WO2011162225A1 - Modificateur de surface - Google Patents

Modificateur de surface Download PDF

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WO2011162225A1
WO2011162225A1 PCT/JP2011/064098 JP2011064098W WO2011162225A1 WO 2011162225 A1 WO2011162225 A1 WO 2011162225A1 JP 2011064098 W JP2011064098 W JP 2011064098W WO 2011162225 A1 WO2011162225 A1 WO 2011162225A1
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group
carbon atoms
formula
hydrogen atom
meth
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PCT/JP2011/064098
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English (en)
Japanese (ja)
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和義 松岡
恭典 宮下
猿渡　欣幸
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大阪有機化学工業株式会社
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Priority claimed from JP2010247944A external-priority patent/JP5683906B2/ja
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Publication of WO2011162225A1 publication Critical patent/WO2011162225A1/fr

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    • 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
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes

Definitions

  • the present invention relates to a surface modifier. More specifically, the present invention relates to, for example, a surface modifier and a surface that can impart hydrophilicity or hydrophobicity to the substrate surface, or can simultaneously impart both hydrophilicity and hydrophobicity to the substrate surface. It relates to a hydrophilizing agent.
  • the surface modifier and the surface hydrophilizing agent of the present invention include a glass surface treating agent, a coating surface treating agent, a printing surface treating agent, a medical material, a biocompatible material, an optical material, a resin film, and a resin sheet. It is expected to be used in a wide range of applications.
  • hydrophilic substrates As surface characteristics required for hydrophilic substrates, antifogging properties, antistatic properties, antifouling properties and the like are known. These surface properties are generally imparted by imparting hydrophilicity to the substrate.
  • a hydrophilic graft polymer in which a hydrophilic acrylamide polymer is used for a graft side chain of a copolymer of (meth) acrylate and acrylamide is known.
  • a hydrophilic graft polymer is anionic because carboxylate is used as a raw material, the hydrophilicity of the hydrophilic graft polymer varies greatly depending on the pH of the water in contact therewith. Have.
  • a hydrophilic layer obtained by applying a mixture of hydrophilic silica and titanium oxide to a film substrate and drying it is proposed as a hydrophilic layer that can be easily fixed to the surface of a hydrophobic resin substrate.
  • This hydrophilic layer is utilized on the surface of a plastic molding by transferring it onto the surface of the plastic molding (see, for example, Patent Document 2).
  • the hydrophilic layer may be cracked or peeled off when subjected to external stress.
  • the conventional modifier capable of modifying the surface characteristics is one having either hydrophilic property or hydrophobic property, in recent years, hydrophilic property and lipophilic property, hydrophilic property and oil repellency property.
  • hydrophilic property and lipophilic property hydrophilic property and oil repellency property.
  • the purpose of the first group of the present invention is to form a thin film having desired properties such as hydrophilicity, water repellency, oleophilicity, oil repellency, and the like, which is difficult to detach from the base material even when contacted with water.
  • a method for producing a (meth) acrylic polymer having an alkoxysilyl group useful for the surface modifier, and a surface modified substrate surface-modified with the surface modifier It is in.
  • the object of the second group of the present invention is to provide a surface modifier that has two conflicting properties such as hydrophilicity and lipophilicity, hydrophilicity and oil repellency, and can be immobilized on a substrate. It is in.
  • Another object of the second group of the present invention is to produce a base material having two contradictory properties such as hydrophilicity and lipophilicity, hydrophilicity and oil repellency, and having a surface modifier fixed thereon. It is an object of the present invention to provide a method for producing a surface-modified base material that can be used.
  • Still another object of the second group of the present invention is that the surface modifier is immobilized on the surface, and the surface modifier is contradictory such as hydrophilicity and lipophilicity, hydrophilicity and oil repellency.
  • the object is to provide a surface-modified substrate that can have both properties.
  • the purpose of the third group of the present invention is to provide a surface hydrophilizing agent that can form a coating with excellent hydrophilicity on the surface of the substrate, which is not easily detached from the substrate even when contacted with water, and
  • An object of the present invention is to provide a surface-hydrophilized base material in which a film comprising a surface hydrophilizing agent is formed on the surface of the base material.
