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WO2013039252A1 - Elément hydrophile et son procédé de fabrication - Google Patents

Elément hydrophile et son procédé de fabrication Download PDF

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Publication number
WO2013039252A1
WO2013039252A1 PCT/JP2012/073962 JP2012073962W WO2013039252A1 WO 2013039252 A1 WO2013039252 A1 WO 2013039252A1 JP 2012073962 W JP2012073962 W JP 2012073962W WO 2013039252 A1 WO2013039252 A1 WO 2013039252A1
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WO
WIPO (PCT)
Prior art keywords
ink
group
hydrophilic
polymer
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/073962
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English (en)
Inventor
Seishi Kasai
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Fujifilm Corp
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Fujifilm Corp
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Filing date
Publication date
Priority claimed from JP2011203055A external-priority patent/JP2013063561A/ja
Priority claimed from JP2011203056A external-priority patent/JP2013063562A/ja
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of WO2013039252A1 publication Critical patent/WO2013039252A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/34—Applying different liquids or other fluent materials simultaneously
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2490/00—Intermixed layers
    • B05D2490/50—Intermixed layers compositions varying with a gradient perpendicular to the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures

Definitions

  • the present invention relates to a hydrophilic member.
  • the invention relates to a hydrophilic member having good adhesion between a base material of every kind and a layer constituting the hydrophilic member and capable of giving a hydrophilic surface with excellent waterproof properties, anti-fogging properties, antifouling properties, and weather resistance to a surface of the base material.
  • Products and members having a resin film surface are used in broad fields, and after being processed and given a function according to a purpose, they are used.
  • their surfaces exhibit hydrophobicity or lipophilicity due to original characteristics of the resin.
  • oils or the like attach as pollutants onto those surfaces, they cannot be easily removed, and when accumulated, they often remarkably lowered functions and characteristics of products and members having those surfaces.
  • hydrophilic members having a surface hydrophilic function on a base material of every kind.
  • JP-A-2008-284715 discloses a hydrophilic member comprising a polyethylene terephthalate substrate having thereon an undercoat layer formed of an aqueous resin composition and a hydrophilic layer formed of a hydrophilic polymer containing a hydrolyzable silyl group at a main chain end or side chain thereof on the undercoat layer.
  • JP-A-2011-73359 discloses a hydrophilic member comprising a polyethylene terephthalate substrate having thereon a hydrophobic undercoat layer formed of a hydrophobic polymer composition and a hydrophilic layer formed of a hydrophilic polymer containing a hydrolyzable silyl group at a main chain end or side chain thereof on the undercoat layer.
  • JP-A-2001-335690 discloses a hydrophilic member having a self-gradient function in which an organosiloxane composition composed of an aqueous resin and an aqueous solution of an organosiloxane is coated on a base material, and the organosiloxane is unevenly distributed on a coating surface due to a difference of surface energy.
  • the hydrophilic member disclosed in JP-A-2008-284715 it is described that the disclosed hydrophilic member has excellent adhesion to a base material made of an inorganic material such as glass and metals and has excellent alkali resistance. Then, it is described that the subject member is formed using an aqueous epoxy resin as an adhesive layer on a PET support, but it is not described that the subject member has a composition gradient layer.
  • JP-A-2011-73359 discloses a hydrophilic member having a double-layer structure of an undercoat layer formed on a substrate and a hydrophilic layer formed on the undercoat layer. However, it is not described that the subject member has a composition gradient layer.
  • JP-A-2001-335690 discloses a hydrophilic member utilizing a material with low surface energy.
  • the hydrophilicity of the surface is lowered due to the presence of the material with low surface energy.
  • the disclosed hydrophilic member encounters such a problem that hydrophilicity, anti-fogging properties, and antifouling properties cannot be achieved.
  • the hydrophilic members of the related art were obtained by laminating, on a base material, a composition containing a hydrophilic material and a material having good affinity with the base material (for example, a hybrid material of a silica sol-gel and an organic polymer), or providing, as an adhesive layer, a material having adhesiveness to a hydrophilic material and a base material to some extent on the base material and laminating the hydrophilic material on the adhesive layer.
  • a base material for example, a hybrid material of a silica sol-gel and an organic polymer
  • hydrophilic members of the related art In view of the fact that in the hydrophilic members of the related art, an interface between layers formed of a different material from each other is present, or the hydrophilicity on the member surface is not sufficient, it could be not always said that the hydrophilic members of the related art satisfy both performances of adhesion and hydrophilicity required for hydrophilic members in recent years.
  • the invention has been made, and its object is to provide a hydrophilic member having a composition gradient structure, which has good adhesion to a base material of every kind and is capable of giving a hydrophilic surface with excellent waterproof properties, anti-fogging properties, antifouling properties, and weather resistance to a surface of the base material.
  • a hydrophilic member comprising a base material and a layer containing the following hydrophilic material (1) and an oligomer or polymer (2), wherein the layer is a composition gradient layer in which a composition of (1) and (2) continuously changes in a thickness direction of the layer in such a manner that a ratio of (1) becomes large, whereas a ratio of (2) becomes small, from the nearest side to the base material toward the farthest side to the base material.
  • a hydrophilic material containing a hydrolyzable silyl group-containing hydrophilic polymer the polymer having at least one hydrolyzable silyl group represented by the following formula (a) at a main chain end or side chain of a molecule thereof and having at least one hydrophilic group in the molecule.
  • each of R 10 and R 11 independently represents a hydrogen atom or a hydrocarbon group; and a represents an integer of from 1 to 3.
  • the oligomer or polymer (2) is different from the hydrophilic material (1).
  • hydrophilic member as set forth above in any one of [1] to [4], wherein the hydrolyzable silyl group-containing hydrophilic polymer is any of a hydrophilic polymer (I) containing a structure represented by the following formula (1-1) and a structure represented by the following formula (1-2), a hydrophilic polymer (II) containing a structure represented by the following formula (II- 1) and a structure represented by the following formula (II-2), or a hydrophilic polymer (III) containing a structure represented by the following formula (III-l) and a structure represented by the following formula ( ⁇ -2).
  • each of R 101 to R 108 independently represents a hydrogen atom or a hydrocarbon group; p represents an integer of from 1 to 3; each of L 101 and L 102 independently represents a single bond or a divalent organic connecting group; each of x and y represents a composition ratio, in which x represents a number satisfying a relation of 0 ⁇ x ⁇ 100, and y represents a number satisfying a relation of 0 ⁇ y ⁇ 100;
  • a 101 represents -OH, -ORa, -COR a , -C0 2 Re, -CON(RaXRb), -N(R a )(R b ), -NHCORo, -NHC0 2 R a , -OCON(R a )(R b ), -NHCON(RaXRb), -S0 3 Re, -OS0 3 Re, -S0 2 Rd, -NHS0 2 Rd, -NHS0 2 Rd,
  • each of R to R independently represents a hydrogen atom or a hydrocarbon group; q represents an integer of from 1 to 3; each of L 201 and L independently represents a single bond or a divalent organic connecting group; A represents -OH, -OR a , -COR a , -C0 2 Re, -CON(R a )(R b ), -N(R a )(R b ), -NHCOR d , -NHC0 2 R a , -OCON(R a )(R b ), -NHCON(R a )(R b ), -S0 3 Re, -OS0 3 Re, -S0 2 R d , -NHS0 2 R d , -S0 2 N(R a )(R b ), -N(R a )(R b )(Rc), -N(R
  • each of R 301 to R 3 " independently represents a hydrogen atom or a hydrocarbon group; r represents an integer of from 1 to 3; each of L 301 to
  • L independently represents a single bond or a divalent organic connecting group; each of x and y represents a composition ratio, in which x represents a number satisfying a relation of 0 ⁇ x ⁇ 100, and y represents a number satisfying a relation of 0 ⁇ y ⁇ 100;
  • a 301 represents -OH, -ORa, -CORa, -C0 2 Re, -CON(R a )(R b ), -N(R a )(R b ), -NHCOR d , -NHC0 2 R a , -OCON(R a )(R b ), -NHCON(R a )(R b ), -S0 3 Re, -OS0 3 Re, -S0 2 R d , -NHS0 2 R d , -S0 2 N(R a )(R b ), -N(R a )(R b )(R
  • hydrophilic member as set forth above in any one of [1] to [5], wherein a structural unit having a hydrophilic group in the hydrolyzable silyl group-containing hydrophilic polymer is contained in an amount of 30 % by mole or more of the whole of the polymer.
  • hydrophilic member as set forth above in any one of [1] to [6], wherein the hydrophilic material (1) further contains colloidal silica.
  • hydrophilic member as set forth above in any one of [2] to [7], wherein the active energy ray-cured oligomer or polymer is an oligomer or polymer obtained by polymerizing a monomer containing at least one member selected from an N-vinyl compound and an acrylate compound.
  • each of RAI to RA 3 independently represents an alkylene group, an arylene group, or a biarylene group; and each of RA 4 to RA 6 independently represents a hydrogen atom, an alkyl group, an aryl group, or a hetero aryl group.
  • At least an ink composition containing the hydrophilic material (1) and an ink composition containing the resin material are used as the at least two kinds of ink compositions, and
  • the inkjet method uses at least a first inkjet head and a second inkjet head, and wherein the method includes
  • the ratio is determined such that a ratio of the first ink becomes large, whereas a ratio of the second ink becomes small, in a thickness direction of the plural layers from the nearest side to the base material toward the farthest side to the base material.
  • At least an ink composition containing the hydrophilic material (1) and an ink composition containing the resin material are used as the at least two kinds of ink compositions, and
  • the inkjet method uses a plurality of inkjet heads, and wherein the method includes a step of supplying a plurality of mixed inks which are a mixture of a first ink containing the ink composition containing the hydrophilic material (1) and a second ink containing the ink composition containing the resin material, and which are different in a mixing ratio from each other, into the plurality of inkjet heads, respectively,
  • hydrophilic member as set forth above in any one of [1] to [11], which is a hydrophilic member formed using, as the at least two kinds of ink compositions, at least an ink composition containing the hydrophilic material (1) and an ink composition containing a resin material containing at least one member selected from an active energy ray-curable monomer and an oligomer or polymer by an inkjet method, wherein
  • the inkjet method uses at least a first inkjet head and a second inkjet head, and wherein the method includes
  • the ratio is determined such that a ratio of the first ink becomes large, whereas a ratio of the second ink becomes small, in a thickness direction of the plural layers from the nearest side to the base material toward the farthest side to the base material.
  • hydrophilic member as set forth above in any one of [1] to [11], which is a hydrophilic member formed using, as the at least two kinds of ink compositions, at least an ink composition containing the hydrophilic material (1) and an ink composition containing a resin material containing at least one member selected from an active energy ray-curable monomer and an oligomer or polymer by an inkj et method, wherein
  • the inkjet method uses a plurality of inkjet heads, and wherein the method includes a step of supplying a plurality of mixed inks which are a mixture of a first ink containing the ink composition containing the hydrophilic material (1) and a second ink containing the ink composition containing the resin material, and which are different in a mixing ratio from each other, into the plurality of inkjet heads, respectively,
  • the invention has successfully obtained a hydrophilic member in which a distinct interface of a different kind does not exist, and both hydrophilicity (on the farthest side to the base material) and adhesion to the base material (on the nearest side to the base material) are made compatible with each other on a high level.
  • a hydrophilic member having a composition gradient layer which has good adhesion to a base material of every kind and is capable of giving a hydrophilic surface with excellent waterproof properties, anti-fogging properties, antifouling properties, and weather resistance to a surface of the base material, and a forming method of the same are provided.
  • Fig. 1 is a schematic view of a hydrophilic member including a composition gradient layer.
  • Fig. 2 is a schematic view of a hydrophilic member including a composition gradient layer.
  • Fig. 3 is an overall configuration view of a composition gradient layer fabrication apparatus.
  • Fig. 4 is a diagrammatic view of an image formation section of a composition gradient layer fabrication apparatus.
  • Figs. 5A, 5B, 5C, 5D and 5E are each a view for explaining the formation of a composition gradient layer by an image formation mixing method.
  • Figs. 6A, 6B and 6C are each a view for explaining other embodiment of an image formation mixing method.
  • Fig. 7 is an overall configuration view of a composition gradient layer fabrication apparatus according to an embodiment of an ink mixing method.
  • Figs. 8 A, 8B and 8C are each a view for explaining the formation of a composition gradient layer by an ink mixing method.
  • Figs. 9A, 9B, 9C and 9D are each a view for explaining deposition positions of respective inks in an image formation mixing method.
  • the invention is concerned with a hydrophilic member comprising a base material and a layer containing the following hydrophilic material (1) and an oligomer or polymer (2), wherein the layer is a composition gradient layer in which a composition of (1) and (2) continuously changes in a thickness direction of the layer in such a manner that a ratio of (1) becomes large, whereas a ratio of (2) becomes small, from the nearest side to the base material toward the farthest side to the base material.
  • hydrophilic material containing a hydrolyzable silyl group-containing hydrophilic polymer (hereinafter also referred to simply as "hydrophilic polymer”), the polymer having at least one hydrolyzable silyl group represented by the following formula (a) at a main chain end or side chain of a molecule thereof and having at least one hydrophilic group in the molecule.
  • hydrophilic polymer the polymer having at least one hydrolyzable silyl group represented by the following formula (a) at a main chain end or side chain of a molecule thereof and having at least one hydrophilic group in the molecule.
  • each of R 10 and R 11 independently represents a hydrogen atom or a hydrocarbon group; and a represents an integer of from 1 to 3.
  • the oligomer or polymer (2) is different from the hydrophilic material (1).
  • Hydrophilic material [Hydrophilic material]
  • the hydrophilic material in the invention contains a hydrolyzable silyl group-containing hydrophilic polymer.
  • the hydrophilic polymer in the invention has at least one hydrolyzable silyl group represented by the following formula (a) at a main chain end or side chain of a molecule thereof and has at least one hydrophilic group in the molecule.
  • each of R 10 and R 11 independently represents a hydrogen atom or a hydrocarbon group; and a represents an integer of from 1 to 3.
  • each R 10 or R 1 1 may be the same as or different from every other R 10 or R 11 .
  • hydrolyzable silyl group of the foregoing hydrolyzable silyl group-containing hydrophilic polymer is preferably bonded to a carbon atom at the main chain or side chain of the polymer.
  • R 1 1 is preferably a hydrogen group or an alkyl group
  • R 10 is preferably a hydrogen atom or a monovalent hydrocarbon group selected among an alkyl group, an aryl group, and an aralkyl group.
  • R 11 represents an alkyl group
  • an alkyl group having a carbon number of from 1 to 10 is preferable.
  • R 10 represents an alkyl group
  • an alkyl group having a carbon number of from 1 to 10 is preferable
  • an aryl group having a carbon number of from 6 to 25 is preferable
  • an aralkyl group having a carbon number of from 7 to 12 is preferable.
  • the hydrophilic polymer which is used in the invention has a hydrophilic group.
  • the hydrophilic group include -NHCOR, -NHC0 2 R, -NHCONR 2 , -CONH 2 , -NR 2 , -CONR 2 , -OCONR 2 , -COR, -OH, -OR, -OM, -C0 2 M, -C0 2 R, -S0 3 M, -OS0 3 M, -S0 2 R, -NHS0 2 R, -S0 2 NR 2 , -P0 3 M, -OP0 3 M, -(CH 2 CH 2 0) n H, -(CH 2 CH 2 0) n CH 3 , and -NR 3 Z[.
  • each R may be the same as or different from every other R, and R represents a hydrogen atom, an alkyl group (preferably a linear or branched alkyl group or cycloalkyl group having a carbon number of from 1 to 18), an aryl group, or an aralkyl group; M represents a hydrogen atom, an alkyl group, an alkali metal, an alkaline earth metal, or an onium; n represents an integer (preferably an integer of from 1 to 100); and Zi represents a halogen ion.
