Patent Application Nos. 223739, 309401, 309402, 310551, 310552, 457416, German Patent Application Publication No. 3435443, JP-A Nos. 54-262047, 63-113536, 63-163351, JP-A-2-262654, JP-A-2-71262, Examples include those described in JP-A-3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
Although the addition amount of antioxidant is suitably selected according to the objective, it is preferable that it is 0.1-8 mass% with respect to the total solid of a hydrophilic composition.

(solvent)
It is also effective to appropriately add an organic solvent to the hydrophilic composition in order to ensure the formation of a uniform coating film on the substrate during the formation of the coating film with the hydrophilic composition.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether And ether solvents.
In this case, it is effective to add in a range that does not cause a problem in relation to VOC (volatile organic solvent), and the amount is preferably 0 to 50% by mass, more preferably 0 to 30% with respect to the entire hydrophilic composition. It is the range of mass%.

(Polymer compound)
In order to adjust the physical properties of the coating film, various polymer compounds can be added to the hydrophilic composition as long as the hydrophilicity is not impaired. High molecular compounds include acrylic polymer, polyvinyl alcohol resin, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl formal resin, shellac, vinyl resin, acrylic resin. Rubber resins, waxes and other natural resins can be used. Two or more of these may be used in combination. Of these, vinyl copolymers obtained by copolymerization of acrylic monomers are preferred. Furthermore, a copolymer containing “carboxyl group-containing monomer”, “methacrylic acid alkyl ester”, or “acrylic acid alkyl ester” as a structural unit is also preferably used as the copolymer composition of the polymer binder.
The addition amount of the polymer compound is appropriately selected according to the purpose, but is preferably 0.001 to 20% by mass, and 0.01 to 15% by mass with respect to the total solid content of the hydrophilic composition. It is more preferable that

[Preparation of hydrophilic composition]
The preparation of the hydrophilic composition can be carried out by dissolving a hydrophilic polymer having at least one hydrophilic group and a hydrolyzable alkoxysilyl group and, if necessary, a specific alkoxide and a catalyst in a solvent such as ethanol, followed by stirring. . The reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time for which stirring is continued is preferably in the range of 1 to 72 hours. By this stirring, hydrolysis and polycondensation of both components are advanced, and organic inorganic A composite sol solution can be obtained.

  The solvent used in preparing the hydrophilic composition is not particularly limited as long as it can uniformly dissolve and disperse these, but for example, an aqueous solvent such as methanol, ethanol, water and the like is preferable.

  As described above, the preparation of the organic-inorganic composite sol liquid (hydrophilic composition) for forming a hydrophilic layer from the hydrophilic composition utilizes a sol-gel method. For the sol-gel method, Sakuo Sakuo “Science of Sol-Gel Method”, Agne Jofusha (published) (1988), Satoshi Hirashima “Functional Thin Film Formation Technology by the Latest Sol-Gel Method” General Technology Center (Published) (1992) and the like, and the methods described therein can be applied to the preparation of the hydrophilic composition in the present invention.

〔Base material〕
The base material used in the present invention uses an acrylic resin or a polycarbonate resin, and products generally marketed can be used.
Examples of the acrylic resin or polycarbonate resin include Polycaace (manufactured by Sumitomo Bakelite Co., Ltd.), Acrylite S (manufactured by Mitsubishi Rayon Co., Ltd.), and the like.
In order to ensure adhesion between the base material and the hydrophilic layer, a primer layer may be provided on the base material surface as necessary. As the primer layer, a commercially available product may be used as long as it has good wettability with the hydrophilic layer. Among these, an aqueous acrylic type is preferable.
Moreover, you may modify | reform the base-material surface. As the reforming method, known methods such as corona treatment, plasma treatment, flame treatment, and calcareous chemical conversion treatment can be used.

  For the purpose of improving the adhesion between the base material and the hydrophilic layer, one or both surfaces of the base material can be subjected to surface hydrophilization treatment by an oxidation method, a roughening method, or the like as desired. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. As a roughening method, it can also be mechanically roughened by sandblasting, brush polishing or the like.