  • the first group of the present invention is: (1) Formula (I):
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrophilic group, a hydrophobic group, a cationic group or an anionic group
  • R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, wherein R 3 , R 4 and R 5 are At least one group of 1 to 4 carbon atoms and R 6 represents an alkylene group of 1 to 12 carbon atoms
  • a surface modifier comprising a (meth) acrylic polymer having an alkoxysilyl group represented by: (2)
  • R 2 may have a hydrogen atom, a hydroxyl group or a fluorine atom, an alkyl group having 2 to 20 carbon atoms, a hydroxyl group or a fluorine atom which may have 6 to 6 carbon atoms.
  • aryl groups an ethylene oxide group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and optionally having a hydroxyl group or a fluorine atom, a hydrogen atom or alkyl having 1 to 4 carbon atoms at one end
  • a propylene oxide group optionally having a fluorine atom
  • Polypropylene oxide group addition mole number is from 2 to 20, wherein (III):
  • R 11 is an alkylene group having 1 to 4 carbon atoms
  • R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 14 is an organic group
  • X ⁇ is a negative group.
  • the surface modifier according to (1) which is a group represented by (3)
  • (4) A surface-modified base material that is surface-modified with the surface modifier according to any one of (1) to (3), (5) Formula (Va):
  • R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, wherein R 3 , R 4 and R 5 are At least one group of 1 to 4 carbon atoms and R 6 represents an alkylene group of 1 to 12 carbon atoms)
  • R 3 , R 4 and R 5 are At least one group of 1 to 4 carbon atoms and R 6 represents an alkylene group of 1 to 12 carbon atoms
  • R 2 may have a hydrogen atom, a hydroxyl group, or a fluorine atom, and the carbon number of 2 to An aryl group having 6 to 20 carbon atoms which may have a 20 alkyl group, a hydroxyl group or a fluorine atom, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end, and a hydroxyl group or a fluorine atom.
  • R 11 is an alkylene group having 1 to 4 carbon atoms
  • R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 14 is an organic group
  • X ⁇ is a negative group. Ion) It is related with the manufacturing method of the (meth) acrylic-type polymer which has the alkoxy silyl group as described in said (5) which is group represented by these.
  • the second group of the present invention is: (1) A two-component surface modifier comprising a liquid I containing a polymer having an alkoxysilyl group and a silane coupling agent having a thiol group, and a liquid II containing a (meth) acryl monomer, (2) A polymer having an alkoxysilyl group has the formula (I):
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrophilic group, a hydrophobic group, a cationic group or an anionic group
  • R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, wherein R 3 , R 4 and R 5 are At least one group of 1 to 4 carbon atoms and R 6 represents an alkylene group of 1 to 12 carbon atoms
  • the two-component surface modifier according to (1) which is a (meth) acrylic polymer having an alkoxysilyl group represented by: (3)
  • R 2 may have a hydrogen atom, a hydroxyl group or a fluorine atom, an alkyl group having 2 to 20 carbon atoms, a hydroxyl group or a fluorine atom which may have 6 to 6 carbon atoms.
  • aryl groups an ethylene oxide group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and optionally having a hydroxyl group or a fluorine atom, a hydrogen atom or alkyl having 1 to 4 carbon atoms at one end
  • a propylene oxide group optionally having a fluorine atom
  • Polypropylene oxide group addition mole number is from 2 to 20, wherein (III):
  • R 11 is an alkylene group having 1 to 4 carbon atoms
  • R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 14 is an organic group
  • X ⁇ is a negative group.
  • the two-component surface modifier according to (2) which is a group represented by: (4) The two-component surface modifier according to (2) or (3), wherein the number of repeating units represented by formula (I) is 1 to 1000, (5)
  • a silane coupling agent having a thiol group has the formula (VIb):
  • R 15 , R 16 and R 17 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R 15 , R 16 and R 17 are And at least one group of R 1 represents an alkoxy group having 1 to 4 carbon atoms, and R 18 represents an alkylene group having 1 to 12 carbon atoms.
  • the (meth) acrylic monomer has the formula (Vb):
  • R 19 represents a hydrogen atom or a methyl group
  • R 20 represents a hydrophilic group, a hydrophobic group, a cationic group or an anionic group
  • R 20 may have a hydrogen atom, a hydroxyl group, or a fluorine atom, and may have a C 2-20 alkyl group, a hydroxyl group, or a fluorine atom.
  • aryl groups an ethylene oxide group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and optionally having a hydroxyl group or a fluorine atom, a hydrogen atom or alkyl having 1 to 4 carbon atoms at one end
  • a propylene oxide group which may have a fluorine atom
  • a propylene oxide which has a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and may have a hydroxyl group or a fluorine atom
  • a polypropylene oxide group wherein the number of added moles of the group is 2 to 20, formula (III):
  • R 11 is an alkylene group having 1 to 4 carbon atoms
  • R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 14 is an organic group
  • X ⁇ is a negative group.