  • R represents a hydrogen atom, an alkyl group (preferably a linear or branched alkyl group or cycloalkyl group having a carbon number of from 1 to 18), an aryl group, or an aralkyl group
  • M represents a hydrogen atom, an alkyl group, an alkali metal, an alkaline earth metal, or an onium
  • n represents an integer (preferably an integer of from 1 to 100)
  • Zi represents a halogen
  • R may further have a substituent, and examples of the substituent include the same groups as those exemplified as a substituent which can be introduced in the case where each of R 101 and R 102 in a structure represented by a formula (1-1) as described later is an alkyl group.
  • R examples 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, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, an isopentyl group, a neopentyl group, a 1-methylbutyl group, an isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group.
  • examples of M include a hydrogen atom; an alkali metal such as lithium, sodium, and potassium; an alkaline earth metal such as calcium and barium; and an onium such as ammonium, iodonium, and sulfonium.
  • the hydrophilic group is preferably -OH, -NHCOCH 3 , -CONH 2 , -CON(CH 3 ) 2 , -COOH, -S0 3 " NMe 4 + , -S0 3 K + , -(CH 2 CH 2 0) n H, a morpholyl group, or the like; more preferably -OH, -NHCOCH 3 , -CONH 2 , -CON(CH 3 ) 2 , -COOH, -S0 3 " K + , or -(CH 2 CH 2 0) n H; and still more preferably -OH, -COOH, or -CONH 2 .
  • the hydrophilic polymer which is used in the invention is preferably a polymer having a group capable causing bonding with a metal alkoxide compound of a metal selected among Si, Ti, Zr, and Al as described later by means of a catalytic action or the like.
  • Examples of the group capable causing bonding with a metal alkoxide compound by means of a Catalytic action include, in addition to the hydrolyzable silyl group represented by the foregoing formula (a), reactive groups such as a carboxyl group, an alkali metal salt of a carboxyl group, a carboxylic acid anhydride group, an amino group, a hydroxyl group, an epoxy group, a methylol group, a mercapto group, an isocyanato group, a blocked isocyanato group, an alkoxy titanate group, an alkoxy aluminate group, an alkoxy zirconate group, an ethylenically unsaturated group, an ester group, and a tetrazole group.
  • reactive groups such as a carboxyl group, an alkali metal salt of a carboxyl group, a carboxylic acid anhydride group, an amino group, a hydroxyl group, an epoxy group, a methylol group
  • a polymer structure having a hydrophilic group and a group capable causing bonding with a metal alkoxide compound by means of a catalytic action include polymers having an ethylenically unsaturated group (for example, an acrylate group, a methacrylate group, an itaconic acid group, a crotonic acid group, a cinnamic acid group, a styrene group, a vinyl group, an allyl group, a vinyl ether group, a vinyl ester group, etc.) vinyl-polymerized therewith, polyesters, polyamides, condensation polymerized polymers such as polyamic acids, and addition polymerized polymers such as polyurethanes.
  • natural cyclic polymer structures such as cellulose, amylose, and chitosan can also be preferably exemplified.
  • the hydrophilic polymer in the invention preferably contains a structural unit having a hydrophilic group.
  • the structural unit having a hydrophilic group is contained in an amount of preferably 30 % by mole or more, and more preferably from 40 to 95 % by mole of the whole of the polymer.
  • the structural unit having a hydrophilic group which is contained in the foregoing hydrophilic polymer, is not particularly limited, for example, a structural unit represented by the following formula (1-2), ( ⁇ -2) or ( ⁇ -2) can be used.
  • the hydrophilic polymer in the invention is preferably any of a hydrophilic polymer
  • each of R 101 to R 108 independently represents a hydrogen atom or a hydrocarbon group; p represents an integer of from 1 to 3; each of L 101 and L 102 independently represents a single bond or a divalent organic connecting group; each of x and y represents a composition ratio, in which x represents a number satisfying a relation of 0 ⁇ x ⁇ 100, and y represents a number satisfying a relation of 0 ⁇ y ⁇ 100; A 101 represents
  • R b , and Rc independently represents a hydrogen atom or a linear or branched alkyl group or cycloalkyl group;
  • R d represents a linear or branched alkyl group or cycloalkyl group;
  • each of Re and Rf independently represents a hydrogen atom, a linear or branched alkyl group or cycloalkyl group, an alkali metal, an alkaline earth metal, or an onium;
  • R g represents a halogen ion, an inorganic anion, or an organic anion.
  • each of R to R independently represents a hydrogen atom or a hydrocarbon group; q represents an integer of from 1 to 3; each of L 201 and L 202 independently represents a single bond or a divalent organic connecting group;
  • a 201 represents -OH, -OR a , -COR a , -C0 2 Re, -CON(R a )(R b ), -N(R a )(R perennial), -NHCOR d , -NHC0 2 R a , -OCON(RaXRb), -NHCON(RaXRb), -S0 3 Re, -OS0 3 Re, -S0 2 Ro, -NHS0 2 Rd, -S0 2 N(R a )(R b ), -N(R a )(R b )(Rc), -N(R a )(R b )(R c), -N(R a )(R
  • R b , and R c independently represents a hydrogen atom or a linear or branched alkyl group or cycloalkyl group;
  • R d represents a linear or branched alkyl group or cycloalkyl group;
  • each of Re and Rf independently represents a hydrogen atom, a linear or branched alkyl group or cycloalkyl group, an alkali metal, an alkaline earth metal, or an onium;
  • R g represents a halogen ion, an inorganic anion, or an organic anion.
  • each of R 301 to R 31 1 independently represents a hydrogen atom or a hydrocarbon group; r represents an integer of from 1 to 3; each of L 301 to L 303 independently represents a single bond or a divalent organic connecting group; each of x and y represents a composition ratio, in which x represents a number satisfying a relation of 0
  • A represents -OH, -ORa, -CORa, -C0 2 Re, -CON(R a )(R b ), -N(R a )(R b ), -NHCOR d , -NHC0 2 R a , -OCON(R a )(R b ), -NHCON(R a )(R b ), -S0 3 Re, -OS0 3 Re, -S0 2 R d , -NHS0 2 R d , -S0 2 N(R a )(R b ), -N(R a )(R b )(R c ), -N(R a )(R b )(R c )(R g ), -P0 3 (R e )(R f ),
  • each of R 101 to R 108 independently represents a hydrogen atom or a hydrocarbon group; p represents an integer of from 1 to 3; each of L 101
  • each of x and y represents a composition ratio, in which x represents a number satisfying a relation of 0 ⁇ x ⁇ 100, and y represents a number satisfying a relation of 0 ⁇ y ⁇ 100;
  • a 101 represents -OH, -ORa, -COR a , -C0 2 Re, -CON(R a )(R b ), -N(R a )(R b ), -NHCOR d , -NHC0 2 R a , -OCON(R a )(R b ), -NHCON(R a )(R b ), -S0 3 Re, -OS0 3 Re, -S0 2 R d , -NHS0 2 3 ⁇ 4, -S0 2 N(R a )(R b ), -N(R a )(R b )(R c
  • each of R 101 to R 108 independently represents a hydrogen atom or a hydrocarbon group.
  • the hydrocarbon group include an alkyl group and an aryl group, and a linear or branched alkyl group or cycloalkyl group having a carbon atom number of from 1 to 8 is preferable.
  • each of R 101 to R 108 is preferably a hydrogen atom, a methyl group, or an ethyl group.
  • Such a hydrocarbon group may further have a substituent.
  • the alkyl group has a substituent
  • the substituted alkyl group is constituted by bonding between a substituent and an alkylene group.
  • a monovalent non-metal atomic group exclusive of hydrogen is used as the substituent.
  • Preferred examples thereof include a halogen atom (for example, -F, -Br, -CI, or -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an alkyldithio group, an aryldithio group, an amino group, an N-alkylamino group, an ⁇ , ⁇ -diarylamino group, an N-alkyl-N-arylamino group, an acyloxy group, a carbamoyloxy group, an N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an N,N-dialkylcarbamoyloxy group, an N,N-diarylcarbamoyloxy group, an N-alkyl-N-arylcarbamoyloxy group, an alkylsulfoxy group, an
  • an aryloxycarbonyl group a carbamoyl group, an N-alkylcarbamoyl group, an ⁇ , ⁇ -dialkylcarbamoyl group, an N-arylcarbamoyl group, an ⁇ , ⁇ -diarylcarbamoyl group, an N-alkyl-N-arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-S0 3 H) and a conjugated base group thereof (hereinafter referred to as "sulfonato group”), an alkoxysulfonyl group, an aryloxysulfonyl group, a sulfinamoyl group, an N-alkylsulfinamoyl group, an N,N-dialkylsulfm
  • alkyl group examples include the same alkyl groups as those exemplified for R 101 to R 108 ; and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a chloromethylphenyl group, a hydroxyphenyl group, a methoxyphenyl group, an ethoxyphenyl group, a phenoxyphenyl group, an acetoxyphenyl group, a benzoyloxyphenyl group, a methylthiophenyl group, a phenylthiophenyl group, a methyl aminophenyl group, a dimethylaminophenyl group, an acetylaminophenyl group, a
  • examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, and a 2-chloro-l-ethenyl group; and examples of the alkynyl group include an ethynyl group, a 1 -propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group.
  • Examples of G 1 in the acyl group (G'CO-) include hydrogen and the foregoing alkyl groups and aryl groups.
  • a halogen atom for example, -F, -Br, -CI, or -I
  • an alkoxy group for example, -F, -Br, -CI, or -I
  • an alkoxy group for example, -F, -Br, -CI, or -I
  • an alkoxy group for example, -F, -Br, -CI, or -I
  • an alkoxy group for example, -F, -Br, -CI, or -I
  • an alkoxy group for example, -F, -Br, -CI, or -I
  • an alkoxy group for example, -F, -Br, -CI, or -I
  • an alkoxy group for example, -F, -Br, -CI, or -I
  • an alkoxy group for example, -F, -Br, -CI, or -I
  • an alkoxy group for example,
  • examples of the alkylene group in the substituted alkyl group include a divalent organic residue obtained by removing any one of hydrogen atoms on an alkyl group having a carbon number of from 1 to 20.
  • a linear alkylene group having a carbon number of more preferably from 1 to 12, and still more preferably from 1 to 8 there can be exemplified a linear alkylene group having a carbon number of more preferably from 1 to 12, and still more preferably from 1 to 8; a branched alkylene group having a carbon number of more preferably from 3 to 12, and more preferably from 3 to 8; and a cyclic alkylene group having a carbon number of preferably from 5 to 10, and more preferably from 5 to 8.
  • Specific examples of the preferred substituted alkyl group obtained by combining the subject substituent with the alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a hydroxymethyl group, a methoxymethyl group, a
  • methoxyethoxyethyl group an allyloxymethyl group, a phenoxymethyl group, a
  • methylthiomethyl group a tolylthiomethyl group, an ethylaminoethyl group, a
  • diethylaminopropyl group diethylaminopropyl group, a morpholinopropyl group, an acetyloxymethyl group, a
  • N-phenylcarbamoyloxyethyl group N-phenylcarbamoyloxyethyl group, an acetylaminoethyl group, an
  • N-methylbenzoylaminopropyl group N-methylbenzoylaminopropyl group, a 2-oxyethyl group, a 2-oxypropyl group, a
  • N-methylcarbamoylethyl group an ⁇ , ⁇ -dipropylcarbamoylmethyl group, an
  • N-(methoxyphenyl)carbamoylethyl group an N-methyl-N-(sulfophenyl)carbamoylmethyl group, a sulfobutyl group, a sulfonatobutyl group, a sulfamoylbutyl group, an
  • N-ethylsulfamoylmethyl group an ⁇ , ⁇ -dipropylsulfamoylpropyl group, an
  • a hydroxymethyl group is preferable from the viewpoint of hydrophilicity.
  • Each of L 101 and L 102 independently represents a single bond or a divalent organic connecting group.
  • the "single bond” as referred to herein means that the main chain of the polymer is bonded directly to X without a connecting chain.
  • each of L 101 and L 102 represents an organic connecting group
  • each of L 101 and L 102 represents a divalent connecting group composed of a non-metal atom or atoms and is composed of from 0 to 60 carbon atoms, from 0 to 10 nitrogen atoms, from 0 to 50 oxygen atoms, from 0 to 100 hydrogen atoms, and from 0 to 20 sulfur atoms.
  • each of L 101 and L 102 is preferably selected among -N ⁇ , an aliphatic group, an aromatic group, a heterocyclic group, and a combination thereof, and more preferably a divalent connecting group composed of -0-, -S-, -CO-, -NH-, or a combination containing -O- or -S- or -CO- or -NH-.
  • a structural unit selected among a methylene group, an ether group, a sulfo group, a sulfonyl group, a sulfinyl group, a thioether group, an ester group, a carbonyl group, an amino group, an amide group, a sulfonamide group, a urea group, a carbamate group, a carbonate group, a -CONHS0 2 - group, a phenylene group, a naphthylene group, an anthracenylene group, a phenanthrylene group, a methylalkylene group, and a dimethylalkylene group, which are a divalent group represented by the following chemical formulae, or a group constituted of a combination thereof.
  • L 101 is preferably a single bond or a connecting group having one or more structures selected from the group consisting of -CONH-, -NHCONH-, -OCONH-, -S0 2 NH-, and -S0 3 -.
  • a 101 represents -OH, -OR a , -C0R a , -C0 2 R e , -CON(R a )(R b ), -N(R a )(R b ), -NHCOR d , -NHC0 2 R a , -OCON(R a )(R b ), -NHCON(R a )(R b ), -S0 3 R e , -OS0 3 R e , -S0 2 R d , -NHS0 2 R d , -S0 2 N(R a )(R b ), -N(R a )(R b )(R c ), -N(R a )(R b )(R c )(R g ), -P0 3 (R e )(R f ), -OP03(Re)(R a )(R
  • R a to R g may be bonded to each other to form a ring; and the formed ring may be a hetero ring containing a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.
  • R a to R g may further have a substituent, and examples of the substituent which can be introduced include
  • suitable examples of the linear or branched alkyl group or cycloalkyl group 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, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, an isopentyl group, a neopentyl group, a 1 -methylbutyl group, an isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group.
  • suitable examples of the alkali metal include lithium, sodium, and potassium; suitable examples of the alkaline earth metal include barium; and suitable examples of the onium include ammonium, iodonium, and sulfonium.
  • halogen ion examples include a fluorine ion, a chlorine ion, and a bromine ion
  • suitable examples of the inorganic anion include a nitrate anion, a sulfate anion, a tetrafluoroborate anion, and a hexafluorophosphate anion
  • suitable examples of the organic anion include a methanesulfonate anion, a trifluoromethanesulfonate anion, a nonafluorobutanesulfonate anion, and a p-toluenesulfonate anion.
  • a 101 is preferably -NHCOCH 3 , -CONH 2 , -CON(CH 3 ) 2 , -COOH, -S0 3 " NMe 4 , -S0 3 ⁇ K , -(CH 2 CH 2 0) n H, a morpholyl group, or the like; and more preferably -NHCOCH 3 , -CONH2, -CON(CH 3 ) 2 , -S0 3 " K + , or -(CH 2 CH 2 0) n H.
  • n preferably represents an integer of from 1 to 100.
  • each of x and y represents a composition ratio of the structural unit represented by the formula (I-l) and the structural unit represented by the formula (1-2) in the hydrophilic polymer (I)
  • x represents a number satisfying a relation of 0 ⁇ x ⁇ 100
  • y represents a number satisfying a relation of 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.
  • a copolymerization ratio of the hydrophilic polymer (I) containing the structures represented by the formulae (I-l) and (1-2) can be arbitrarily set such that the amount of the structural unit represented by the formula (1-2) having a hydrophilic group falls within the foregoing range.
  • the structural unit having a hydrophilic group in the hydrolyzable silyl group-containing hydrophilic polymer is contained in an amount of 30 % by mole or more of the whole of the polymer.
  • y/x is 30/70 or more, the hydrophilicity does not become insufficient, whereas when y/x is not more than 99/1, the amount of the hydrolyzable silyl group is sufficient, sufficient curing is obtained, and the layer strength is sufficient.