[Hydrophilic layer]
The thickness of the hydrophilic layer is 50 nm to 1000 nm. Preferably it is 50-2000 nm, More preferably, it is 50-500 nm. If the thickness is small, sufficient hydrophilic effect may not be exhibited. Moreover, when the thickness is large, defects such as uneven drying may occur. The thickness of the hydrophilic layer can be adjusted by the solid content concentration of the hydrophilic composition, the coil diameter of the bar coater, and the like, and can be performed by a known method.

The center line average average height Ra of the hydrophilic layer is preferably 1 nm to 10 nm. More preferably, it is 2-5 micrometers.
When the surface roughness is increased, the wettability to water is improved and the hydrophilicity, antifogging property and antifouling property are improved. When the center line average average height Ra is in the above range, both good hydrophilicity and wear resistance can be achieved.
The centerline average height can be evaluated with an optical interference type roughness meter, and the centerline average height is defined as Ra.
When the hydrophilic layer becomes rough, interference fringes are generated on the surface of the coating film and visibility is lowered. If it is too smooth, the rub resistance may decrease.

The Tg (glass transition temperature) of the hydrophilic layer is preferably 40 ° C. to 150 ° C. from the viewpoint of film strength, and the elastic modulus of the hydrophilic layer is preferably 1 GPa to 7 GPa. Tg can be measured with a dynamic viscoelasticity measuring device, and the peak temperature of the loss elastic modulus is Tg. As the elastic modulus, the storage elastic modulus obtained by the same measurement as Tg can be used.
When Tg is low, there is a drawback that the surface of the coating film tends to stick and dust or the like adheres. If Tg is too high, the coating film tends to be brittle, which may adversely affect the abrasion resistance.

  The hydrophilic layer in the present invention preferably has a light transmittance of 85% or more. More preferably, it is 87% or more, and particularly preferably 90% or more. If the light transmittance is lower than 85%, the visibility is lowered. As means for further reducing the light transmittance, there are a method of reducing the thickness of the hydrophilic layer and a method of reducing the particle diameter or suppressing the addition amount when inorganic particles are used in combination. The light transmittance can be measured using ASTM D1033 method.

The hydrophilicity is generally measured by a water droplet contact angle. The surface of the goggles of the present invention has a contact angle of airborne water droplets measured at 20 ° C. of 15 ° or less, preferably 10 ° or less. It is preferable that the water droplet contact angle is 15 ° or less because excellent antifogging properties can be exhibited.
In the goggles of the present invention, the water droplet contact angle at 20 ° C. of the hydrophilic layer surface is 15 ° or less, and the light transmittance is 85% or more. A waterdrop contact angle at 20 ° C. of the hydrophilic layer surface of 15 ° or less and a light transmittance of 85% or more is preferable because goggles with excellent visibility can be obtained.

[Middle layer]
It is preferable to have an intermediate layer containing a compound having a hydrolyzable alkoxysilyl group between the base material and the hydrophilic layer. By providing the intermediate layer, the adhesion between the substrate and the hydrophilic layer can be improved, which is preferable.
When it has the said intermediate | middle layer between the said base material and the said hydrophilic layer, it is preferable that the thickness of an intermediate | middle layer is 10-100 nm. By making the thickness of the intermediate layer in the above range, sufficient adhesion can be ensured, and there is no problem such as occurrence of interference fringes in the coating film, which is excellent in visibility and preferable.
The intermediate layer in the goggles of the present invention is formed by coating a coating solution containing a compound having at least one hydrolyzable alkoxysilyl group, and is chemically bonded to the hydrophilic layer by a condensation reaction.

(Compound having hydrolyzable alkoxysilyl group)
The compound having a hydrolyzable alkoxysilyl group used in the intermediate layer of the goggles of the present invention alone or a hydrolyzate thereof has two or more reactive groups in the molecule, at least one of which is a substrate And at least one of the remaining is bonded to the hydrophilic polymer and / or metal alkoxide of the hydrophilic layer, thereby cross-linking the substrate and the hydrophilic layer. The compound having a hydrolyzable alkoxysilyl group may be added to the hydrophilic layer, but it is preferable to provide it as a separate layer between the substrate and the hydrophilic layer from the viewpoint of compatibility with hydrophilicity.