  • the two-component surface modifier according to (6) which is a group represented by: (8) After applying a liquid I containing a polymer having an alkoxysilyl group and a silane coupling agent having a thiol group to the substrate, the surface of the substrate coated with the liquid I contains a (meth) acrylic monomer
  • a method for producing a surface-modified base material characterized by applying a liquid II and reacting a silane coupling agent having a thiol group with a (meth) acrylic monomer, (9)
  • a polymer having an alkoxysilyl group has the formula (I):
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrophilic group, a hydrophobic group, a cationic group or an anionic group
  • R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, wherein R 3 , R 4 and R 5 are At least one group of 1 to 4 carbon atoms and R 6 represents an alkylene group of 1 to 12 carbon atoms
  • the method for producing a surface-modified substrate according to (8) which is a (meth) acrylic polymer having an alkoxysilyl group represented by: (10)
  • R 2 may have a hydrogen atom, a hydroxyl group, or a fluorine atom, and may have a C 2-20 alkyl group, a hydroxyl group, or a fluorine atom.
  • aryl groups an ethylene oxide group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and optionally having a hydroxyl group or a fluorine atom, a hydrogen atom or alkyl having 1 to 4 carbon atoms at one end
  • a propylene oxide group which may have a fluorine atom
  • a propylene oxide which has a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and may have a hydroxyl group or a fluorine atom
  • Polypropylene oxide group addition mole number is from 2 to 20, the formula (III):
  • R 11 is an alkylene group having 1 to 4 carbon atoms
  • R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 14 is an organic group
  • X ⁇ is a negative group.
  • R 15 , R 16 and R 17 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R 15 , R 16 and R 17 are And at least one group of R 1 represents an alkoxy group having 1 to 4 carbon atoms, and R 18 represents an alkylene group having 1 to 12 carbon atoms.
  • the (meth) acrylic monomer has the formula (Vb):
  • R 19 represents a hydrogen atom or a methyl group
  • R 20 represents a hydrophilic group, a hydrophobic group, a cationic group or an anionic group
  • R 20 may have a hydrogen atom, a hydroxyl group, or a fluorine atom, and may have a C 2-20 alkyl group, a hydroxyl group, or a fluorine atom.
  • aryl groups an ethylene oxide group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and optionally having a hydroxyl group or a fluorine atom, a hydrogen atom or alkyl having 1 to 4 carbon atoms at one end
  • a propylene oxide group which may have a fluorine atom
  • a propylene oxide which has a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and may have a hydroxyl group or a fluorine atom
  • Polypropylene oxide group addition mole number is from 2 to 20 groups of formula (III):
  • R 11 is an alkylene group having 1 to 4 carbon atoms
  • R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 14 is an organic group
  • X ⁇ is a negative group.
  • coated The surface of the substrate can be modified by applying a II liquid containing a (meth) acrylic monomer to the surface of the material and reacting the silane coupling agent having a thiol group with the (meth) acrylic monomer. . Therefore, by using the two-component surface modifier of the present invention, it is possible to provide a surface modification method for a substrate.
  • the third group of the present invention is: (1) Formula (IX):
  • R 1 is a hydrogen atom or a methyl group
  • R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms
  • 3 , at least one of R 4 and R 5 is an alkoxy group having 1 to 4 carbon atoms
  • R 6 is an alkylene group having 1 to 6 carbon atoms
  • Y is an oxygen atom or an NH-group
  • X silicon atom-containing monomer represented by formula (X):
  • R 1 , R 6 and Y are the same as above, R 8 is an alkylene group having 1 to 4 carbon atoms, R 9 and R 10 are each independently a hydrogen atom or an alkyl having 1 to 4 carbon atoms.