  • a mass average molecular weight of the polymer having structures represented by the formulae (I-l) and (1-2) is preferably from 1,000 to 1,000,000, more preferably from 1 ,000 to 500,000, and most preferably from 1 ,000 to 200,000.
  • hydrophilic polymer (I) containing the structures represented by the formulae (I-l) and (1-2) are hereunder shown along with mass average molecular weights (M.W.) thereof, but it should not be construed that the invention is limited thereto.
  • M.W. mass average molecular weights
  • the polymers described below as specific examples are a random copolymer or a block copolymer in which the described respective structural units are contained in the described molar ratio. 0 6 6 ) 1 /80 T /20 IW.W.32,000
  • Each of compounds for synthesizing the hydrophilic polymer containing the structures represented by the formulae (I-l) and (1-2) is commercially available or can also be easily synthesized.
  • the general radical polymerization method is described in, for example, Shin Kobunshi Jikken-gaku (New Polymer Experimentology) 3 (published by Kyoritsu Shuppan Co., Ltd. (1996)): Synthesis and Reaction 1 of Polymer (edited by The Society of Polymer Science, Japan and published by Kyoritsu Shuppan Co., Ltd. (1992)); Shin Jikken Kagaku Koza (New Experimental Chemistry Course) 19: Polymer Chemistry (I) (edited by The Chemical Society of Japan and published by Maruzen Co., Ltd. (1996)); and Busshitsu Kogaku Koza (Material Engineering Course): Polymer Synthesis Chemistry (published by Tokyo Denki University Press (1995)). These can be applied.
  • each of R to R independently represents a hydrogen atom or a hydrocarbon group; q represents an integer of from 1 to 3; each of L 201
  • A represents -OH, -OR a , -COR a , -C0 2 Re, -CON(R a )(R b ), -N(R a )(R b ), -NHCORj, -NHC0 2 R a , -OCON(R a )(R b ), -NHCON(R a )(R b ), -S0 3 Re, -OS0 3 3 ⁇ 4, -S0 2 R d , -NHS0 2 R ⁇ i, -S0 2 N(R a )(R b ), -N(R a )(R b )(Rc), -N(R a )(R b )(R c )(R g ), -P0 3 (R e )(R f ), -OP0 3 (Re)
  • hydrophilic polymer (II) containing the structures represented by the formulae (II- 1) and ( ⁇ -2) has the structural structure represented by the foregoing formula ( ⁇ -2) and has the partial structure represented by the foregoing formula (II- 1) at an end of the polymer chain.
  • each of R 201 to R 205 independently represents a hydrogen atom or a hydrocarbon group.
  • examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear or branched alkyl group or cycloalkyl group having a carbon atom number of from 1 to 8 is preferable.
  • examples thereof include the same groups as those exemplified for R 101 to R 108 in the foregoing formulae (1-1) and (1-2).
  • Each of L 201 and L 202 independently represents a single bond or a divalent organic connecting group.
  • the "single bond" as referred to herein means that the main chain of the polymer is bonded directly to A and the Si atom without a connecting chain.
  • specific examples and preferred examples thereof include the same groups as those exemplified for L 101 in the foregoing formula (I- 1).
  • a 201 represents -OH, -OR a , -COR a , -C0 2 Re, -CON(R a )(R b ), -N(R a )(R b ), -NHCOR d , -NHC0 2 R a , -OCON(R a )(R b ), -NHCON(R a )(R b ), -S0 3 Re, -OS0 3 Re, -S0 2 R d , -NHS0 2 R d , -S0 2 N(R a )(R b ), -N(R a )(R b )(Rc), -N(R a )(R b )(Rc)(R g ), -P0 3 (Re)(R f ), -OP0 3 (Re)(R f ), or -P0 3 (R d )(Re).
  • q represents an integer of from 1 to 3, preferably from 2 to 3, and more preferably 3.
  • Each of L 201 and L 202 is preferably -CH 2 CH 2 CH 2 S-, -CH 2 S-, -CONHCH(CH 3 )CH 2 -, -CONH-, -CO-, -C0 2 -, or -CH 2 -.
  • the hydrophilic polymer (II) containing the structures represented by the formulae (II- 1) and ( ⁇ -2) can be, for example, synthesized by radical polymerizing a hydrophilic monomer (for example, acrylamide, acrylic acid, or a potassium salt of 3-sulfopropyl methacrylate) in the presence of a chain transfer agent (described in Kanji KAMACHI and Tsuyoshi ENDO, Radical Polymerization Handbook, NTS) or an iniferter (described in Macromolecules, 1986, 19, pages 287, et seq., Otsu).
  • a chain transfer agent described in Kanji KAMACHI and Tsuyoshi ENDO, Radical Polymerization Handbook, NTS
  • an iniferter described in Macromolecules, 1986, 19, pages 287, et seq., Otsu).
  • chain transfer agent examples include 3-mercaptopropionic acid, 2-aminoethanethiol hydrochloride, 3-mercaptopropanol, 2-hydroxyethyl disulfide, and 3-mercaptopropyl trimethoxysilane.
  • a hydrophilic monomer for example, acrylamide
  • acrylamide may be radical polymerized using a radical polymerization initiator having a reactive group without using a chain transfer agent.
  • the hydrophilic polymer (II) containing the structures represented by the formulae (II- 1) and ( ⁇ -2) can be synthesized by radical polymerizing a radical polymerizable monomer represented by the following formula (i) by using a silane coupling agent having chain transfer ability in radical polymerization as represented by the following formula (ii). Since the silane coupling agent (ii) has chain transfer ability, a polymer in which a silane coupling group is introduced at a main chain end of the polymer in the radical polymerization can be synthesized.
  • R 201 to R 205 , L 201 , L 202 , A 201 , and q are synonymous with those in the foregoing formula (II- 1).
  • these compounds are commercially available or can also be easily synthesized.
  • the radical polymerizable monomer represented by the formula (i) has the hydrophilic group A 201 , and this monomer functions as one structural unit in the hydrophilic polymer.
  • a molar number of the structural unit of the formula ( ⁇ -2) relative to a molar number of the structural unit of the formula (II- 1), which has a hydrolyzable silyl group is preferably in the range of from 1,000 to 10 times, more preferably in the range of from 500 to 20 times, and most preferably in the range of from 200 to 30 times.
  • the hydrophilicity does not become insufficient, whereas when the molar number of the structural unit of the formula (II-2) is not more than 1000 times, the amount of the hydrolyzable silyl group is sufficient, sufficient curing is obtained, and the layer strength is sufficient.
  • a mass average molecular weight of the hydrophilic polymer (II) containing the structures represented by the formulae (II- 1) and (II-2) is preferably from 1,000 to 1,000,000, more preferably from 1,000 to 500,000, and most preferably from 1,000 to 200,000.
  • hydrophilic polymer (II) which may be suitably used in the invention are hereunder shown, but it should not be construed that the invention is limited thereto.
  • * expresses a bonding position with the polymer.
  • the hydrophilic polymer (III) contains structures represented by the following formulae (III- 1 ) and ( ⁇ -2).
  • the hydrophilic polymer (III) is preferably a hydrophilic graft polymer in which a side chain having a hydrophilic group is introduced into a trunk polymer having a reactive group.
  • each of R 301 to R 31 1 independently represents a hydrogen atom or a hydrocarbon group; r represents an integer of from 1 to 3; each of L 301 to
  • L independently represents a single bond or a divalent organic connecting group; each of x and y represents a composition ratio, in which x represents a number satisfying a relation of 0 ⁇ x ⁇ 100, and y represents a number satisfying a relation of 0 ⁇ y ⁇ 100;
  • a 301 represents -OH, -OR,, -COR a , -C0 2 Re, -CON(R a )(R b ), -N(R a )(R b ), -NHCOR d , -NHC0 2 R a , -OCON(R a )(R b ), -NHCON(R a XR b ), -S0 3 Re, -OS0 3 Re, -S0 2 R d , -NHS0 2 R d , -S0 2 N(R a )(R b ), -N(R a )(R b )(
  • each of R 301 to R 31 1 independently represents a hydrogen atom or a hydrocarbon group.
  • examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear or branched alkyl group or cycloalkyl group having a carbon atom number of from 1 to 8 is preferable.
  • examples thereof include the same groups as those exemplified for R 101 to R 108 in the foregoing formulae (1-1) and (1-2), and preferred ranges thereof are also the same.
  • Each of L , L , and L independently represents a single bond or a divalent organic connecting group.
  • the "single bond” as referred to herein means that the main chain
  • each of L , L , and L represents a divalent organic connecting group
  • specific examples and preferred examples thereof include the same groups as those exemplified for L 101 in the foregoing formula (1-1).
  • a 301 represents -OH, -OR a , -COR a , -C0 2 Re, -CON(R a )(R b ), -N(R a )(R lake), -NHCORd, -NHC0 2 R a , -OCON(R a )(R b ), -NHCON(R a )(R b ), -S0 3 Re, -OS0 3 Re, -S0 2 R d , -NHS0 2 R d , -S0 2 N(R a )(R b ), -N(R a )(R b )(Rc), -N(R a )(R b )(R c )(R g ), -P0 3 (R e )(R f ), -OP0 3 (Re)(R f ), or
  • r represents an integer of from 1 to 3, preferably from 2 to 3, and more preferably 3.
  • This hydrophilic graft polymer can be prepared by adopting a method which is generally known as a synthesis method of graft polymer.
  • a method which is generally known as a synthesis method of graft polymer is described in Graft Polymerization and Its Application, written by Fumio IDE and published by Kobunshi Kankokai (1977) and Shin Kobunshi Jikken-gaku (New Polymer Experimentology) 2: Synthesis and Reaction of Polymer, edited by The Society of Polymer Science, Japan and published by Kyoritsu Shuppan Co., Ltd. (1995). These can be applied.
  • the synthesis method of graft polymer is basically classified into three methods of (1) a method of polymerizing a branched monomer from a trunk polymer, (2) a method of bonding a branched polymer with a trunk polymer, and (3) a method of copolymerizing a branched polymer on a trunk polymer (macromer method).
  • a method of polymerizing a branched monomer from a trunk polymer (2) a method of bonding a branched polymer with a trunk polymer
  • a method of copolymerizing a branched polymer on a trunk polymer (macromer method).
  • the hydrophilic graft polymer which is used in the invention can be fabricated by using any of these three methods, in particular, the "macromer method (3)" is excellent from the viewpoints of manufacture adaptability and control of the layer structure.
  • the graft polymer which is used in the invention can be first synthesized by copolymerizing a hydrophilic macromonomer synthesized by the foregoing method (corresponding to a precursor of the hydrophilic polymer side chain) with a monomer having a reactive group.
  • hydrophilic macromonomers macromonomers derived from a carboxyl group-containing monomer such as acrylic acid and methacrylic acid; sulfonic acid based macromonomers derived from a monomer such as 2-acrylamido-2-methylpropanesulfonic acid, vinylstyrenesulfonic acid, and salts thereof; amide based macromonomers such as acrylamide and methacrylamide; amide based macromonomers derived from an N-vinylcarboxylic acid amide monomer such as N-vinylacetamide and N-vinylformamide; macromonomers derived from a hydroxyl group-containing monomer such as hydroxyethyl methacrylate, hydroxyethyl acrylate, and glycerol monomethacrylate; and macromonomers derived from an alkoxy group or ethylene oxide group-containing monomer such as methoxyethyl acrylate, methoxypolyethylene glycol acrylate, and
  • monomers having a polyethylene glycol chain or a polypropylene glycol chain can be usefully used as the macromonomer of the invention.
  • the useful polymer has a mass average molecular weight (hereinafter referred to simply as "molecular weight") in the range of from 400 to 100,000, preferably in the range of from 1,000 to 50,000, and especially preferably in the range of from 1,500 to 20,000.
  • molecular weight is 400 or more, effective hydrophilicity is obtained, whereas when the molecular weight is not more than 100,000, the polymerizability with a copolymerizable monomer for forming a main chain tends to become high. All of them are preferable.
  • 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.
  • a copolymerization ratio of the hydrophilic polymer (III) can be arbitrarily set such that the amount of the structural unit represented by the formula (III-2) having a hydrophilic group falls within the foregoing range.
  • the structural unit having a hydrophilic group in the hydrolyzable silyl group-containing hydrophilic polymer is contained in an amount of 30 % by mole or more of the whole of the polymer.
  • y/x is 30/70 or more, the hydrophilicity does not become insufficient, whereas when y/x is not more than 99/1, the amount of the hydrolyzable silyl group is sufficient, sufficient curing is obtained, and the layer strength is sufficient.
  • hydrophilic polymer (III) those having a mass average molecular weight of not more than 1 ,000,000 are preferably used.
  • the molecular weight is more preferably in the range of from 1,000 to 1 ,000,000, and still more preferably in the range of from 20,000 to 100,000.
  • the solubility in a solvent does not become deteriorated, and there is no problem in handling such that the viscosity of the coating solution is low and that a uniform coating is easily formed. Therefore, such is preferable.
  • hydrophilic polymer (III) containing the structures represented by the formulae (III- 1 ) and (III-2) are hereunder shown along with mass average molecular weights (M.W.) thereof, but it should not be construed that the invention is limited thereto.
  • M.W. mass average molecular weights
  • the hydrophilic polymer (I), (II), or (III) may be a copolymer with other monomer.
  • examples of other monomer to be used include known monomers such as acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, and maleic acid imide.
  • acrylic acid ester examples include methyl acrylate, ethyl acrylate, n-propyl or isopropyl acrylate, n-butyl, isobutyl, sec -butyl 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, chlorobenzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl acrylate, furfuryl acrylate, tetrahydrofurfury
  • methacrylic acid ester examples include methyl methacrylate, ethyl methacrylate, n-propyl or isopropyl methacrylate, n-butyl, isobutyl, sec-butyl 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,
  • methacrylate methoxybenzyl methacrylate, chlorobenzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, and
  • acrylamide examples include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide,
  • methacrylamide examples include methacrylamide,
  • vinyl ester examples include vinyl acetate, vinyl butyrate, and vinyl benzoate.
  • styrene examples include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, propylstyrene, cyclohexyl styrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, and carboxy styrene.
  • a proportion of such other monomer to be used for the synthesis of a copolymer a sufficient amount for improving various physical properties is necessary.
  • the function as the hydrophilic layer may be sufficient and that advantages to be brought by the addition of the specified hydrophilic polymer (I), the specified hydrophilic polymer (II), and/or the specified hydrophilic polymer (III) may be sufficiently obtained, it is preferable that the proportion is not excessively high.
  • a total proportion of other monomer in the specified hydrophilic polymer (I), the specified hydrophilic polymer (II), and/or the specified hydrophilic polymer (III) is preferably not more than 80 % by mass, and more preferably not more than 50 % by mass.
  • the measurement of a copolymerization ratio of the hydrophilic polymer (I), (II) or (III) can be achieved by a nuclear magnetic resonance apparatus (NMR) or by preparing a calibration curve with a standard substance, followed by measuring by an infrared spectral photometer.
  • NMR nuclear magnetic resonance apparatus
  • the hydrophilic polymer (I), (II) or (III) may be used solely or in admixture of two or more kinds thereof.
  • the hydrophilic polymer (I), (II), or (III) is used in an amount of preferably from 20 to 99.5 % by mass, and more preferably from 30 to 99.5 % by mass relative to the whole of solids of the hydrophilic composition.
  • the foregoing hydrophilic polymer forms a crosslinked layer in a state where it is mixed with a hydrolysis and polycondensation product of the metal alkoxide.
  • the hydrophilic polymer which is an organic component participates in the layer strength and layer flexibility.
  • the viscosity of the hydrophilic polymer falls within the range of from 0.1 to 100 mPa-s (measured in a 5 % aqueous solution at 20°C), preferably from 0.5 to 70 mPa s, and more preferably from 1 to 50 mPa-s, good layer physical properties are imparted.