Although the specific example of the compound which has a hydrolysable alkoxy silyl group used for this invention is enumerated, it is not limited to these compounds.
N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminophenoxydimethylvinylsilane, aminophenyltrimethoxysilane, 3-amino Propyltriethoxysilane, bis (trimethoxysilylpropyl) amine, (p-chloromethyl) phenyltrimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 3-mercaptopropyltrimethoxysilane, (3-glycid Xylpropyl) -3-mercaptopropyldimethoxysilane, vinyltrichlorosilane, tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, and the like.

  Among these, tetramethoxysilane, methyltrimethoxysilane, tetraethoxysilane, and methyltriethoxysilane are preferable, and tetramethoxysilane and methyltrimethoxysilane are more preferable.

The intermediate layer can be formed by applying a coating solution containing the above coupling agent on a substrate, and then applying, heating, and drying a hydrophilic layer forming coating solution.
As a coating method, the same method as the hydrophilic layer coating described above can be applied. Further, in the heat drying, like the hydrophilic layer, the heating temperature is preferably 150 ° C. or less, and the heating time is preferably within 1 hour.
In addition to the coupling agent, the intermediate layer forming coating solution contains an appropriate solvent and other necessary components.
As a specific example of the solvent, the same solvent as that used for forming the hydrophilic layer can be used. More preferably, water, acetone, methyl ethyl ketone, methanol, ethanol, 1-propanol, chloroform, toluene, ethyl acetate, dioxane, ethylene glycol monomethyl ether, etc. are mentioned. The amount of the solvent used is preferably 50 to 99% by mass, more preferably 70 to 95% by mass with respect to the entire intermediate layer coating solution.
Specific examples of other necessary components include inorganic particles such as colloidal silica similar to those used for forming the hydrophilic layer, surfactants, and the like.

[Other layers]
The goggles of the present invention can be used by appropriately adding another layer as necessary. The layer structure added as needed is described below.

(Undercoat layer)
One or more undercoat layers can be provided between the substrate and the hydrophilic layer. As the material for the undercoat layer, a hydrophilic resin or water-dispersible latex can be used.
Examples of hydrophilic resins include polyvinyl alcohol (PVA), cellulose resins [methyl cellulose (MC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.], chitins, chitosans, starch, and ether bonds. Examples thereof include resins [polyethylene oxide (PEO), polyethylene glycol (PEG), polyvinyl ether (PVE), etc.], resins having a carbamoyl group [polyacrylamide (PAAM), polyvinyl pyrrolidone (PVP), etc.], and the like. Moreover, the polyacrylic acid salt which has a carboxyl group, maleic acid resin, alginate, gelatins, etc. can also be mentioned.
Among these, at least one selected from polyvinyl alcohol resins, cellulose resins, resins having an ether bond, resins having a carbamoyl group, resins having a carboxyl group, and gelatins is preferable, and in particular, polyvinyl alcohol (PVA) Of these, gelatin resins are preferred.