  • Group) A surface hydrophilizing agent characterized by containing a (meth) acrylic polymer obtained by polymerizing a monomer component containing a nitrogen atom-containing monomer represented by (2) The weight ratio of the silicon atom-containing monomer represented by the formula (IX) and the nitrogen atom-containing monomer represented by the formula (X) (silicon atom-containing monomer / nitrogen atom-containing monomer) is 3/97 to 95 / 5, the surface hydrophilizing agent according to (1), (3) The above (1) or (2), wherein the monomer component further contains a monomer copolymerizable with a silicon atom-containing monomer represented by the formula (IX) and a nitrogen atom-containing monomer represented by the formula (X) A surface hydrophilizing agent according to claim 1, (4) A
  • the surface hydrophilizing agent according to (3) which is at least one selected from the group consisting of: (5)
  • the silicon atom-containing monomer represented by the formula (IX) in which the amount of the monomer that can be copolymerized with the silicon atom-containing monomer represented by the formula (IX) and the nitrogen atom-containing monomer represented by the formula (X)
  • the surface hydrophilizing agent according to (3) or (4) which is 0 to 100 parts by weight per 100 parts by weight of the total amount of the nitrogen atom-containing monomer represented by formula (X) and (6)
  • the present invention relates to a surface-hydrophilized base material in which a film comprising the surface hydrophilizing agent according to any one of 1) to (5) is formed on the surface of the base material.
  • a thin film having a desired property such as hydrophilicity, water repellency, oleophilicity, oil repellency is formed even if it is in contact with water and does not easily come off from the base material.
  • Surface modifying agent, surface modified substrate surface modified by the surface modifying agent, and method for producing (meth) acrylic polymer having alkoxysilyl group useful for the surface modifying agent are examples of surface modifying agent, surface modified substrate surface modified by the surface modifying agent, and method for producing (meth) acrylic polymer having alkoxysilyl group useful for the surface modifying agent .
  • a surface modifier that has two conflicting properties such as hydrophilicity and lipophilicity, hydrophilicity and oil repellency, and can be immobilized on a substrate.
  • a base material having a surface modifier that is immobilized on a base material, which has two contradictory properties such as hydrophilicity and lipophilicity and hydrophilicity and oil repellency is manufactured.
  • a method for producing a surface-modified substrate, wherein the surface modifier is immobilized on the surface for example, hydrophilicity and lipophilicity, hydrophilicity and oil repellency, and so on.
  • a surface modified substrate having both properties is provided.
  • a surface hydrophilizing agent that can form a coating film having excellent hydrophilicity on the surface of the base material, which does not easily come off from the base material even in contact with water, and Provided is a surface hydrophilized substrate in which a coating comprising a surface hydrophilizing agent is formed on the substrate surface.
  • the first group of surface modifiers of the present invention has the formula (I):
  • R 1 is a hydrogen atom or a methyl group.
  • R 2 is a hydrophilic group, a hydrophobic group, a cationic group or an anionic group.
  • the properties imparted to the substrate by the surface modifier can be adjusted. For example, when imparting hydrophilicity to the substrate, an organic group having hydrophilicity is selected, and when imparting hydrophobicity to the substrate, an organic group having hydrophobicity is selected.
  • R 2 examples include a hydrogen atom, a hydroxyl group, or an alkyl group having 2 to 20 carbon atoms that may have a fluorine atom, an aryl group having 6 to 20 carbon atoms that may have a hydroxyl group or a fluorine atom, An ethylene oxide group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and optionally having a hydroxyl group or a fluorine atom, a hydroxyl group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end Alternatively, an ethylene oxide group which may have a fluorine atom has a polyethylene oxide group having an addition mole number of 2 to 20, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end, a hydroxyl group or a fluorine atom.
  • a propylene oxide group which may have a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and a hydroxyl group or a fluorine atom which may have a fluorine atom.
  • R 11 is an alkylene group having 1 to 4 carbon atoms
  • R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 14 is an organic group
  • X ⁇ is a negative group. Ion
  • the group etc. which are represented by these are mentioned, this invention is not limited only to this illustration. Among these groups, the group represented by the formula (III) is preferable from the viewpoint of increasing the coating film strength.
  • R 7 and R 8 are each independently an alkylene group having 1 to 4 carbon atoms.
  • R 7 is preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group, more preferably a methylene group or an ethylene group.
  • R 8 is preferably a methylene group or an ethylene group.
  • R 11 is an alkylene group having 1 to 4 carbon atoms.
  • R 11 is preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group, more preferably a methylene group or an ethylene group.
  • R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 14 is an organic group. Specific examples of the organic group include an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a carboxyalkyl group having 2 to 6 carbon atoms. However, the present invention is limited only to such examples. Is not to be done.
  • X ⁇ is an anion.