  • the foregoing hydrophilic polymer grafted with a hydrophilic group is very high in hydrophilicity as compared with conventional hydrophilic polymers in which a hydrophilic group thereof is substituted with a polymer chain. That is, in a layer containing the foregoing hydrophilic polymer grafted with a hydrophilic group, a water droplet on the layer surface is liable to spread as compared with a layer containing a conventional hydrophilic polymer.
  • the hydrophilic group grafted with a polymer chain is high in rotationality and mobility and is able to make the hydrophilicity of the layer surface more uniform. It may be considered that since the hydrophilic member of the invention has a hydrophilic group with high rotationality and mobility, it is excellent in effects such as anti-fogging properties. In addition, it may be assumed that since the hydrophilic member of the invention contains an oligomer or polymer, it is excellent in effects such as adhesion.
  • hydrophilic member of the invention by allowing the foregoing hydrophilic material and the oligomer or polymer to have a composition gradient, the effects including anti-fogging properties and adhesion are made compatible with each other.
  • the water droplet contact angle in air of the foregoing hydrophilic polymer grafted with a hydrophilic group is preferably from 0 to 5°.
  • a value of the subject water droplet contact angle in air is very small as compared with values (from about 10 to 20°) which the conventional hydrophilic polymers exhibit.
  • a hydrophilic member exhibiting such a very small water droplet contact angle in air is called "super-hydrophilic material".
  • the foregoing hydrophilic polymer (I) is contained in the hydrophilic material, for the purpose of obtaining good curing properties, it is preferable to contain a crosslinking agent.
  • a crosslinking agent may be contained in the case where the foregoing hydrophilic polymer (II) or (III) is contained in the hydrophilic material.
  • an alkoxy compound containing an element selected among Si, Ti, Zr, and Al (also referred to as "metal alkoxide”) is especially preferable.
  • the metal alkoxide is a hydrolyzable, polymerizable compound having a functional group which is polycondensable upon hydrolysis in a structure thereof and working a function as a crosslinking agent, and when metal alkoxides are polycondensed with each other, a firm crosslinked layer having a crosslinking structure is formed.
  • the metal alkoxide can also be chemically bonded with the foregoing hydrophilic polymer.
  • the metal alkoxide can be represented by the following formula (V-l) or formula (V-2).
  • R 20 represents a hydrogen atom, an alkyl group, or an aryl group
  • each of R 21 and R 22 represents an alkyl group or an aryl group
  • Z represents Si, Ti, or Zr
  • m represents an integer of from 0 to 2.
  • a carbon number thereof is preferably from 1 to 4.
  • the alkyl group or the aryl group may have a substituent, and examples of the substituent which can be introduced include a halogen atom, an amino group, and a mercapto group.
  • this compound is a low-molecular weight compound and preferably has a molecular weight of not more than 2,000.
  • Z represents Si
  • examples thereof include trimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane,
  • trimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, and phenyltrimethoxysilane are especially preferable.
  • Z represents Ti
  • examples thereof include trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyltrimethoxy titanate, methyltriethoxy titanate, ethyltriethoxy titanate, diethyldiethoxy titanate, phenyltrimethoxy titanate, and phenyltriethoxy titanate.
  • Z represents Zr, namely zirconium is contained in the hydrolyzable compound
  • examples thereof include zirconates corresponding to the above-exemplified titanium-containing compounds.
  • the central metal is Al
  • examples thereof include trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, and triisopropoxy aluminate.
  • tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane are especially preferable.
  • the metal alkoxide compound of a metal selected among Si, Ti, Zr, and Al is used in an amount of preferably from 0 to 80 % by mass, and more preferably from 0 to 70 % by mass relative to the whole of solids of the hydrophilic composition.
  • the metal alkoxide compound of a metal selected among Si, Ti, Zr, and Al is used in an amount of preferably from 0 to 80 % by mass, and more preferably from 0 to 70 % by mass relative to the whole of solids of the hydrophilic composition.
  • the hydrolyzable silyl group-containing hydrophilic polymer and further the crosslinking agent such as a metal alkoxide compound undergo hydrolysis and polycondensation to form an organic/inorganic composite sol solution, and a hydrophilic layer having high hydrophilicity and high layer strength is formed by this sol solution.
  • a curing catalyst for accelerating the hydrolysis and polycondensation reaction.
  • an acidic catalyst, a basic catalyst, or a metal complex catalyst as the curing catalyst which is used in the invention.
  • a catalyst capable of undergoing hydrolysis and polycondensation of the foregoing crosslinking agent such as a metal alkoxide compound and accelerating a reaction for generating bonding with a hydrolyzable silyl group-containing hydrophilic polymer is selected, and an acid or a basic compound is used as it is, or a material in a dissolved state of an acid or a basic compound in a solvent such as water and an alcohol (these will be also referred to collectively as “acidic catalyst” and “basic catalyst”, respectively) is used.
  • a concentration at the time of dissolving the acid or basic compound in a solvent is not particularly limited, and it may be properly selected according to characteristics of the acid or basic compound to be used, a desired content of the catalyst, and the like.
  • concentration of the acid or basic compound constituting the catalyst is high, the hydrolysis and polycondensation rate tends to become fast.
  • concentration of the acid or basic compound constituting the catalyst is high, the hydrolysis and polycondensation rate tends to become fast.
  • a basic catalyst having a high concentration there may be the case where a precipitate is formed in the sol solution. Therefore, in the case of using a basic catalyst, its concentration is desirably not more than 1 N as reduced into a concentration in the aqueous solution.
  • the kind of the acidic catalyst or basic catalyst is not particularly limited, in the case where it is needed to use a catalyst having a high concentration, a catalyst constituted of an element such that it does not substantially remain in a coating after drying may be useful.
  • the acidic catalyst include hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carboxylic acids such as carbonic acid, formic acid, and acetic acid, substituted carboxylic acids in which R of a structural formula represented by RCOOH is substituted with other element or a substituent, and sulfonic acids such as benzenesulfonic acid.
  • the basic catalyst include ammoniacal bases such as ammonia water and amines such as ethylamine and aniline.
  • the catalyst which can be used in the hydrophilic material of the invention is especially preferably a metal complex catalyst.
  • the metal complex catalyst which can be used for the formation of a hydrophilic layer is able to accelerate hydrolysis and polycondensation of a metal alkoxide compound of a metal selected among Si, Ti, Zr, and Al to generate bonding with the hydrophilic polymer.
  • the metal complex catalyst is especially preferably a metal complex constituted of a metal element selected among those belonging to the groups 2A, 3B, 4A, and 5A of the periodic table and an oxo or hydroxyl oxygen-containing compound selected among ⁇ -diketones, keto esters, hydroxycarboxylic acids or esters thereof, amino alcohols, and enolic active hydrogen compounds.
  • elements of the group 2A such as Mg, Ca, St, and Ba
  • elements of the group 3B such as Al and Ga
  • elements of the group 4A such as Ti and Zr
  • elements of the group 5A such as V, Nb, and Ta
  • complexes obtained from Zr, Al, or Ti are excellent and preferable.
  • examples of the oxo or hydroxyl oxygen-containing compound which constitutes a ligand of the foregoing metal complex include ⁇ -diketones such as acetylacetone, acetylacetone (2,4-pentanedione), and 2,4-heptanedione, keto esters such as methyl acetoacetate, ethyl acetoacetate, and butyl acetoacetate, hydroxycarboxylic acids and esters thereof such as lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, and methyl tartarate, keto alcohols such as 4-hydroxy-4-methyl-2-pentanone, 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, and 4-hydroxy-2-heptanone, amino alcohols such as monoethanolamine, ⁇ , ⁇ -dimethylethanolamine, N-methyl-monoethanolamine, diethanolamine
  • the ligand is preferably an acetylacetone derivative.
  • the acetylacetone derivative refers to a compound having a substituent on the methyl group, methylene group or carbonyl carbon of acetylacetone.
  • the substituent which is substituted on the methyl group of acetylacetone include a linear or branched alkyl group, a linear or branched acyl group, a linear or branched hydroxyalkyl group, a linear or branched carboxyalkyl group, a linear or branched alkoxy group, and a linear or branched alkoxyalkyl group each having a carbon number of from 1 to 3;
  • examples of the substituent which is substituted on the methylene group of acetylacetone include a linear or branched carboxyalkyl group and a linear or branched hydroxyalkyl group each having a carbon number of from 1 to 3 as well as a carboxyl group; and examples of the substituent which is
  • acetylacetone derivative examples include acetylacetone, ethylcarbonylacetone, n-propylcarbonylacetone, isopropylcarbonylacetone, diacetylacetone, 1 -acetyl- 1 -propionyl-acetylacetone, hydroxy ethylcarbonylacetone,
  • the complex of the foregoing acetylacetone derivative with the foregoing metal element is a mononuclear complex in which from 1 to 4 acetylacetone derivative molecules are coordinated per metal element.
  • coordination number of the metal element is greater than the total coordination number of the acetylacetone derivative, ligands commonly used in usual complexes such as a water molecule, a halogen ion, a nitro group, and an ammonio group may be coordinated on the metal element.
  • Examples of the preferred metal complex include a tris(acetylacetonato)aluminum complex salt, a di(acetylacetonato)aluminum aquo complex salt, a
  • mono(acetylacetonato)aluminum chloro complex salt a di(diacetylacetonato)aluminum complex salt, ethylacetoacetate aluminum diisopropylate, aluminum tris(ethylacetoacetate), cyclic aluminum oxide isopropylate, a tris(acetylacetonato)barium complex salt, a
  • di(acetylacetonato)titanium complex salt a tris(acetylacetonato)titanium complex salt, a diisopropoxy bis(acetylacetonato)titanium complex salt, zirconium tris(ethylacetoacetate), and a zirconium tris(benzoic acid) complex salt.
  • These metal complexes exhibit excellent stability in an aqueous coating solution and are excellent in an effect for accelerating the gelation in a sol-gel reaction at the time of heat drying.
  • ethylacetoacetate aluminum diisopropylate, aluminum tris(ethylacetoacetate), a di(acetylacetonato)titanium complex salt, and zirconium tris(ethylacetoacetate) are especially preferable.
  • a counter salt of the foregoing metal complex is omitted.
  • the kind of the counter salt is arbitrary so far as it is a water-soluble salt which keeps the electric charge as a complex compound neutral. Salts which can be stoichiometrically kept neutral, for example, nitrates, halogenic acid salts, sulfates, and phosphates, are useful.
  • the behavior of a silica sol-gel reaction of the metal complex is described in detail in J. Sol-Gel. Sci. and Tec, 16, 209 (1999). As its reaction mechanism, the following scheme may be presumed.
  • the metal complex takes a coordination structure and is stable in a coating solution and in a dehydration condensation reaction which starts with a heating and drying step after coating, accelerates crosslinking according to a mechanism similar to an acid catalyst.
  • the use of this metal complex made it possible to improve the stability with time of the coating solution and the surface quality of the layer and to satisfy all of high hydrophilicity and high durability.
  • a catalyst which is able to accelerate hydrolysis and polycondensation of an alkoxide compound of a metal selected among Si, Ti, Z, and Al to generate bonding with the hydrophilic polymer may be used in combination.
  • Such a catalyst examples include compounds exhibiting acidity, for example, hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carboxylic acids such as carbonic acid, formic acid, and acetic acid, and substituted carboxylic acids in which R of a structural formula represented by RCOOH is substituted with other element or a substituent, and sulfonic acids such as benzenesulfonic acid; and basic compounds, for example, ammoniacal bases such as ammonia water and amines such as ethylamine and aniline.
  • hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide
  • carboxylic acids such as carbonic acid, formic acid, and acetic acid
  • RCOOH substituted carboxylic acids in which R of a structural formula represented by RCOOH
  • the foregoing metal complex catalyst is easily available as a commercial product and is also obtainable by a known synthesis method, for example, a reaction between each metal chloride and an alcohol.
  • the hydrophilic material in the invention may contain an inorganic fine particle for the purposes of enhancing the hydrophilicity, preventing the generation of a crack of the layer, and enhancing the layer strength.
  • examples of the inorganic fine particle which is suitably used include silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, and mixtures thereof.
  • the inorganic fine particle has an average particle size of preferably from 5 nm to 10 ⁇ , and more preferably from 0.5 to 3 ⁇ .
  • the particle size of the inorganic fine particle falls within the foregoing range, it is possible to form a composition gradient layer with high durability and excellent hydrophihcity in which the inorganic fine particle is stably dispersed in the hydrophilic layer, and the layer strength of the hydrophilic layer is sufficiently kept.
  • a colloidal silica dispersion is especially preferable and is easily available as a commercial product.
  • a content of the inorganic fine particle is preferably not more than 80 % by mass, and more preferably not more than 50 % by mass relative to the whole of solids of the hydrophilic layer.
  • a surfactant for the purpose of enhancing coating surface properties of the composition gradient layer, it is preferable to use a surfactant.
  • the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, ampholytic surfactants, and fluorine based surfactants.
  • the nonionic surfactant which is used in the invention is not particularly limited, and conventionally known nonionic surfactants can be used.
  • examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyrylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono-fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenated castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N,N-bis-2-hydroxyalkylamines, polyoxyethylene al
  • anionic surfactant which is used in the invention is not particularly limited, and conventionally known anionic surfactants can be used. Examples thereof include fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts,
  • dialkylsulfosuccinic acid ester salts linear alkylbenzenesulfonic acid salts, branched alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts,
  • alkylphenoxypolyoxyethylene propylsulfonic acid salts polyoxyethylene alkylsulfophenyl ether salts, an N-methyl-N-oleyltaurin sodium salt, N-alkylsulfosuccinic acid monoamide disodium salts, petroleum sulfonic acid salts, sulfated beef tallow oil, sulfuric acid ester salts of a fatty acid alkyl ester, alkylsulfuric acid ester salts, polyoxyethylene alkyl ether sulfuric acid ester salts, fatty acid monoglyceride sulfuric acid ester salts, polyoxyethylene alkylphenyl ether sulfuric acid ester salts, polyoxyethylene styrylphenyl ether sulfuric ester salts, alkylphosphoric acid ester salts, polyoxyethylene alkyl ether phosphoric acid ester salts, polyoxyethylene alkylphenyl ether phosphoric acid ester salts, a partially saponified
  • the cationic surfactant which is used in the invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
  • ampholytic surfactant which is used in the invention is not particularly limited, and conventionally known ampholytic surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric acid esters, and imidazolines.
  • the "polyoxyethylene” can also be given a different reading as “polyoxyalkylene” such as polyoxymefhylene, polyoxypropylene, and polyoxybutylene.
  • those surfactants can also be used.
  • examples of the preferred surfactant include fluorine based surfactants containing a perfluoroalkyl group in a molecule thereof.
  • fluorine based surfactant include anionic types such as perfluoroalkylcarboxylic acid salts, perfluoro- alkylsulfonic acid salts, and perfluoroalkylphosphoric acid esters; ampholytic types such as perfluoroalkylbetaines; cationic types such as perfluoroalkyltrimethylammonium salts; and nonionic types such as perfluoroalkylamine oxides, perfluoroalkyl ethylene oxide adducts, oligomers containing a perfluoroalkyl group and a hydrophilic group, oligomers containing a perfluoroalkyl group and a lipophilic group, oligomers containing a perfluoroalkyl group, a hydrophilic group, and a lipophilic group, oligomers containing
  • the surfactant is used in an amount in the range of preferably from 0.001 to 10 % by mass, and more preferably from 0.01 to 5 % by mass relative to a non- volatile component in the hydrophilic material of the invention.
  • the surfactant can be used solely or in combination of two or more kinds thereof.
  • Fluorine Based Surfactant 5 Fluorine Based Surfactant 6
  • an ultraviolet ray absorber can be used from the viewpoints of an enhancement of the weather resistance and an enhancement of the durability of the composition gradient layer.
  • ultraviolet ray absorber examples include benzotriazole based compounds described in JP-A-58-185677, JP-A-61-190537, JP-A-2-782, JP-A-5-197075, and JP-A-9-34057; benzophenone based compounds described in JP-A-46-2784, JP-A-5- 194483, and U.S. Patent No.