Examples of the water-dispersible latex include acrylic latex, polyester latex, NBR resin, polyurethane latex, polyvinyl acetate latex, SBR resin, polyamide latex and the like. Among these, acrylic latex is preferable.
The above hydrophilic resin and water-dispersible latex may be used alone or in combination of two or more, or a hydrophilic resin and a water-dispersible latex may be used in combination.
Moreover, you may use the crosslinking agent which bridge | crosslinks the said hydrophilic resin and water-dispersible latex.
As a cross-linking agent applicable to the present invention, a cross-linking agent that forms a cross-link by known heat can be used. General thermal crosslinking agents include those described in “Crosslinking agent handbook” by Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha (1981). The number of functional groups of the crosslinking agent used in the present invention is not particularly limited as long as it is 2 or more and can be effectively crosslinked with a hydrophilic resin or water-dispersible latex. Specific examples of the thermal crosslinking agent include polycarboxylic acids such as polyacrylic acid, amine compounds such as polyethyleneimine, ethylene or propylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene ethylene glycol diglycidyl ether, polyethylene or Polyepoxy compounds such as polypropylene glycol glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyaldehyde compounds such as glyoxal and terephthalaldehyde, tri Range isocyanate, hexamethylene diisocyanate, diphenylmethane isocyanate, xylylene Polyisocyanate compounds such as isocyanate, polymethylene polyphenyl isocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol / tolylene diisocyanate addition reaction product, block polyisocyanate Examples thereof include compounds, silane coupling agents such as tetraalkoxysilane, metal cross-linking agents such as acetylacetonate of aluminum, copper and iron (III), and polymethylol compounds such as trimethylolmelamine and pentaerythritol. Among these thermal cross-linking agents, a water-soluble cross-linking agent is preferable from the viewpoint of easy preparation of the coating solution and prevention of a decrease in hydrophilicity of the produced hydrophilic layer.
Wherein the hydrophilic resin and / or water-dispersible latex total amount in the undercoat layer is preferably from 0.01 to 20 g / m ^2, 0.1 to 10 g / m ² is more preferable.

In the present invention, the intermediate layer forming composition containing a compound having a hydrolyzable alkoxysilyl group having a thickness of 10 to 100 nm between the acrylic resin or polycarbonate resin substrate and the hydrophilic layer is coated. It is preferable to provide an intermediate layer formed as described above.
Among the compounds having a hydrolyzable alkoxysilyl group, preferred are tetramethoxysilane, methyltrimethoxysilane, tetraethoxysilane, and methyltriethoxysilane, and particularly preferred are tetramethoxysilane and methyltrimethoxysilane.

(Protective layer)
A protective layer may be provided on the hydrophilic layer. The protective layer has a function of preventing damage to the hydrophilic surface during handling, transportation, storage, and the like, and deterioration of hydrophilicity due to adhesion of dirt substances. As the protective layer, the hydrophilic polymer layer used in the release layer can be used.

[Surface free energy]
The degree of hydrophilicity of the hydrophilic layer surface is generally measured by a water droplet contact angle. However, on a very hydrophilic surface such as the present invention, the water droplet contact angle may be 10 ° or less, and even 5 ° or less, and there is a limit to the mutual comparison of the hydrophilicity. . On the other hand, as a method for evaluating the degree of hydrophilicity of the solid surface in more detail, there is a measurement of surface free energy. Various methods have been proposed. In the present invention, as an example, the surface free energy was measured using the Zisman plot method. Specifically, using the property that an aqueous solution of an inorganic electrolyte such as magnesium chloride increases in surface tension with the concentration, after measuring the contact angle in the air at room temperature using the aqueous solution, the horizontal axis indicates the surface of the aqueous solution. Take the value obtained by converting the contact angle into cos θ on the vertical axis and plot the points of aqueous solutions of various concentrations to obtain a linear relationship, and the surface tension when cos θ = 1, that is, the contact angle = 0 °, It is a measurement method defined as the surface free energy of a solid. The surface tension of water is 72 mN / m, and it can be said that the higher the surface free energy value, the higher the hydrophilicity.
A hydrophilic layer having a surface free energy measured by such a method in the range of 70 mN / m to 95 mN / m, preferably 72 mN / m to 93 mN / m, more preferably 75 mN / m to 90 mN / m, Excellent performance and good performance.

[Production of goggles]
The goggles in the present invention refer to tools that are worn on the face to protect the eyes during sports or processing operations. The main goggles include swimming, skiing, military, survival games, motorcycles, and various types of work.
(Agitation of hydrophilic composition)
It is preferable to stir the hydrophilic composition before applying it to the substrate for the purpose of improving the hydrolysis / condensation rate of the alkoxysilyl group. The stirring time is preferably 10 minutes to 10 hours, more preferably 30 to 2 hours.
More preferably, the catalyst is added to a composition containing a hydrophilic polymer and stirred for the above time.