  • X - include Preferable examples of the alkyl chloride ions of 1 to 4 carbon atoms, a monovalent dialkyl sulfate ions an alkyl group with a carbon number of 1 to 4, having 6 to 8 carbon atoms aryl chloride ions, carbon atoms in the alkyl group
  • Alkyl sulfate halide ions, halogen ions, acetate ions, borate ions, citrate ions, tartaric acid ions, hydrogen sulfate ions, bisulfite ions, sulfate ions, phosphate ions and the like having a number of 1 to 4 may be mentioned. Is not limited to such examples.
  • Examples of the halogen atom in the alkyl sulfate halide ion include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the halogen atom in the halogen ion include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • X - Among the alkyl chloride ions of 1 to 4 carbon atoms, an aryl chloride ions monovalent number dialkyl sulfate ion and carbon 6-8 carbon atoms in the alkyl group 1 to 4 are preferred.
  • the monomer having a group represented by the formula (IV) include methyl chloride salt of N, N-dimethylaminoethyl (meth) acrylate, dimethyl sulfate salt of N, N-dimethylaminoethyl (meth) acrylate, Diethyl sulfate of N, N-dimethylaminoethyl (meth) acrylate, benzyl chloride salt of N, N-dimethylaminoethyl (meth) acrylate, methyl chloride salt of N, N-dimethylaminopropyl (meth) acrylate, N, N N-dimethylaminopropyl (meth) acrylate dimethyl sulfate, N, N-dimethylaminopropyl (meth) acrylate diethyl sulfate, N, N-dimethylaminopropyl (meth) acrylate benzyl chloride salt, N,
  • N, N-dimethylaminoethyl (meth) acrylate methyl chloride salt, N, N-dimethylaminoethyl (meth) acrylate diethyl sulfate salt and the like because they are inexpensive and easily available Is preferred.
  • R 2 as the hydrophilic group, for example, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms having at least one hydroxyl group, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end is used.
  • examples include 20 polyethylene glycol groups, 1 to 10 polypropylene glycol groups having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end, and groups represented by the formula (III).
  • the present invention is not limited to such examples.
  • the group represented by the formula (III) is preferable from the viewpoint of increasing the coating film strength.
  • examples of the hydrophobic group include an alkyl group having 2 to 20 carbon atoms which may have a fluorine atom, and an aryl group having 6 to 20 carbon atoms which may have a fluorine atom.
  • the present invention is not limited to such examples.
  • an alkyl group having 2 to 20 carbon atoms having 3 or more fluorine atoms and an aryl group having 6 to 20 carbon atoms having 3 or more fluorine atoms are preferable.
  • examples of the cationic group include a group represented by the formula (IV), but the present invention is not limited to such examples.
  • examples of the anionic group include a carboxyethenylphenoxide dodecyl group and a carboxyacetylaminoethyl group, but the present invention is not limited to such examples.
  • the lower limit of the number of repeating units represented by formula (I) is preferably 1 or more, more preferably 10 or more.
  • the upper limit of the number of repeating units represented by formula (I) is preferably 1000 or less, more preferably 500 or less.
  • R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, At least one of R 3 , R 4 and R 5 is an alkoxy group having 1 to 4 carbon atoms.
  • the reason why at least one of R 3 , R 4 and R 5 is an alkoxy group having 1 to 4 carbon atoms is to fix the surface modifier to the substrate by chemical bonding.
  • R 3 it is preferable that at least one of the radicals R 4 and R 5 is an alkoxy group having 1 to 4 carbon atoms, R 3, R 4 and at least two groups having a carbon number of R 5 More preferably, it is an alkoxy group having 1 to 4 and more preferably all of R 3 , R 4 and R 5 are alkoxy groups having 1 to 4 carbon atoms.
  • R 4 and R 5 are alkoxy groups having 1 to 4 carbon atoms.
  • the alkyl groups having 1 to 4 carbon atoms a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
  • the alkoxy groups having 1 to 4 carbon atoms a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.
  • R 6 is an alkylene group having 1 to 12 carbon atoms.
  • R 6 an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 6 carbon atoms is more preferable.
  • the alkoxysilyl group represented by the formula (II) is present at least at one end of the (meth) acrylic polymer, but from the viewpoint of sufficiently expressing the properties of the (meth) acrylic polymer, (meth) acrylic It is preferably present only at one end of the polymer.
  • the alkoxysilyl group represented by the formula (II) is present only at one end of the (meth) acrylic polymer, from the viewpoint of sufficiently expressing the properties of the (meth) acrylic polymer at the other end.
  • a group such as a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a residue of a polymerization initiator is preferably present.