  • An addition amount of the ultraviolet ray absorber is properly chosen depending upon the purpose, and in general, it is preferably from 0.5 to 15 % by mass as reduced into a solid.
  • an antioxidant can be contained in the hydrophilic material.
  • the antioxidant include those described in EP-A-223739, EP-A-309401, EP-A-309402, EP-A-310551, EP-A-310552, EP-A-459416, DE-A-3435443, JP-A-54-262047, JP-A-63- 113536, JP-A-63- 163351, JP-A-2-262654, JP-A-2-71262, JP-A-3-121449, JP-A-5-61166, JP-A-5- 119449, and U.S. Patents Nos. 4,814,262 and 4,980,275.
  • An addition amount of the antioxidant is properly chosen depending upon the purpose and is preferably from 0.1 to 8 % by mass as calculated as solids.
  • various polymers can be added in the hydrophilic material which is used for forming the hydrophilic member of the invention within the range where the hydrophilicity is not hindered.
  • the polymer which can be used include acrylic polymers, polyvinyl alcohol resins, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl formal resins, shellac, vinyl based resins, acrylic resins, rubber based resins, waxes, and other natural resins.
  • these polymers may be used in combination with two or more kinds thereof.
  • vinyl based copolymers obtained by copolymerization with an acrylic monomer are preferable.
  • copolymers containing, as a structural unit, a "carboxyl group-containing monomer”, an "alkyl methacrylate”, or an “alkyl acrylate” are also preferably used.
  • a leveling additive for example, a matting agent, a wax for the purpose of adjusting layer physical properties, and a tackifier for the purpose of improving adhesion to the substrate within the range where the hydrophilicity is not hindered can be contained as the need arises.
  • examples of the tackifier include adhesive polymers having a high molecular weight, as described on pages 5 to 6 of JP-A-2001-49200 (for example, copolymers made of an ester of (meth)acrylic acid and an alcohol having an alkyl group having a carbon number of from 1 to 20, an ester of (meth)acrylic acid and an alicyclic alcohol having a carbon number of from 3 to 14, and an ester of (meth)acrylic acid and an aromatic alcohol having a carbon number of from 6 to 14); and low-molecular weight tackiness-imparting resins having a polymerizable unsaturated bond.
  • adhesive polymers having a high molecular weight as described on pages 5 to 6 of JP-A-2001-49200 (for example, copolymers made of an ester of (meth)acrylic acid and an alcohol having an alkyl group having a carbon number of from 1 to 20, an ester of (meth)acrylic acid and an alicyclic alcohol having a carbon number
  • an antimicrobial agent can be contained in the hydrophilic material.
  • a hydrophilic layer it is preferable to contain a hydrophilic, water-soluble antimicrobial agent.
  • a composition gradient layer capable of giving a surface-hydrophilic member which is excellent in antimicrobial properties, anti-fungal properties, and anti-algal properties is obtained without impairing the surface hydrophilicity.
  • antimicrobial agent a compound which does not reduce the hydrophilicity of the hydrophilic member formed of a composition gradient layer.
  • examples of such an antimicrobial agent include inorganic antimicrobial agents and water-soluble organic antimicrobial agents.
  • the antimicrobial agent ones exhibiting an antimicrobial effect against fungi existing in the surroundings, such as bacteria represented by Staphylococcus aureus and Escherichia coli, and Eumycetes such as fungi and yeasts are useful.
  • the oligomer which can be used in the invention is not limitative, for example, it refers to a polymer having a molecular weight of from 1,000 to 5,000.
  • the polymer as referred to herein means, for example, a polymer having a molecular weight of 5,000 or more, and preferably a compound having a molecular weight of from 5,000 to 10,000.
  • oligomer or polymer which can be used in the invention is not particularly limited, examples thereof include oligo- or polyethylene terephthalate, oligo- or polycarbonate, oligo- or polypropylene, oligo- or polyethylene, cyclic oligo- or polyolefins, a norbornene oligomer or polymer, oligo- or polystyrene, a styrene-acrylate co-oligomer or copolymer, an acrylonitrile-styrene co-oligomer or copolymer, oligo- or polyethylene naphthalate, oligo- or polyether sulfone, oligo- or polysulfone, nylon (oligomer or polymer), a urethane oligomer or polymer, an oligo- or polyacrylate, an oligo- or polymethacrylate, cellulose acetate (oligomer or polymer), cellulose triacetate, cellophane
  • a urethane oligomer or polymer an oligo- or polyacrylate, an oligo- or polymethacrylate, and oligo- or polystyrene are preferable, and a urethane oligomer or polymer is especially preferable.
  • a content of the oligomer or polymer in the ink is preferably 10 % by mass or more relative to a total mass of the ink.
  • the content of the oligomer or polymer in the ink is more preferably in the range of 30 % by mass or more and not more than 80 % by mass, still more preferably in the range of 30 % by mass or more and not more than 70 % by mass, and especially preferably in the range of 40 % by mass or more and not more than 60 % by mass.
  • the urethane oligomer or polymer in the invention refers to an oligomer of urethane or a polymer of urethane (also referred to as "polyurethane"), respectively. Of these, a urethane oligomer is more preferably used. As reasons why it is preferable to use the urethane polymer or oligomer, it may be assumed that in addition to the fact that the urethane polymer or oligomer has good adhesion to the base material, it is able to form a tough polymer blend layer due to an interaction between the hydrophilic material and a hydrogen bond.
  • the urethane oligomer or polymer of the invention is preferably an oligomer or polymer containing a urethane bond and a urea bond, or an oligomer or polymer having a urethane bond and a reactive group.
  • an oligomer or polymer having an alkylene linkage with high flexibility an oligomer or polymer having a functional group capable of undergoing reaction and curing by energy, and the like can be preferably used.
  • JUX-33 manufactured by Aica Inc.
  • the like can be preferably used.
  • oligomer or polymer having a urethane bond and a reactive group is more preferably an oligomer or polymer having a repeating unit represented by the following formula (A).
  • each of RAi to RA 3 independently represents an alkylene group, an arylene group, or a biarylene group; and each of RA 4 to RA 6 independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
  • an alkylene group having a carbon number of from 1 to 10 is preferable.
  • arylene group a phenylene group or a naphthylene group is preferable.
  • biarylene group a biphenylene group or a binaphthylene group is preferable.
  • alkyl group an alkyl group having a carbon number of from 1 to 10 is preferable.
  • aryl group a phenyl group or a naphthyl group is preferable.
  • a pyridyl group is preferable.
  • urethane polymer or oligomer represented by the foregoing formula (A) As the urethane polymer or oligomer represented by the foregoing formula (A), UN-1225 (manufactured by Negami Chemical Industrial Co., Ltd.), CN962, CN965, and CN971 (all of which are manufactured by Sartomer Company Inc.), and the like can be preferably used.
  • the "active energy ray-cured oligomer or polymer” in the invention expresses an oligomer or polymer compound that is a polymer of an active energy ray-curable monomer.
  • the oligomer as referred to in the invention is not limitative, for example, it refers to a polymer having a molecular weight of from 1,000 to 5,000.
  • the polymer as referred to in the invention for example, refers to a polymer having a molecular weight of 5,000 or more, and preferably a compound having a molecular weight of from 5,000 to 10,000.
  • the resin material which can be used in the invention may . contain at least one member selected from an active energy ray-curable monomer and an active energy ray-cured oligomer or polymer.
  • the "active energy rays" as referred to in the invention are not particularly limited so far as they are able to impart energy capable of generating an initiating species upon irradiation thereof, and they broadly include oc-rays, ⁇ -rays, X-rays, ultraviolet rays, visible light, electron beams, and the like. Above all, from the viewpoints of curing sensitivity and easiness of availability of apparatus, ultraviolet rays and electron beams are preferable, and ultraviolet rays are especially preferable.
  • the curable monomer which is used in the invention is preferably a monomer which can be cured upon irradiation with ultraviolet rays as the active energy rays.
  • the curable monomer is not particularly limited so far as it is cured upon irradiation with active energy rays, and any of radical polymerizable compounds and cationic polymerizable compounds can be used. From the viewpoints of stability and compound variation, radical polymerizable compounds are preferable, and compounds having an unsaturated double bond are more preferable.
  • any compound having at least one radical polymerizable ethylenically unsaturated bond in a molecule thereof may be used, and compounds having a chemical form such as a monomer, an oligomer, and a polymer are included.
  • the radical polymerizable compound may be used solely, and may be used in combination of two or more kinds thereof in an arbitrary ratio for the purpose of enhancing the desired characteristics. From the standpoint of controlling performances such as reactivity and physical properties, it is preferable to use two or more kinds of radical polymerizable compounds in combination.
  • N-vinyl lactam as the compound having an unsaturated double bond. This is because in addition to the fact that the N-vinyl lactam is able to form a resin having good adhesion to the base material by curing, not only it is able to form a tough polymer blend layer due to an interaction between the hydrophilic material and a hydrogen bond, but the flexibility of an oligomer and a polymer formed after curing is high, thereby enabling one to achieve energy relaxation against an external impact or a deformation force.
  • N-vinyl lactam examples include compounds represented by the following formula (A).
  • n represents an integer of from 1 to 5. From the viewpoints of flexibility after the ink is cured, adhesion to the base material, and availability of a raw material, n is preferably an integer of from 2 to 4. N-Vinylpyrrolidone or N-vinyl caprolactam in which n is an integer of 2 or 4, respectively is more preferable, and N-vinyl caprolactam in which n is 4 is especially preferable. N- Vinyl caprolactam is preferable because it is excellent in safety, versatile, and relatively inexpensively available, and in particular, good ink curing properties and adhesion of the cured layer to the base material are obtainable.
  • N-vinyl lactam may have a substituent such as an alkyl group and an aryl group on a lactam ring thereof and may be connected with a saturated or unsaturated ring structure.
  • a content of the N-vinyl lactam in the ink is preferably 10 % by mass or more relative to a total mass of the ink. What the N-vinyl lactam is contained in an amount of 10 % by mass or more of the whole of the ink is preferable because an ink which is excellent in curing properties, flexibility of the cured layer, and adhesion of the cured layer to the base material can be provided.
  • the content of the N-vinyl lactam in the ink is more preferably in the range of 30 % by mass or more and not more than 80 % by mass.
  • the N-vinyl lactam is a compound having a relatively high melting point.
  • the content of the N-vinyl lactam in the ink is still more preferably in the range of 30 % by mass or more and not more than 70 % by mass, and especially preferably in the range of 40 % by mass or more and not more than 60 % by mass.
  • N-vinyl lactam may be contained solely, or may be contained in admixture of plural kinds thereof in the ink.
  • examples of other compounds having an unsaturated double bond include radical polymerizable compounds such as unsaturated carboxylic acids, e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, and salts thereof, anhydrides having an ethylenically unsaturated group, acrylonitrile, styrene, and a variety of unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes.
  • unsaturated carboxylic acids e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, and salts thereof, anhydrides having an ethylenically unsaturated group, acrylonitrile, styrene, and a variety of unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes
  • examples thereof include acrylic acid derivatives such as 2-hydroxyethyl acrylate, butoxyethyl acrylate, 2-ethylhexyl acrylate, carbitol acrylate, tetrafurfuryl acrylate, bis(4-acryloxypolyethoxyphenyl)propane, neopentyl glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, N-methylolacrylamide, diacetone acrylate,
  • radical polymerizable or crosslinkable monomers, oligomers, and polymers which are commercially available or known in the industry and which are described in Crosslinking Agent Handbook, edited by Shinzo YAMASHITA (published by Taiseisha Ltd. (1981)); UV-EB Curing Handbook (Raw Material Volume), edited by Kiyoshi KATO (published by Kobunshi Kankokai (1985)); Applications and Markets of UV EB Curing Technologies, page 79, edited by RadTech Japan (published by CMC Publishing Co., Ltd. (1989)); Polyester Resin Handbook, written by Eiichiro TAKIYAMA (published by The Nikkan Kogyo Shimbun, Ltd. (1988)); and so on are useful.
  • a ratio (mass ratio) of the N-vinyl lactam to the compound other than the N-vinyl lactam in the ink is preferably from 30/70 to 70/30, more preferably from 40/60 to 60/40, and still more preferably from 55/45 to 45/55.
  • radical polymerizable compound examples of polymerizable compound materials of a photocuring type which are used for a photopolymerizable composition disclosed in, for example, JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-9-134011, etc. are known, and these materials are also applicable to the ink composition of the invention.
  • a vinyl ether compound as the radical polymerizable compound.
  • the vinyl ether compound which is suitably used include di- or trivinyl ether compounds such as ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hydroxyethyl monovinyl ether, and trimethylolpropane trivinyl ether; and monovinyl ether compounds such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, hydroxybutyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-O-propylene carbonate, and diethylene glycol monovin
  • vinyl ether compounds from the viewpoints of curing properties, adhesion, and surface hardness, divinyl ether compounds and trivinyl ether compounds are preferable, and divinyl ether compounds are especially preferable.
  • the vinyl ether compound may be used solely, or may be properly used in combination of two or more kinds thereof.
  • a photopolymerization initiator is contained in the resin material.
  • the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, and coumarins.
  • the photopolymerization initiators are also described in JP-A-2008-134585, paragraphs [0141] to [0159], and these can also be suitably used in the invention.
  • the photopolymerization initiator is used in an amount preferably ranging from 0.1 to 15 parts by mass, and more preferably ranging from 1 to 10 parts by mass based on 100 parts by mass of the organic component having a polymerizable group.
  • a photosensitizer may be used.
  • the photosensitizer include n-butylamine, triethylamine, tri-n-butyl phosphine, Michler's ketone, and thioxanthone.
  • auxiliary agents such as azide compounds, thiourea compounds, and mercapto compounds may be combined and used.
  • commercially available photosensitizers include "KAYACURE DMBI” and “KAYACURE EPA", all of which are manufactured by Nippon Kayaku Co., Ltd., and "LUCIRIN TPO", manufactured BASF AG.
  • the base material which is used in the invention is not particularly limited. Any of glasses, plastics, metals, ceramics, woods, stones, cements, concretes, fibers, textiles, papers, leathers, combinations thereof, and laminates thereof can be suitably utilized. As the base material, glass substrates and plastic substrates are more preferable, and plastic substrates are especially preferable.
  • any glasses such as soda-lime glass, lead glass, and boro-silicate glass may be used.
  • float sheet glass, figured sheet glass, ground sheet glass, wire glass, crosswire glass, tempered glass, laminated glass, vacuum glass, security glass, and high-heat insulating Low-E multilayered glass can be used depending upon the purpose.
  • the foregoing hydrophilic layer can be coated on a raw sheet glass as it is, for the purpose of enhancing the adhesion of the hydrophilic layer, one surface or both surfaces of the sheet glass can be subjected to a surface hydrophilization treatment such as an oxidation method and a roughing method as the need arises.
  • Examples of the foregoing oxidation method include a corona discharge treatment, a glow discharge treatment, a chromic acid treatment (wet type), a flame treatment, a hot blast treatment, and an ozone or ultraviolet ray irradiation treatment.
  • a corona discharge treatment a glow discharge treatment, a chromic acid treatment (wet type), a flame treatment, a hot blast treatment, and an ozone or ultraviolet ray irradiation treatment.
  • a corona discharge treatment a glow discharge treatment, a chromic acid treatment (wet type), a flame treatment, a hot blast treatment, and an ozone or ultraviolet ray irradiation treatment.
  • a chromic acid treatment wet type
  • the plastic substrate which is used in the invention is not particularly limited, and examples thereof include films or sheets made of a polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, polystyrene, a polycarbonate, polymethylpentene, polysulfone, polyether ketone, an acrylic resin, a nylon, a fluorocarbon resin, a polyimide, polyether imide, polyether sulfone, or the like.
  • polyester films made of polyethylene terephthalate, polyethylene naphthalate, etc. are preferable.
  • plastic substrates with excellent transparency are preferable. Translucent or printed plastic substrates are also used depending upon the application.