  A hydrophilic layer can be formed by applying the hydrophilic composition on goggles having an appropriate base material, heating and drying. The heating temperature and heating time for forming the hydrophilic layer are not particularly limited as long as the solvent and the time in which the solvent in the sol solution is removed and a strong film can be formed, but from the viewpoint of improving the production suitability and the condensation rate. The heating temperature is preferably 20 to 200 ° C, more preferably 60 to 150 ° C. The heating time is preferably 10 seconds to 2 hours, more preferably 1 minute to 1 hour.

  The goggles can be produced by a known application method, and there is no particular limitation. For example, spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, film applicator method, screen printing method Methods such as bar coater method, brush coating, and sponge coating can be applied.

  The said coating method can apply | coat to the base-material surface by means, such as brush coating, spray coating, roller coating, dip coating, for example. The coating amount is not particularly limited, but generally it is considered that a range of about 0.1 to 500 μm is sufficient. Conditions for drying the coating film can be selected according to the type of the hydrophilic composition. For example, when an aqueous coating material containing a base resin containing a hydrolyzable silyl group, a hydroxyl group and an epoxy group as essential functional group components and a metal chelate compound is used, it is about 1 to 72 hours at room temperature or when heated. Drying can be performed at 40 ° C. to 200 ° C. for about 1 minute to 24 hours.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In addition, with a part means a mass part.

[Example 1]
Use a bar coater (coil diameter 0.08Φ) on the surface of a polycarbonate resin substrate (Sumitomo Bakelite Polycarbonate ACK100 5mm thick) that has been thoroughly dried after washing with a neutral detergent so that the film thickness after drying is 10nm. The intermediate layer-forming composition was coated and dried by heating at 100 ° C. for 10 minutes.
Subsequently, the following hydrophilic coating solution (1) was coated with a bar coater (coil diameter 0.08Φ) so that the film thickness after drying was 100 nm, and heat-dried at 100 ° C. for 10 minutes.
The hydrophilic processing member which has the hydrophilic layer film thickness of Table 1 was obtained. The hydrophilic layer thickness of the hydrophilic treatment member was confirmed by observing the cross section of the member with a scanning electron microscope.

<Hydrophilic layer coating solution (1)>
・ 500g of the following sol-gel preparation (1)
・ 30 g of 5% by weight aqueous solution of the following anionic surfactant
・ Purified water 450g

<Sol-gel preparation liquid (1)>
The mixture was prepared by mixing 5 g of a hydrophilic polymer (formula-1) in 200 g of ethyl alcohol, 10 g of acetylacetone, 10 g of tetraethyl orthotitanate and 100 g of purified water and stirring at room temperature for 2 hours.

<Adjustment of intermediate layer forming composition>
10 parts of tetramethoxysilane, 10 parts of methyltrimethoxysilane and titanium acetylacetonate were added in an amount equivalent to the number of moles of the alkoxysilyl group of the alkoxysilyl compound, 900 parts of distilled water and 1000 parts of ethanol were added, and 20 ° C. Was stirred for 30 minutes to obtain an intermediate layer forming composition.

[Examples 2-9, 18-22 Comparative Examples 1-7, 10-13]
Examples 2 to 9 and 18 to 22 Comparative Examples 1 to 7 were the same as Example 1 except that the base material, hydrophilic polymer, intermediate layer thickness, and hydrophilic layer thickness shown in Table 1 were changed. 10-13 hydrophilic members were obtained.

[Examples 10, 13 to 17, Comparative Example 8]
The hydrophilic layer coating solution (1) used in Example 1 was changed to the hydrophilic layer coating solution (2), and the base material, hydrophilic polymer, intermediate layer thickness, hydrophilic layer membrane described in Table 1 were used. The hydrophilic members of Examples 10, 13 to 17, and Comparative Example 8 were obtained in the same manner as Example 1 except that the thickness was changed.