  • a (meth) acrylic polymer having a repeating unit represented by the formula (I) and having an alkoxysilyl group represented by the formula (II) at least at one end is, for example, the formula (Va):
  • Examples of the (meth) acrylic monomer represented by the formula (Va) include N- (meth) acryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine, N- (meth) acryloylamino Examples include ethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine, methoxytriethylene glycol (meth) acrylate, and 2,2,2-trifluoroethyl methacrylate. It is not limited. These (meth) acrylic monomers may be used alone or in combination of two or more.
  • N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine is, for example, disclosed in JP-A-9-95474, JP-A-9-95586, and JP-A-11-222470. Can be easily prepared with high purity.
  • alkoxysilyl group-containing compound represented by the formula (VIa) examples include 1-thiopropyl-3-trimethoxysilane, 1-thiopropyl-3-triethoxysilane, 1-thiopropyl-3-triisopropoxysilane, 1 -Thiopropyl-3-methyldimethoxysilane, 1-thiopropyl-3-methyldiethoxysilane, 1-thiopropyl-3-methyldipropoxysilane, and the like, but the present invention is not limited to such examples. .
  • These alkoxysilyl group-containing compounds may be used alone or in combination of two or more.
  • the amount of the alkoxysilyl group-containing compound represented by the formula (VIa) is not particularly limited, but is usually preferably about 0.01 to 10 parts by weight per 100 parts by weight of the total amount of monomers to be subjected to polymerization.
  • (meth) acrylic monomer represented by the formula (Va) may be used in combination with another polymerizable monomer as long as the object of the present invention is not inhibited.
  • Examples of other polymerizable monomers include styrene, ⁇ -hydroxystyrene, p-hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid.
  • polymerization initiator examples include azoisobutyronitrile, methyl azoisobutyrate, azobisdimethylvaleronitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, benzophenone derivatives, phosphine oxide derivatives, benzoketone derivatives, phenylthioether derivatives, azides Derivatives, diazo derivatives, disulfide derivatives and the like can be mentioned, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more.
  • the amount of the polymerization initiator is not particularly limited, but is usually about 0.01 to 5 parts by weight per 100 parts by weight of the total amount of monomers to be subjected to polymerization including the (meth) acrylic monomer represented by the formula (Va). Preferably there is.
  • Examples of the method for polymerizing the (meth) acrylic monomer represented by the formula (Va) include a solution polymerization method, but the present invention is not limited to such examples.
  • the (meth) acrylic monomer represented by the formula (Va) is polymerized by a solution polymerization method, for example, the (meth) acrylic monomer represented by the formula (Va) is dissolved in a solvent and obtained.
  • Polymerization can be performed by adding a polymerization initiator while stirring the solution.
  • the solvent examples include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, and xylene.
  • Alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol
  • ketones such as acetone and methyl ethyl ketone
  • ethers such as diethyl ether and tetrahydrofuran
  • aromatic hydrocarbons such as benzene, toluene, and xylene.
  • Compounds, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such as cyclohexane, and acetic acid esters such as methyl
  • the amount of the solvent is usually about 10 to 80% by weight of the monomer in a solution obtained by dissolving the monomer to be polymerized containing the (meth) acrylic monomer represented by the formula (Va) in the solvent. It is preferable to adjust so that.
  • the polymerization conditions such as polymerization temperature and polymerization time when polymerizing the (meth) acrylic monomer represented by the formula (Va) are determined depending on the type of monomer and the amount used, the type of polymerization initiator and the amount used. It is preferable to adjust accordingly.
  • the atmosphere when the (meth) acrylic monomer represented by the formula (Va) is polymerized is preferably an inert gas.
  • the inert gas include nitrogen gas and argon gas, but the present invention is not limited to such examples.
  • a (meth) acrylic polymer having an alkoxysilyl group can be obtained by polymerizing the (meth) acrylic monomer represented by the formula (Va) and other monomers used as necessary as described above. .
  • the viscosity average molecular weight of the (meth) acrylic polymer having an alkoxysilyl group can be measured by, for example, gel permeation chromatography.
  • the viscosity average molecular weight of the (meth) acrylic polymer having an alkoxysilyl group is preferably 100 or more, more preferably 500 or more, and (meth) having an alkoxysilyl group from the viewpoint of sufficiently expressing the surface modification effect. From the viewpoint of increasing the solubility of the acrylic polymer, it is preferably 100,000 or less, more preferably 50,000 or less.