  • a thickness of the base material which can be used is usually from about 25 ⁇ to 1,000 ⁇ , preferably from 25 ⁇ to 250 ⁇ , and more preferably from 30 ⁇ to 90 ⁇ .
  • a width of the base material which can be used is arbitrary, from the standpoints of handling, yield, and productivity, it is usually not more than 1,000 mm, preferably not more than 800 mm, and still more preferably not more than 600 mm.
  • a transparent support can be handled lengthily in a roll form, and a length thereof is usually within 200 m, and preferably within 100 m.
  • an average roughness Ra value thereof is preferably not more than 1 ⁇ , more preferably not more than 0.8 ⁇ , and still more preferably not more than 0.7 ⁇ .
  • the hydrophilic member according to the invention is concerned with a hydrophilic member comprising a base material and a layer containing the following hydrophilic material (1) and an oligomer or polymer (hereinafter also referred to as "resin material (2)”), wherein the layer is a composition gradient layer in which a composition of (1) and (2) continuously changes in a thickness direction of the layer in such a manner that a ratio of (1) becomes large, whereas a ratio of (2) becomes small, from the nearest side to the base material toward the farthest side to the base material.
  • a layer thickness of the composition gradient layer in the invention is not particularly limited, it is preferably 1 ⁇ or more, more preferably from 1 ⁇ to 20 ⁇ , and still more preferably from 3 ⁇ to 10 ⁇ . So far as the layer thickness of the composition gradient layer falls within this range, a hydrophilic member exhibiting good hydrophilicity can be obtained.
  • Fig. 1 schematically shows a cross section of a composition gradient layer which is contained in a hydrophilic member to be formed in the invention.
  • a hydrophilic member 1 according to the invention includes a pattern composed of a composition gradient layer 3 on a base material 2.
  • the composition continuously changes from the hydrophilic material (1) to the resin (2) in a thickness direction from a farthest side A to the base material 2 toward a nearest side B to the base material 2 (namely, in a direction of an arrow in Fig. 1).
  • the "thickness direction” as referred to herein means a "layer thickness direction” of the composition gradient layer 3.
  • composition continuously changes from the hydrophilic material (1) to the resin (2) in a thickness direction that when the composition gradient layer is divided into every region of a certain thickness (for example, from 0.1 to 5 ⁇ ) in the thickness direction, and a proportion of a mass of the resin (2) in each region relative to a total mass of the resin (2) and the hydrophilic material (1) (hereinafter also referred to as "content of resin”) is measured, a difference in the content of resin between adjacent regions to each other is not more than 50 %, and more preferably not more than 30 %.
  • the difference in the content of resin between adjacent regions to each other is not more than 50 %, the change in the content of resin does not become step-by-step, so that high adhesion and hydrophilicity can be obtained.
  • the difference in the content of resin between certain two adjacent regions to each other may be 0 %.
  • the content of resin on the farthest side A to the base material of the composition gradient layer 3 is preferably from 0 to 50 %, more preferably from 0 to 30 %, and still more preferably substantially 0 % (from 0 to 0.2 %).
  • the content of resin on the nearest side B to the base material of the composition gradient layer 3 is preferably from 50 to 100 %, more preferably from 70 to 100 %, and still more preferably substantially 100 % (from 99 to 100 %).
  • the content of resin in each region can be determined by, for example, a depth direction profile of XPS.
  • a configuration of the composition gradient layer 3 is not particularly limited so far as the content of resin continuously changes as described above, a configuration shown in Fig. 2, in which a plurality of layers having a different content of resin from each other are laminated, is exemplified as a preferred configuration.
  • a hydrophilic member la shown in Fig. 2 includes the composition gradient layer 3 on the base material 2, and the composition gradient layer 3 includes a plurality of layers 3-1 , 3-2, 3-3, 3-4 and 3-5 having a different content of resin from each other.
  • the content of resin becomes large continuously within the range of from 0 % to 100 % from the layer 3-5 on the farthest side A to the base material 2 toward the layer 3-1 on the nearest side B to the base material 2 (namely, in a direction of an arrow in Fig. 2).
  • a difference in the content of resin between adjacent two layers to each other is not more than 50 %, and preferably not more than 30 %.
  • the content of resin of the layer 3-5 on the farthest side A to the base material 2 is preferably from 0 % to 20 %, and more preferably from 0 % to 15 %.
  • the content of resin of the layer 3-1 on the nearest side B to the base material 2 is preferably from 80 % to 100 %, and more preferably from 85 % to 100 %.
  • a number of layers to be laminated is not particularly limited.
  • the layer number is preferably from 3 to 10 layers, and more preferably from 3 to 7 layers.
  • a thickness of each layer is preferably from 0.1 ⁇ to 5 ⁇ , and more preferably from 0.3 ⁇ to 3 ⁇ . It is preferable that the thickness of each layer is substantially identical (an error in the thickness falls within the range of ⁇ 0.5 ⁇ ).
  • a region obtained by dividing the composition gradient layer 3 into a thickness of from 0.1 ⁇ to 5 ⁇ in the thickness direction may be considered as "layer".
  • the content of resin in each region can be determined by, for example, a depth direction profile of XPS.
  • the invention is also concerned with a forming method of the hydrophilic member of the invention, which comprises ejecting at least two kinds of ink compositions of an ink composition containing the foregoing hydrophilic material (1) and an ink composition containing the foregoing resin material (2) onto the base material by an inkjet method.
  • the ink composition which is used in the invention is roughly classified into an ink composition containing the foregoing hydrophilic material (1) and an ink composition containing the foregoing resin material.
  • the ink composition may contain, in addition to the foregoing hydrophilic material (1) and the foregoing resin material, a solvent, a binder component, and other additives.
  • the ink composition may be used solely as an ink, or two or more kinds of ink compositions may be mixed and used as an ink.
  • an ink containing an ink composition containing the foregoing hydrophilic material (1) and an ink containing an ink composition containing the foregoing resin material may be each independently used as two or more kinds of inks, or a mixture of an ink containing an ink composition containing the foregoing hydrophilic material (1) and an ink containing an ink composition containing the foregoing resin material may be used as a mixed ink.
  • the ink may contain, in addition to the foregoing hydrophilic material (1) and the foregoing resin material, a solvent, a binder component, and other additives.
  • the ink composition according to the invention is prepared by mixing the foregoing hydrophilic material (1), the foregoing resin material, and a solvent.
  • the solvent can be properly chosen from water and organic solvents and used.
  • the solvent is preferably a liquid having a boiling point of 50°C or higher, and more preferably an organic solvent having a boiling point in the range of from 60°C to 300°C.
  • a solid content concentration in the ink composition is from 1 to 70 % by mass, and more preferably from 5 to 60 % by mass.
  • the obtained ink has a viscosity range with good workability.
  • Examples of the solvent include alcohols, ketones, esters, nitriles, amides, ethers, ether esters, hydrocarbons, and halogenated hydrocarbons.
  • examples thereof include alcohols (for example, methanol, ethanol, propanol, butanol, benzyl alcohol, ethylene glycol, propylene glycol, ethylene glycol monoacetate, cresol, etc.), ketones (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cyclohexanone, etc.), esters (for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, butyl formate, ethyl lactate, etc.), aliphatic hydrocarbons (for example, hexane, cyclohexane, etc.), halogenated hydrocarbon
  • solvents can be used solely or in admixture of two or more kinds thereof.
  • the preferred solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, isopropanol, and butanol.
  • the ink composition according to the invention can contain, in addition to the foregoing hydrophilic material (1) and the foregoing resin material, other additives such as a surface tension modifier, an antifouling agent, a water resistance imparting agent, and a chemical resistance imparting agent.
  • other additives such as a surface tension modifier, an antifouling agent, a water resistance imparting agent, and a chemical resistance imparting agent.
  • a viscosity of the ink according to the invention is preferably from 5 to 40 cP, more preferably from 5 to 30 cP, and still more preferably from 8 to 20 cP.
  • a surface tension of the ink is preferably from 10 to 40 mN/m, more preferably from 15 to 35 mN/m, and still more preferably from 20 to 30 mN/m.
  • composition gradient layer by the inkjet method according to the invention is hereunder described.
  • the ink containing an ink composition containing the foregoing hydrophilic material (1) and the ink containing an ink composition containing the foregoing resin material are each independently ejected as two or more kinds of inks onto the base material by the inkjet method, or a mixed ink which is a mixture of the ink containing an ink composition containing the hydrophilic material and the ink containing an ink composition containing the resin material is ejected onto the base material by the inkjet method.
  • the inkjet method is not limited on the inkjet recording system so far as it is a method for undergoing image recording by an inkjet printer.
  • Examples thereof include known systems such as a charge control system of ejecting an ink composition by utilizing an electrostatic attractive force; a drop-on-demand system utilizing a vibration pressure of a piezoelectric element (pressure pulse system); an acoustic inkjet system of ejecting an ink composition by converting electric signals into acoustic beams, irradiating them on the ink composition, and utilizing a radiation pressure; and a thermal inkjet system of heating an ink composition to form air bubbles and utilizing a generated pressure (Bubble Jet (registered trademark)).
  • a charge control system of ejecting an ink composition by utilizing an electrostatic attractive force such as a drop-on-demand system utilizing a vibration pressure of a piezoelectric element (pressure pulse system); an acoustic inkjet system of ejecting an in
  • the control of droplets of the ink is carried out chiefly by a printer head.
  • a printer head For example, in the case of a thermal inkjet system, it is possible to control a droplet ejection amount by a structure of the print head. That is, it is possible to eject the droplets in a desired size by changing the size of an ink chamber, a heating part, or a nozzle.
  • ejection of droplets having a plurality of sizes by providing a plurality of print heads having a different size in the heating part or nozzle.
  • an ejecting method (image formation method) of the ink onto the base material there is exemplified an image formation mixing method in which the ink containing an ink composition containing the hydrophilic material and the ink containing an ink composition containing the resin material are supplied into separate inkjet heads, respectively and simultaneously ejected while adjusting a ratio in an ejection amount of the both inks, and mixed on the base material.
  • a mixing ink method in which plural kinds of mixed inks previously prepared by mixing the ink containing an ink composition containing the hydrophilic material and the ink containing an ink composition containing the resin material, which mixed inks are different in a ratio between the both inks from each other, are supplied into inkjet heads, and the mixed inks having a different ratio between the ink containing an ink composition containing the hydrophilic material and the ink containing an ink composition containing the resin material from each other are successively ejected by selecting the head in order, thereby forming an image.
  • Each of the foregoing inks can be prepared by mixing the respective materials.
  • the materials may be stirred using a stirrer.
  • a stirring time is not particularly limited, it is usually from 30 minutes to 60 minutes, and preferably from 30 minutes to 40 minutes.
  • a temperature is usually from 10°C to 40°C, and preferably from 20°C to 35°C.
  • the above-prepared inks can be mixed and used.
  • the method of the invention is preferably a forming method of a hydrophilic member including a base material and a layer containing the foregoing hydrophilic material (1) and an oligomer or polymer (resin (2)), wherein the layer is a composition gradient layer in which a composition of (1) and (2) continuously changes in a thickness direction of the layer in such a manner that a ratio of (1) becomes large, whereas a ratio of (2) becomes small, from the nearest side to the base material toward the farthest side to the base material, which comprises ejecting at least two kinds of ink compositions of an ink containing an ink composition containing the foregoing hydrophilic material (1) and an ink containing an ink composition containing the foregoing resin material onto the base material by an inkjet method, wherein
  • At least an ink composition containing the foregoing hydrophilic material (1) and an ink composition containing the foregoing resin material are used as the at least two kinds of ink compositions, and
  • the inkjet method uses at least a first inkjet head and a second inkjet head, and wherein the method includes
  • the ratio is determined such that a ratio of the first ink becomes large, whereas a ratio of the second ink becomes small, in a thickness direction of the plural layers from the nearest side to the base material toward the farthest side to the base material.
  • the composition gradient layer can be manufactured adopting a technology of the inkjet system.
  • the invention is also concerned with a hydrophilic member formed by the foregoing image formation method.
  • Fig. 3 is an overall configuration view of a composition gradient layer fabrication apparatus 100 according to the image formation mixing method
  • Fig. 4 is a diagrammatic view of an image formation section 10 of the composition gradient layer fabrication apparatus 100.
  • the composition gradient layer fabrication apparatus 100 is configured to include the image formation section 10, and for the image formation section 10, an inkjet image formation apparatus of a flat head type is used.
  • the image formation section 10 is configured to include a stage 30 on which a base material 20 is loaded; a suction chamber 40 for suctioning and holding the base material 20 loaded on the stage 30; and an inkjet head 50A (hereinafter referred to as “inkjet head 1”) and an inkjet head 50B (hereinafter referred to as “inkjet head 2”), each of which ejects each ink toward the base material 20.
  • a stage 30 on which a base material 20 is loaded
  • a suction chamber 40 for suctioning and holding the base material 20 loaded on the stage 30
  • an inkjet head 50A hereinafter referred to as "inkjet head 1"
  • an inkjet head 50B hereinafter referred to as “inkjet head 2”
  • the stage 30 has a width dimension which is greater than the diameter of the base material 20 and is configured so as to be movable freely in the horizontal direction by means of a non-illustrated movement mechanism.
  • a movement mechanism it is possible to use, for example, a rack-and-pinion mechanism, a ball screw mechanism, or the like.
  • a stage control part 43 (not illustrated in Fig. 4) is able to move the stage 30 to a desired position by controlling the movement mechanism.
  • a lot of suction holes 31 are formed on a base material holding surface of the stage 30.
  • the suction chamber 40 is provided on the lower surface of the stage 30, and the base material 20 on the stage 30 is suctioned and held by means of vacuum suction of the suction chamber 40 by a pump 41 (not shown in Fig. 4).
  • the stage 30 includes a heater 42 (not shown in Fig. 4), and it is possible to heat the base material 20 suctioned and held on the stage 30.
  • the inkjet heads 1 and 2 eject inks supplied from an ink tank 60 A (hereinafter referred to as “ink tank 1”) and an ink tank 60B (hereinafter referred to as “ink tank 2”) at desired positions on the transparent support 20, and here, heads having an actuator of a piezoelectric system are used, respectively.
  • the inkjet heads 1 and 2 are respectively arranged and fixed as closely as possible to each other, by means of a non-illustrated fixing device.
  • the inks supplied from the ink tanks 1 and 2 into the inkjet heads 1 and 2 are referred to as “ink 1" and “ink 2", respectively.
  • the ink containing an ink composition containing the foregoing hydrophilic material (1) (hereinafter also referred to as “hydrophilic ink”) is referred to as the "ink 1"; and the ink containing an ink composition containing the forgoing resin material (2) (hereinafter also referred to as “resin ink”) is referred to as the "ink 2".
  • composition gradient layer fabrication apparatus 100 The fabrication of a composition gradient layer using the thus configured composition gradient layer fabrication apparatus 100 is described by reference to Figs. 5 A, 5B, 5C, 5D and 5E.
  • the base material 20 is loaded on the stage 30 of the image formation section 10 which is situated in a nitrogen atmosphere.
  • the base material 20 is loaded in such a manner that a rear surface thereof comes into contact with the stage 30.
  • the base material 20 is suctioned onto the stage 30 by the suction chamber 40 and heated.
  • the ink 2 is laminated by ejecting the ink 2 from the inkjet head 2 while moving the stage 30 by means of a movement mechanism (moving it in the leftward direction in Fig. 5A).
  • the ink is not ejected from the inkjet head 1. It is preferable to dry the layer 24-1 of the ink 2 formed in this way to such an extent that the solvent component in the ink 2 is not completely evaporated off (in a state of semi-drying or semi-curing). Specifically, drying is performed with less energy than the energy applied at the time of usual drying (full drying or full curing).
  • the terms “semi-drying” and “full drying” include the meanings of “semi-curing” and “full curing” in the case of using of a curing type composition such as a sol-gel curing type composition as the ink according to the invention.
  • the layer ejected in the foregoing forming step it is preferable to include a step of semi-drying the layer ejected in the foregoing forming step.