<Hydrophilic layer coating solution (2)>
-Colloidal silica dispersion 20% by weight aqueous solution 100g
(Snowtex C, Nissan Chemical Industries, Ltd., average particle size 10-20 nm)
・ 500g of the above sol-gel preparation
・ 30 g of 5% by weight aqueous solution of the above anionic surfactant
・ Purified water 450g

<Sol-gel preparation liquid (2)>
In 200 g of ethyl alcohol, 10 g of acetylacetone, 10 g of tetraethyl orthotitanate, and 100 g of purified water, 8 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 g of a hydrophilic polymer (formula-1) are mixed, and at room temperature for 2 hours. Stir to prepare.

[Examples 11 and 12]
The hydrophilic layer coating solution (1) used in Example 1 was changed to the hydrophilic layer coating solution (3), and the base material, hydrophilic polymer, intermediate layer thickness, hydrophilic layer membrane described in Table 1 were used. The hydrophilic members of Examples 11 and 12 were obtained in the same manner as Example 1 except that the thickness was changed.

<Hydrophilic layer coating solution (3)>
-Colloidal silica dispersion 40% by weight aqueous solution 30g
(Snowtex ZL, Nissan Chemical Industries, Ltd., average particle size 70-100 nm)
・ 500g of the above sol-gel preparation (2)
・ 30 g of 5% by weight aqueous solution of the above anionic surfactant
・ Purified water 450g

[Comparative Example 9]
The hydrophilic layer coating solution (1) used in Example 1 was changed to the hydrophilic layer coating solution (4), and the base material, hydrophilic polymer, intermediate layer thickness, and hydrophilic layer membrane described in Table 1 were used. A hydrophilic member of Comparative Example 9 was obtained in the same manner as in Example 1 except that the thickness was changed.

<Hydrophilic layer coating solution (4)>
-Colloidal silica dispersion 40% by weight aqueous solution 30g
(MP2040, Nissan Chemical Industries, Ltd., average particle size 250 nm)-500 g of the sol-gel preparation (2)
・ 30 g of 5% by weight aqueous solution of the above anionic surfactant
・ Purified water 450g

(Synthesis of hydrophilic polymer (Formula-1))
A 500 ml three-necked flask is charged with 21.0 g of acrylamide, 4.3 g of acrylamide-3- (ethoxysilyl) propyl, and 260 g of 1-methoxy-2-propanol, and 2,2′-azobis (2-methyl) under a nitrogen stream at 80 ° C. 1.9 g of dimethyl propionate) was added. The mixture was kept at the same temperature with stirring for 6 hours, and then cooled to room temperature. Thereafter, the reaction solution was poured into 2 liters of acetone, and the precipitated solid was collected by filtration. The obtained solid was washed with acetone to obtain a hydrophilic polymer (Formula-1). The mass after drying was 22.1 g. The mass average molecular weight of the polymer determined by GPC (polyethylene oxide standard) was 20,500.
Hydrophilic polymers (Formula-2) to (Formula-6) were also synthesized by the same method.

(Synthesis of hydrophilic polymer (formula-7))
In a three-necked flask, add 25 g of acrylamide, 3.5 g of 3-mercaptopropyltrimethoxysilane, and 51.3 g of dimethylformamide, and heat to 65 ° C. in a nitrogen stream to obtain 2,2′-azobis (2,4-dimethylvaleronitrile). 0.25 g was added to start the reaction. After stirring for 6 hours, the mixture was returned to room temperature and poured into 1.5 L of ethyl acetate, and a solid precipitated. Thereafter, filtration was performed, and the product was sufficiently washed with ethyl acetate and dried (yield 21 g). It was confirmed by GPC (polystyrene standard) that the polymer had a mass average molecular weight of 13000. The viscosity of the 5% aqueous solution was 2.5 mPa · s, and the functional group density of the hydrophilic group was 13.4 meq / g.
The hydrophilic polymers (Formula-8) and (Formula-9) were synthesized in the same manner.

  The hydrophilic polymers used in Examples and Comparative Examples are shown below.