  • the surface modifier of the present invention contains the (meth) acrylic polymer having the alkoxysilyl group, and may be composed of only the (meth) acrylic polymer having the alkoxysilyl group. May be contained.
  • the solvent examples include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, and xylene.
  • Alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol
  • ketones such as acetone and methyl ethyl ketone
  • ethers such as diethyl ether and tetrahydrofuran
  • aromatic hydrocarbons such as benzene, toluene, and xylene.
  • Compounds, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such as cyclohexane, and acetic acid esters such as methyl
  • the amount of the solvent is not particularly limited. Usually, the concentration of the (meth) acrylic polymer having an alkoxysilyl group in a solution obtained by dissolving the (meth) acrylic polymer having an alkoxysilyl group in the solvent is 10 to 10%. It is preferable to adjust so that it may become about 80 weight%.
  • the surface-modified base material that has been surface-modified using the surface modifier of the present invention can be produced by applying the surface modifier of the present invention to the substrate.
  • the base material has a hydroxyl group on the surface.
  • a base material on which silica is vapor-deposited can be suitably used.
  • Examples of the material of the substrate include, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyamides represented by nylon, polyimide, polyurethane, urea resin, polylactic acid, polyvinyl alcohol, polyvinyl acetate, acrylic resin, polysulfone, polycarbonate, Examples include ABS resin, AS resin, silicone resin, glass, ceramic, metal, and the like, but the present invention is not limited to such examples.
  • the surface modifier of the present invention is more firmly fixed to a substrate having a hydroxyl group on the surface, it is preferably used for a substrate having a hydroxyl group on the surface.
  • a substrate having no hydroxyl group on the surface it is preferable to modify the surface so that the hydroxyl group exists on the surface.
  • the surface modifier of the present invention can firmly fix the surface modifier of the present invention on the surface of the substrate even when a substrate on which silica is deposited is used as the substrate.
  • the base material used for the base material on which silica is deposited is, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyamide represented by nylon, polyimide, polyurethane, urea resin, polylactic acid, polyvinyl alcohol, polyvinyl acetate,
  • the resin is formed of a resin such as an acrylic resin, polysulfone, polycarbonate, ABS resin, AS resin, or silicone resin, the resin usually has a hydrophobic property. It is thought that it is difficult to fix firmly to the surface of the resin substrate).
  • the surface modifier of the present invention when silica is vapor-deposited on the surface of the resin base material, the surface modifier of the present invention can be firmly fixed to the resin base material on which silica is vapor-deposited.
  • Examples of the method for depositing silica on the surface of the resin substrate include a vacuum deposition method, a sputtering method, and a chemical vapor deposition method, but the present invention is not limited to such examples.
  • a vacuum deposition method a sputtering method, and a chemical vapor deposition method
  • the present invention is not limited to such examples.
  • silica when silica is deposited on the surface of a resin substrate by vacuum deposition, the resin substrate is placed in a vacuum container, degassed under heating, and then vapor of alkoxysilane such as tetramethoxysilane is placed in the vacuum container.
  • Silica can be vapor-deposited on the surface of the resin base material by introducing into the resin base.
  • the amount of silica deposited on the surface of the resin base material varies depending on the type of resin used for the resin base material and cannot be determined unconditionally, it is appropriately determined according to the type of resin. It is preferable that the amount of the surface modifier is usually fixed to the surface of the resin substrate on which silica is deposited.
  • the shape of the base material is not particularly limited, and examples thereof include a film, a sheet, a plate, a rod, and a molded body formed into a predetermined shape.
  • the present invention is not limited only to such examples.
  • Examples of the method for applying the surface modifier of the present invention to the substrate include a flow coating method, a spray coating method, a dipping method, a brush coating method, and a roll coating method, but the present invention is only such examples. It is not limited to.
  • the atmosphere when the surface modifier of the present invention is applied to the substrate may be usually air.
  • coating the surface modifier of this invention to a base material may be normal temperature normally, and may be heating.
  • the application amount of the surface modifier of the present invention when the surface modifier of the present invention is applied to a substrate cannot be determined unconditionally because it varies depending on the application of the substrate. It is preferable to adjust appropriately.
  • After applying the surface modifier of the present invention to the substrate it is preferable to heat the substrate from the viewpoint of increasing production efficiency.
  • the temperature at which the base material is heated varies depending on the heat-resistant temperature of the base material and cannot be determined unconditionally. However, a temperature suitable for the base material is usually selected within the range of 50 to 150 ° C. Is preferred.