  • a step of semi-drying for example, after completion of ejecting the ink, it is preferable to hold the system at an environmental temperature of from 40 to 120°C for a certain time, and it is more preferable to hold the system at an environmental temperature of from 50 to 100°C for a certain time.
  • the holding time is preferably from 10 to 120 seconds, and more preferably from 20 to 90 seconds.
  • a mixed layer 24-2 of the ink 1 and the ink 2 is formed on the layer 24-1 of the ink 2 in a semi-dried state.
  • the formation of this mixed layer 24-2 is carried out by ejecting the ink 1 from the inkjet head 1 and simultaneously ejecting the ink 2 from the inkjet head 2 while moving the stage 30. At that time, an ejection amount of the ink 1 and an ejection amount of the ink 2 are adjusted to a desired ratio.
  • the ink 1 and the ink 2 are ejected by adjusting the ejection amounts of respective nozzles of the inkjet heads 1 and 2 in such a manner that the ejection amount of the ink 2 is 75 %, whereas the ejection amount of the ink 1 is 25 %.
  • the "ejection amount" of the ink as referred to in this specification means a total amount of the ink to be ejected for the purpose of forming each layer.
  • a "droplet amount" of an ink droplet to be ejected from the inkjet head, as described later means an amount of one ink droplet.
  • the adjustment of the ratio in the ejection amounts of the inks from the inkjet heads 1 and 2 may also be made by a dot pitch density of image formation.
  • the ink 1 and the ink 2 which have been ejected in the respective ejection amounts are diffused and mixed, thereby laminating the mixed layer 24-2. Since the layer 24-1 of the ink 1 is in a semi-dried state, the solvent of the ink of the mixed layer 24-2 formed thereon is received in the layer 24-1 of the ink 1 and does not wet and spread to a very great extent. That is, the heating temperature by the heater 42 needs to be adjusted in accordance with easiness of evaporation of the ink. Depending on the type of the solvent, it is possible to form an image by setting the substrate temperature to a temperature lower than 70°C as described above, for example, about 50°C.
  • a step of diffusing and mixing the ejected first ink and the ejected second ink it is preferable to include a step of diffusing and mixing the ejected first ink and the ejected second ink.
  • Examples of a method for achieving diffusion and mixing include a method of utilizing convection by heating and a method of utilizing ultrasonic waves.
  • the two inkjet heads are arranged as closely as possible to each other, and hence, it is possible to prevent only one of the inks from drying and causing insufficient diffusion and mixing within the layer.
  • a droplet of the ink 1 ejected from the inkjet head 1 and a droplet of the ink 2 ejected from the inkjet head 2 may be allowed to collide with each other in the air during flight and land and combine with each other, following by deposition.
  • each of the two inkjet heads is configured so as to have a greater width than the width of the objective base material (shorter one), and one layer is formed by one scanning. According to this, the ink 1 and the ink 2 are easily mixed with each other.
  • the base material 20 may be subjected to an ultrasonic treatment by controlling the stage 30. At that time, in order that nodes by ultrasonic waves may be hardly generated, it is preferable to carry out this treatment while sweeping the frequency of the ultrasonic waves or changing the position of the base material 20.
  • the mixed layer 24-2 formed in this way is in a semi-dried state similar to the layer 24-1 of the ink 2, the mixed layer 24-2 is in a state where the resin material contained in the ink 2 and the foregoing hydrophilic material contained in the ink 1 are mixed in a ratio of 75/25 and superimposed.
  • a mixed layer 24-3 is formed on the mixed layer 24-2.
  • the inks are simultaneously ejected from the inkjet head 1 and the inkjet head 2 while moving the stage 30.
  • both of the ink 1 and the ink 2 are ejected at a ratio of the ejection amount of 50 %.
  • the mixed layer 24-2 Since the mixed layer 24-2 is also in a semi-dried state, the solvent in the ink of the mixed layer 24-3 formed thereon is received in the mixed layer 24-2. As shown in Fig. 5E, after the ink ejection, the mixed layer 24-3 is laminated by diffusing and mixing the two inks.
  • the mixed layer 24-3 is also semi-dried similar to the layer 24-1 of the ink 2.
  • the mixed layer 24-3 is in a state where the resin material contained in the ink 2 and the hydrophilic material contained in the ink 1 are mixed in a ratio of 50/50 and superimposed.
  • the composition gradient layer 3 having a composition component ratio which changes from 100 % for the ink 2 to 100 % for the ink 1 from the side B toward the side A is formed.
  • the diffusion may progress to a certain extent in the upper and lower layers.
  • the state is avoided in which there is no interface between the upper and lower layers, i.e., the layers attain a state where they are completely mixed, so that there is no distinction between the upper and lower layers.
  • a dummy pattern may be laminated in a region of the composition gradient layer which does not function, followed by measuring a height of the dummy pattern by an optical displacement sensor using a laser, or the like.
  • an optical displacement sensor using a laser, or the like.
  • a droplet amount of the ink droplet ejected from each of the first inkjet head and the second inkjet head is preferably from 0.3 to 100 pL, more preferably from 0.5 to 80 pL, and still more preferably from 0.7 to 70 pL.
  • a droplet size of the ink droplet ejected from each of the first inkjet head and the second inkjet head is preferably from 1 to 300 ⁇ , more preferably from 5 to 250 ⁇ , and still more preferably from 10 to 200 ⁇ .
  • the ink having a smaller ratio of the ejection amount between the first ink and the second ink it is preferable that at least one of the droplet amount and the droplet size of the ink droplet to be ejected from the inkjet head is smaller than that in the ink in which the foregoing ratio is larger.
  • the ink droplet of the ink in which the foregoing ratio is smaller is from 0.3 to 60 pL
  • the ink droplet of the ink in which the foregoing ratio is larger is from 1 to 100 pL. According to this, it is possible to shorten the time for diffusion and mixing, or to enhance the uniformity of mixing.
  • the "droplet size" of the ink droplet as referred to herein means a length of the droplet diameter, and it can be measured from a photograph of the flying state at the time of inkjet ejection.
  • the composition gradient layer 3 having a composition ratio which changes from 100 % for the ink 2 to 100 % for the ink 1 from the side B toward the side A is formed.
  • it is not always required to fabricate a layer in such a manner that the ink 2 or the ink 1 is 100 % on the side B or the side A. So far as the composition gradient layer 3 is obtainable, the ratio of the ink 2 or the ink 1 on the side B or the side A can be arbitrarily changed.
  • the ratio of the ink 2 or the ink 1 on the side B or the side A can be properly adjusted depending upon characteristics of the composition gradient layer which is intended to be obtained, such as adhesion and hydrophilicity.
  • the inks are simultaneously ejected at the inkjet head 1 and the inkjet head 2, thereby forming the respective layers.
  • the inks may be ejected sequentially.
  • the ink 2 is ejected on the whole surface of the layer 24-1 of the ink 2 from inkjet head 2.
  • the ink 1 is ejected on the whole surface from the inkjet head 1.
  • the mixed layer 24-2 can be similarly formed.
  • the ink having a smaller ejection amount, which is ejected subsequently may be ejected at a higher dot pitch density by a smaller droplet (the droplet amount is smaller, or the droplet size is smaller). According to this, the time required for diffusion and mixing can be shortened.
  • the ink it is also possible to deposit the ink to be ejected subsequently in a superimposed fashion, on the positions where the ink ejected first has been deposited.
  • the dots are separated from each other, when a droplet is deposited at the same position before drying, the respective inks are easily mixed with each other.
  • Fig. 9A shows the ink 2 (24-2-B-l) which has been deposited on the layer 24-1 of the ink layer 1.
  • the ink 1 is ejected by intermittent ejection from the inkjet head 1.
  • the inkjet head 1 performs ejection in such a manner that the ejected ink 1 (24-2-A-l) is deposited in a superimposed fashion at the same position as the ink 2 (24-2-B-l) deposited at the first scanning.
  • Fig. 9C shows the ink 2 (24-2-B-2) which has been deposited between the dots of the ink 2 (24-2-B-l).
  • the inkjet head 1 performs ejection in such a manner that the ink 1 is deposited in a superimposed fashion at the same positions as the ink 2 (24-2-B-2).
  • the inkjet head 1 performs ejection in such a manner that the ejected ink 1 (24-2-A-2) is deposited in a superimposed fashion at the same positions as the ink 2 (24-2-B-2) deposited in the second scanning.
  • the inks are ejected onto the whole surface of the layer 24-1 of the ink 1 and then diffused and mixed.
  • the inks are ejected onto the whole surface of the layer 24-1 of the ink 1 and then diffused and mixed.
  • the respective mixed layers are formed using two pure inks of the ink 1 and the ink 2, but an ink obtained by mixing these inks may be used in combination.
  • it may be considered to form a mixed layer by simultaneously using inks of three types composed of two pure inks and a mixed ink of the ink 1 and the ink 2 in a mixing ratio of 50/50.
  • the number of inkjet heads increases in accordance with the mixed ink, the two pure inks are sufficiently mixed together in advance in the mixed ink, and therefore, the time required for diffusion and mixing after ejection of the ink can be shortened.
  • the method of the invention is preferably a forming method of a hydrophilic member including a base material and a layer containing the foregoing hydrophilic material (1) and an oligomer or polymer (resin (2)), wherein the layer is a composition gradient layer in which a composition of (1) and (2) continuously changes in a thickness direction of the layer in such a manner that a ratio of (1) becomes large, whereas a ratio of (2) becomes small, from the nearest side to the base material toward the farthest side to the base material, which comprises ejecting at least two kinds of ink compositions of an ink composition containing the foregoing hydrophilic material (1) and an ink composition containing the resin material onto the base material by an inkjet method, wherein
  • At least an ink composition containing the foregoing hydrophilic material (1) and an ink composition containing the foregoing resin material are used as the at least two kinds of ink compositions, and
  • the inkjet method uses a plurality of inkjet heads, and wherein the method includes a step of supplying a plurality of mixed inks which are a mixture of the first ink containing an ink composition containing the foregoing hydrophilic material (1) and the second ink containing an ink composition containing the foregoing resin material, and which are different in a mixing ratio from each other, into the plurality of inkjet heads, respectively, a selecting step of successively selecting one inkjet head from the plurality of inkjet heads and successively selecting the inkjet head into which the mixed ink having a high ratio of the second ink is supplied, a forming step of ejecting the mixed ink from the selected inkjet head, thereby forming one layer, and
  • a plurality of mixed inks which are a mixture of the first ink and the second ink and in which the inks are mixed in a different ratio, respectively are supplied into the respective inkjet heads, and the respective layers are formed by ejecting the mixed ink from the inkjet head into which the mixed ink having a low ratio of the first ink is supplied sequentially, thereby laminating a plurality of layers on the base material.
  • a composition gradient layer can be manufactured adopting the technology of an inkjet system.
  • the invention is also concerned with a hydrophilic member formed by the foregoing image formation method.
  • Fig. 7 is an overall configuration view of a composition gradient layer fabrication apparatus 101 according to a second embodiment.
  • the composition gradient layer fabrication apparatus 101 according to the present embodiment includes an image formation section 11, and the image formation section 11 includes ink tanks 60-1 to 60-5 which store five kinds of inks, and inkjet heads 50-1 to 50-5 into which inks are supplied from the respective ink tanks 60-1 to 60-5.
  • the inkjet heads 50-1 to 50-5 eject inks supplied from the respective ink tanks 60-1 to 60-5 onto the base material 20.
  • the inks supplied from the ink tanks 60-1 to 60-5 into the inkjet heads 50-1 to 50-5 have respective mix ratios of the ink 1 and the ink 2 of 0/100, 25/75, 50/50, 75/25, and 100/0. That is, a pure ink of the ink 2 is supplied from the ink tank 60-1, a pure ink of the ink 1 is supplied from the ink tank 60-5, and mixed inks in which the ink 1 and the ink 2 are mixed in prescribed ratios are supplied from the ink tanks 60-2 to 60-4.
  • the base material 20 is loaded on the stage 30 and then suctioned and heated.
  • a layer 28-1 of the ink 2 is formed by laminating one layer or a plurality of layers of the ink 2 on the suctioned and heated base material.
  • the ink 2 is laminated by ejecting an ink supplied from the ink tank 60-1 (mixing ratio of the ink 1 and the ink 2: 0/100) from the inkjet head 50-1 while moving the stage 30 by means of a movement mechanism (moving it in the leftward direction in Fig. 8A). At that time, an ink is not ejected from the other inkjet heads 50-2 to 50-5.
  • the thus formed layer 28-1 of the ink 2 is a layer similar to the layer 24-1 of the ink 2 shown in Figs. 5 A to 5E.
  • the ink is dried to such an extent that the solvent in the ink 2 is evaporated (semi-dried or semi-cured), the hydrophilic material contained in the ink 1 is superimposed thereon.
  • this ink mixing method it is also preferable to include a step of semi-drying the layer ejected in the foregoing forming step.
  • a step of semi-drying for example, after completion of ejecting the ink, it is preferable to hold the system at an environmental temperature of from 40 to 120°C for a certain time, and it is more preferable to hold the system at an environmental temperature of from 50 to 100°C for a certain time.
  • the holding time is preferably from 10 to 120 seconds, and more preferably from 20 to 90 seconds.
  • a mixed layer 28-2 is formed on the layer 28-1 of the ink 2 by ejecting a mixed ink (a mixed ink of the ink 1 and the ink 2 in a mixing ratio of 25/75) supplied from the ink tank 60-2 by the inkjet head 50-2.
  • the mixed ink is ejected from the inkjet head 50-2 while moving the stage 30. Similar to the embodiment by the image formation mixing method, since the layer 28-1 of the ink 2 is in a semi-dried state, the solvent of the ink of the mixed layer 28-2 formed thereon is received in the layer 28-1 of the ink 2 and does not wet and spread to a very great extent. In consequence, the heating temperature needs to be adjusted in accordance with easiness of evaporation of the ink.
  • the mixed layer 28-2 assumes a state where the hydrophilic material contained in the ink 1 and the resin material contained in the ink 2 are superimposed each other.
  • a mixed layer 28-3 is formed on the mixed layer 28-2 by ejecting a mixed ink (a mixed ink of the ink 1 and the ink 2 in a mixing ratio of 50/50) supplied from the ink tank 60-3 by the inkjet head 50-3 (not illustrated in Figs. 8A, 8B and 8C).
  • a mixed ink a mixed ink of the ink 1 and the ink 2 in a mixing ratio of 50/50
  • the mixed layer 28-2 Since the mixed layer 28-2 is in a semi-dried state, the solvent of the ink of the mixed layer 28-3 formed thereon is received in the mixed layer 28-2. Furthermore, the mixed layer 28-3 is also semi-dried.
  • the respective mixed layers (28-2 to 28-4) are laminated by ejecting the respective mixed inks in order from the largest mixing ratio of the ink 2 (i.e., in order from the smallest mixing ratio of the ink 1), and finally, a layer 28-5 composed of 100 % of the ink 1 (layer of the ink 1) is formed by ejecting the ink 1 (ink having a mixing ratio of the ink 1 and the ink 2 of 100/0) supplied from the ink tank 60-5 by the inkjet head 50-5 (Fig. 8C).
  • the composition gradient layer 3 having a composition component ratio which changes from 100 % for the ink 2 to 100 % for the ink 1 is formed.
  • a droplet amount of the ink droplet ejected from the inkjet head is preferably from 0.5 to 150 pL, more preferably from 0.7 to 130 pL, and still more preferably from 1 to 100 pL.
  • a droplet size of the ink droplet ejected from the inkjet head is preferably from 2 to 450 ⁇ , more preferably from 5 to 350 ⁇ , and still more preferably from 10 to 250 ⁇ .
  • the ink mixing method of the present embodiment since sufficient mixing is achieved at the stage of the ink, it is possible to fabricate a composition gradient layer with high precision on a change of the hydrophilic gradient.
  • a time is not required for diffusing and mixing two kinds of functional inks, and therefore, there is brought such an advantage that the process time may be shortened.