[Evaluation method]
Contact angle to water: The contact angle of the hydrophilic coating film surface was determined using ultrapure water using a contact angle meter DropMaster500 manufactured by Kyowa Interface Science Co., Ltd.
Transmittance: Measured according to ASTM D1003.
Repeated rubbing property: Nonwoven fabric (BEMCOT manufactured by Asahi Kasei Co., Ltd.) moistened with distilled water was repeatedly rubbed 5000 times with a surface pressure of 500 gf / cm ² and a stroke of 30 mm on the surface of the obtained member. The product was defective and scratches could not be confirmed, but the contact angle with water was 20 ° or more. The contact angle with water was 15 ° or less and no scratch was confirmed.
Anti-fogging property: 40 to 50 ° C. humidified steam was applied to the surface of the obtained member, and the case where clouding occurred within 30 seconds was poor, and the case where clouding did not occur for 30 seconds or more was considered excellent.
Temperature cycle property: The obtained member was allowed to stand for 2 hours in an environment of -40 ° C and then left for 2 hours in an environment of 85 ° C and 20% RH. This was defined as one cycle, and after 20 cycles, the coating film surface was observed and evaluated according to the following rank.
Excellent: Observed visually and with an optical microscope (400 times), no change from before the test.
Good: Visually unchanged from before the test, but observed with an optical microscope and partially cracked.
Defect: A crack was observed on the surface of the coating film visually and with an optical microscope.

  The results are shown in Table 1.

Claims (5)

  A goggle having a hydrophilic layer containing a hydrophilic polymer on a base of an acrylic resin or a polycarbonate resin, wherein the hydrophilic polymer has at least one hydrophilic group and a hydrolyzable alkoxysilyl group. A goggle having a hydrophilic layer thickness of 50 nm to 1000 nm, a water droplet contact angle at 20 ° C. of the hydrophilic layer surface of 15 ° or less, and a light transmittance of 85% or more.   The goggles according to claim 1, further comprising an intermediate layer including a compound having a hydrolyzable alkoxysilyl group and having a thickness of 10 to 100 nm between the base material and the hydrophilic layer. The hydrophilic polymer (I) having a structure represented by the following general formulas (I-1) and (I-2), represented by the general formulas (II-1) and (II-2) The hydrophilic polymer (II) containing a structure or the hydrophilic polymer (III) containing a structure represented by the general formulas (III-1) and (III-2), Goggles according to 2.

In general formulas (I-1) and (I-2), R ^{101 to} R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 to 3, and L ¹⁰¹ and L ¹⁰² each independently represent a single bond or a polyvalent organic linking group. x and y represent a composition ratio, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ¹⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.

In general formulas (II-1) and (II-2), R ^{201 to} R ²⁰⁵ each independently represents a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to 3, and L ²⁰¹ and L ²⁰² each independently represent a single bond or a polyvalent organic linking group. A ²⁰¹ is _{-OH, -OR a, -COR a,} -CO 2 R e, -CON (R a) (R b), - N (R a) (R b), - NHCOR d, -NHCO 2 R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.

In formulas (III-1) and ^(III-2), each represent R 301 ^{to R 311} independently represent a hydrogen atom or a hydrocarbon group. r represents an integer of 1 to 3, and L ^{301 to} L ³⁰³ each independently represent a single bond or a polyvalent organic linking group. x and y represent a composition ratio, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ³⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , -OCON (R _a ) (R _b ), -NHCON (R _a ) (R _b ), -SO ₃ R _e , -OSO ₃ R _e , -SO ₂ R _d , -NHSO ₂ R _d , -SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. The hydrophilic group or ^{A 101} is -CONH _2, goggles according to claim 1 is at least one selected from -COOH and -OH. The hydrolyzable alkoxysilyl group, a _{-Si (OCH 3) n, -Si} (OC 2 H 5) n and _{-Si (OC 3 H 7) n} ( n represents an integer of 2-3) The goggles according to any one of claims 1 to 4, which have at least one selected alkoxysilyl group.