  • the number of layers is not particularly limited thereto. Any number of layers may be formed so far as the layers can be laminated so as to achieve a gradient of the mixing ratio of the respective inks. Incidentally, it is necessary to prepare ink tanks and inkjet heads corresponding to the number of layers to be formed.
  • the composition gradient layer 3 having a composition component ratio which changes from 100 % for the ink 2 to 100 % for the ink 1 is formed.
  • it is not always required to adopt a composition component ratio in which the ink 2 is 100 %, or the ink 1 is 100 %. So far as the composition gradient layer 3 is obtainable, the foregoing composition component ratio can be arbitrarily changed.
  • composition component ratio can be properly adjusted depending upon characteristics of the composition gradient layer which is intended to be obtained, such as adhesion and hydrophilicity.
  • Methylpyrrolidone manufactured by Wako Pure Chemical Industries, 450 g
  • the numerical values are a molar ratio, and a structural unit having a hydrophilic group is contained in an amount of 70 % by mole of the whole of the polymer.
  • a mass average molecular weight of this polymer is 15,000.
  • a hydrophilic member having a composition gradient layer having a thickness of 10 ⁇ was formed by the following inkjet image formation method A and heat dried at 100°C. Thereafter, the hydrophilic member was evaluated with respect to adhesion of the composition gradient layer to the base material, hydrophilicity, waterproof properties, anti-fogging properties, antifouling properties, and weather resistance.
  • the hydrophilic ink Bl and the resin ink Al were respectively filled in the ink tank 1 and the ink tank 2 as shown in Fig. 3.
  • the inks to be supplied into the inkjet head 1 and the inkjet head 2 are the hydrophilic ink Bl and the resin ink Al, respectively.
  • an ink droplet to be ejected from the inkjet head 2 was controlled so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇ , and the resin ink Al was ejected from the inkjet head 2 in a nitrogen gas atmosphere.
  • the ink layer 1 was formed without ejecting the hydrophilic ink Bl from the inkjet head 1 (namely, a ratio (% by mass) of an ejection amount of the ink ejected from the inkjet head 2 to an ejection amount of the ink ejected from the inkjet head 1 is 100/0) and semi-cured upon drying at 80°C for 30 seconds.
  • an ink droplet of the hydrophilic ink Bl to be ejected from the inkjet head 1 was adjusted so as to have a droplet amount of 5 pL and a droplet size of 20 ⁇
  • an ink droplet of the resin ink Al to be ejected from the inkjet head 2 was adjusted so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇ .
  • an ink droplet of the hydrophilic ink Bl was adjusted so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇
  • an ink droplet of the resin ink Al was adjusted so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇
  • an ink droplet of the hydrophilic ink Bl was adjusted so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇
  • an ink droplet of the resin ink Al was adjusted so as to have a droplet amount of 5 pL and a droplet size of 20 ⁇ .
  • an ink droplet of the hydrophilic ink Bl was adjusted so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇ .
  • a layer thickness of each of the ink layers 1 to 5 after full drying was adjusted to 2 ⁇ .
  • the fabricated hydrophilic member was subjected to a cross hatch test (EN ISO2409). Evaluation criteria were made in conformity with ISO2409, and the results were shown by a point system of evaluation of from point 0 to point 5.
  • the evaluation is made such that the point 0 is the highest in the adhesion, whereas the point 5 is the lowest in the adhesion.
  • a water droplet contact angle in air on the surface of the composition gradient layer of the hydrophilic member was measured using DropMaster 500, manufactured by manufactured by Kyowa Interface Science Co., Ltd.
  • the hydrophilic member having a size of 120 cm 2 was subjected to a rubbing treatment with a sponge at 20 reciprocations while applying a load of 2 kg, and a layer retention rate was measured from a change of mass before and after the treatment.
  • the coated sample was covered on a plastic cup charged with warm water at 80°C, and a state of fogging was visually decided according to the following criteria.
  • the hydrophilic member was exposed in a sunshine carbon arc-type accelerated weather resistance tester for 500 hours and evaluated with respect to adhesion, hydrophilicity, waterproof properties, anti-fogging properties, and antifouling properties according to the foregoing methods.
  • the evaluation was decided according to the following criteria.
  • Performance is equal to that before the exposure in all of the items.
  • a hydrophilic member having a composition gradient layer having a layer thickness of 10 ⁇ was formed by the following inkjet image formation method B by using five print heads in which five kinds of the foregoing inks also including the inks Al and Bl had been filled in order of Al (lowermost layer), Gl, G2, G3, and Bl (uppermost layer). After heat drying at 100°C, the hydrophilic member was evaluated with respect to adhesion of the composition gradient layer to the base material, hydrophilicity, waterproof properties, anti-fogging properties, antifouling properties, and weather resistance. The results are shown in the following Table 1.
  • the inks Al, Gl, G2, G3 and Bl were respectively filled in the ink tanks 60-1 to 60-5 as shown in Fig. 7.
  • the inks to be supplied into the inkjet heads 50-1 to 50-5 are the inks Al , Gl, G2, G3 and Bl, respectively.
  • the ink Al was ejected from the inkjet head 50-1 in a nitrogen gas atmosphere while controlling ink droplets to be ejected from the inkjet head so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇ .
  • the thus formed ink Al layer was semi-cured upon drying at 80°C for 30 seconds.
  • the ink Gl was similarly ejected from the inkjet head 50-2, and the ink Gl layer was laminated and semi-dried. This was also repeated with respect to the inks G2, G3 and Bl, lamination and semi-curing were repeated, and finally, full drying (at 110°C for 60 seconds) was performed to form a composition gradient layer.
  • a layer thickness of each of the ink layers Al, Gl, G2, G3 and Bl after full curing was adjusted to 2 ⁇ .
  • Hydrophilic members having a composition gradient layer having a layer thickness of 10 ⁇ were formed in the same method as that in Example 1, except that the hydrophilic polymer and the urethane oligomer or polymer contained in the hydrophilic ink and the resin ink were respectively replaced by those described in the following Table 1, and heat dried at 100°C. Thereafter, each of the hydrophilic members was evaluated with respect to adhesion of the composition gradient layer to the base material, hydrophilicity, waterproof properties, anti-fogging properties, antifouling properties, and weather resistance. The results are shown in the following Table 1.
  • the numerical values express a molar ratio at which the respective structural units are contained.
  • Hydrophilic inks containing the hydrophilic polymers of the foregoing Compound 2 and Compound 3 are corresponding to B2 and B3, respectively.
  • the adhesion between the base material and the composition gradient layer, the hydrophilicity, the waterproof properties, the anti-fogging property, the antifouling properties, and the weather resistance are good; and it is exhibited that the composition gradient layers fabricated by various inkjet methods A (image formation mixing method) and B (ink mixing method) are effective from the standpoint of practical use. Then, the two kinds of inkjet methods are equal in the effects to each other, so that it is possible to form a composition gradient layer having sufficient functions by any of these methods.
  • the inks containing a urethane exhibited good performances as compared with the inks containing other resin.
  • the urethane compound enhances an aggregation between the gradient layer and the base material and within the gradient layer due to a hydrogen bond interaction, thereby forming a firm layer.
  • Comparative Example 1 in the case of using an ink containing only the hydrophilic compound used in the invention and forming a hydrophilic member by means of usual inkjet image formation, the adhesion to the hydrophobic resin base material is not revealed because of the hydrophilic layer, and the separation easily occurs.
  • Comparative Example 2 since the hydrophilic compound and the urethane material are laminated, an interface with different kinds between hydrophobicity and hydrophilicity is present, sufficient adhesion to the base material is not revealed, and the problem of weather resistance that is an index of the durability becomes remarkable.
  • N-Vinyl caprolactam manufactured by Sigma-Aldrich: 50 g
  • Dipropylene glycol diacrylate (manufactured by Akcros Chemicals): 40 g
  • IRGACURE 184 (manufactured by Ciba Specialty Chemicals Inc.): 4 g
  • LUCIRIN TPO manufactured by BASF AG: 6 g
  • the numerical values are a molar ratio, and a structural unit having a hydrophilic group is contained in an amount of 70 % by mole of the whole of the polymer.
  • a mass average molecular weight of this polymer is 15,000.
  • a hydrophilic member having a composition gradient layer having a thickness of 10 ⁇ was formed by the following inkjet image formation method A and heat dried at 100°C. Thereafter, the hydrophilic member was evaluated with respect to adhesion of the composition gradient layer to the base material, hydrophilicity, waterproof properties, anti-fogging properties, antifouling properties, and weather resistance.
  • the hydrophilic ink Bl and the resin ink Al were respectively filled in the ink tank 1 and the ink tank 2 as shown in Fig. 3.
  • the inks to be supplied into the inkjet head 1 and the inkjet head 2 are the hydrophilic ink Bl and the resin ink Al , respectively.
  • an ink droplet to be ejected from the inkjet head 2 was controlled so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇ , and the resin ink Al was ejected from the inkjet head 2 in a nitrogen gas atmosphere.
  • the ink layer 1 was formed without ejecting the hydrophilic ink Bl from the inkjet head 1 (namely, a ratio (% by mass) of an ejection amount of the ink ejected from the inkjet head 2 to an ejection amount of the ink ejected from the inkjet head 1 is 100/0) and semi-cured upon drying at 80°C for 30 seconds.
  • curing was performed with energy (accumulated exposure amount with a metal halide lamp: 1,000 mJ/cm ) which is smaller than energy giving full curing.
  • an ink droplet of the hydrophilic ink Bl to be ejected from the inkjet head 1 was adjusted so as to have a droplet amount of 5 pL and a droplet size of 20 ⁇
  • an ink droplet of the resin ink Al to be ejected from the inkjet head 2 was adjusted so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇ .
  • an ink droplet of the hydrophilic ink Bl was adjusted so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇
  • an ink droplet of the resin ink Al was adjusted so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇
  • an ink droplet of the hydrophilic ink Bl was adjusted so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇
  • an ink droplet of the resin ink Al was adjusted so as to have a droplet amount of 5 pL and a droplet size of 20 ⁇ .
  • an ink droplet of the hydrophilic ink Bl was adjusted so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇ .
  • a layer thickness of each of the ink layers 1 to 5 after full curing was adjusted to 2 ⁇ .
  • the adhesion, the hydrophilicity, the waterproof properties, the anti-fogging properties, the antifouling properties, and the weather resistance were evaluated in the same manners as those in Examples 1 to 10 and Comparative Examples 1 to 2.
  • a hydrophilic member having a composition gradient layer having a layer thickness of 10 ⁇ was formed by the following inkjet image formation method B by using five print heads in which five kinds of the foregoing inks also including the inks Al and Bl had been filled in order of Al (lowermost layer), Gl, G2, G3, and Bl (uppermost layer). After heat drying at 100°C, the hydrophilic member was evaluated with respect to adhesion of the composition gradient layer to the base material, hydrophilicity, waterproof properties, anti-fogging properties, antifouling properties, and weather resistance. The results are shown in the following Table 2.
  • the inks Al , Gl, G2, G3 and Bl were respectively filled in the ink tanks 60-1 to 60-5 as shown in Fig. 7.
  • the inks to be supplied into the inkjet heads 50-1 to 50-5 are the inks Al, Gl, G2, G3 and Bl, respectively.
  • the ink Al was ejected from the inkjet head 50-1 in a nitrogen gas atmosphere while controlling ink droplets to be ejected from the inkjet head so as to have a droplet amount of 10 pL and a droplet size of 30 ⁇ .
  • the thus formed ink Al layer was semi-cured. Specifically, curing was performed with energy (accumulated exposure amount with a metal halide lamp: 1,000 mJ/cm 2 ) which is smaller than energy giving full curing.
  • the ink Gl was similarly ejected from the inkjet head 50-2, and the ink Gl layer was laminated and semi-cured. This was also repeated with respect to the inks G2, G3 and Bl, lamination and semi-curing were repeated, and finally, full curing (accumulated exposure amount with a metal halide lamp: 5,000 mJ/cm 2 ) was performed to form a composition gradient layer.
  • a film thickness of each of the ink layers Al , Gl , G2, G3 and Bl after full curing was adjusted to 2 ⁇ .
  • Hydrophilic members having a composition gradient layer having a layer thickness of 10 ⁇ were formed in the same method as that in Example 11 , except that the hydrophilic polymer and the curable monomer contained in the hydrophilic ink and the resin ink were respectively replaced by those described in the following Table 2, and heat dried at 100°C. Thereafter, each of the hydrophilic members was evaluated with respect to adhesion of the composition gradient layer to the base material, hydrophilicity, waterproof properties, anti-fogging properties, antifouling properties, and weather resistance. The results are shown in the following Table 2.
  • the numerical values express a molar ratio at which the respective structural units are contained.
  • Hydrophilic inks containing the hydrophilic polymers of the foregoing Compound 2 and Compound 3 are corresponding to B2 and B3, respectively.
  • the adhesion between the base material and the composition gradient layer, the hydrophilicity, the waterproof properties, the anti-fogging property, the antifouling properties, and the weather resistance are good; and it is exhibited that the composition gradient layers fabricated by various inkjet methods A (image formation mixing method) and B (ink mixing method) are effective from the standpoint of practical use. Then, the two kinds of inkjet methods are equal in the effects to each other, so that it is possible to form a composition gradient layer having sufficient functions by any of these methods.
  • the inks containing an N-vinyl lactam exhibited good performances as compared with the inks containing only other curable monomer.
  • the curable monomer dissolved a part of the base material, so that an interface was mixed to improve the adhesion, an aggregation within the gradient layer was enhanced due to a hydrogen bond interaction between the monomers, thereby forming a firm layer.
  • Comparative Example 3 in the case of using an ink containing only the hydrophilic compound used in the invention and forming a hydrophilic member by means of usual inkjet image formation, the adhesion to the hydrophobic resin base material is not revealed because of the hydrophilic layer, and the separation easily occurs.
  • Comparative Example 4 since the hydrophilic compound and the curable material are laminated, an interface with different kinds between hydrophobicity and hydrophilicity is present, sufficient adhesion to the base material is not revealed, and the problem of weather resistance that is an index of the durability becomes remarkable.

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  • Wood Science & Technology (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un élément hydrophile qui comprend une matière de base; et une couche contenant une matière hydrophile (1) et un oligomère ou polymère (2), la couche est une couche à gradient de composition dans laquelle une composition de (1) et (2) change de façon continue dans une direction d'épaisseur de la couche d'une manière telle qu'un rapport de (1) devient important, alors qu'un rapport de (2) devient faible, du côté le plus proche de la matière de base vers le côté le plus éloigné de la matière de base, la matière hydrophile (1) est une matière hydrophile contenant un polymère hydrophile contenant un groupe silyle hydrolysable, le polymère ayant au moins un groupe silyle hydrolysable représenté par la formule (a) tel que défini ici à une extrémité de chaîne principale ou une chaîne latérale d'une molécule de celui-ci et ayant au moins un groupe hydrophile dans la molécule, et l'oligomère ou le polymère (2) est différent du polymère hydrophile (1).
PCT/JP2012/073962 2011-09-16 2012-09-12 Elément hydrophile et son procédé de fabrication Ceased WO2013039252A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111334183A (zh) * 2020-04-29 2020-06-26 温州好惠报企业管理有限公司 一种水性可紫外光固化涂料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06171026A (ja) * 1992-12-10 1994-06-21 Mitsubishi Paper Mills Ltd 剥離用シート及びその製造方法
JP2008284715A (ja) * 2007-05-15 2008-11-27 Fujifilm Corp 親水性部材
JP2008310007A (ja) * 2007-06-14 2008-12-25 Seiko Epson Corp 光学物品とその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06171026A (ja) * 1992-12-10 1994-06-21 Mitsubishi Paper Mills Ltd 剥離用シート及びその製造方法
JP2008284715A (ja) * 2007-05-15 2008-11-27 Fujifilm Corp 親水性部材
JP2008310007A (ja) * 2007-06-14 2008-12-25 Seiko Epson Corp 光学物品とその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111334183A (zh) * 2020-04-29 2020-06-26 温州好惠报企业管理有限公司 一种水性可紫外光固化涂料及其制备方法

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