  • the (meth) acrylic polymer having an alkoxysilyl group contained in the surface modifier of the present invention is fixed to the substrate by applying the surface modifier of the present invention to the substrate. can do.
  • the surface-modified base material of the present invention has an alkoxysilyl group because the (meth) acrylic polymer having an alkoxysilyl group contained in the surface modifier of the present invention is immobilized on the surface thereof.
  • the properties of the (meth) acrylic polymer can be imparted to the base material, and it can be prevented from being washed away when moisture adheres as in the case of using a conventional surfactant.
  • the surface modifying substrate according to the surface modifying agent of the present invention can be adjusted by appropriately adjusting the properties of the (meth) acrylic polymer having an alkoxysilyl group, for example, hydrophilicity, hydrophobicity, lipophilicity, repellency. Desired properties such as oiliness can be imparted to the substrate.
  • the surface modifier of the present invention does not need to polymerize the monomer composition on the surface of the base material as in the invention described in Patent Document 5, and the base modifier is simply applied to the surface of the base material. Since the surface of the material can be modified, there is an advantage that a surface modified substrate having a modified substrate surface can be easily produced in a short time.
  • the second group two-component surface modifier of the present invention contains a liquid I containing a polymer having an alkoxysilyl group and a silane coupling agent having a thiol group, and a (meth) acrylic monomer. II liquid.
  • liquid I contains a polymer having an alkoxysilyl group and a silane coupling agent having a thiol group.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrophilic group, a hydrophobic group, a cationic group or an anionic group
  • R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, wherein R 3 , R 4 and R 5 are At least one group of 1 to 4 carbon atoms and R 6 represents an alkylene group of 1 to 12 carbon atoms
  • the (meth) acrylic-type polymer which has the alkoxy silyl group represented by these is mentioned.
  • R 1 is a hydrogen atom or a methyl group.
  • R 2 is a hydrophilic group, a hydrophobic group, a cationic group or an anionic group.
  • the (meth) acrylic polymer having an alkoxysilyl group only one type of hydrophilic group, hydrophobic group, cationic group and anionic group may exist, or two or more types exist. It may be.
  • the properties imparted to the substrate by the surface modifier of the present invention can be adjusted by the types of the hydrophilic group, hydrophobic group, cationic group and anionic group.
  • hydrophilicity when imparting hydrophilicity to the substrate, a hydrophilic group is selected, and when imparting hydrophobicity to the substrate, a hydrophobic group is selected. Furthermore, for example, when a hydrophilic group and a hydrophobic group are selected, hydrophilicity and hydrophobicity can be imparted to the (meth) acrylic polymer having an alkoxysilyl group.
  • R 2 examples include a hydrogen atom, a hydroxyl group, or an alkyl group having 2 to 20 carbon atoms that may have a fluorine atom, an aryl group having 6 to 20 carbon atoms that may have a hydroxyl group or a fluorine atom, An ethylene oxide group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and optionally having a hydroxyl group or a fluorine atom, a hydroxyl group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end Alternatively, an ethylene oxide group which may have a fluorine atom has a polyethylene oxide group having an addition mole number of 2 to 20, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end, a hydroxyl group or a fluorine atom.
  • a propylene oxide group which may have a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and a hydroxyl group or a fluorine atom which may have a fluorine atom.
  • R 11 is an alkylene group having 1 to 4 carbon atoms
  • R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 14 is an organic group
  • X ⁇ is a negative group. Ion
  • the group etc. which are represented by these are mentioned, this invention is not limited only to this illustration. Among these groups, the group represented by the formula (III) is preferable from the viewpoint of increasing the coating film strength.
  • R 7 and R 8 are each independently an alkylene group having 1 to 4 carbon atoms.
  • R 7 is preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group, more preferably a methylene group or an ethylene group.
  • R 8 is preferably a methylene group or an ethylene group.
  • R 11 is an alkylene group having 1 to 4 carbon atoms.
  • R 11 is preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group, more preferably a methylene group or an ethylene group.
  • R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 14 is an organic group. Specific examples of the organic group include an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a carboxyalkyl group having 2 to 6 carbon atoms. However, the present invention is limited only to such examples. Is not to be done.
  • X ⁇ is an anion.
  • X - include Preferable examples of the alkyl chloride ions of 1 to 4 carbon atoms, a monovalent dialkyl sulfate ions an alkyl group with a carbon number of 1 to 4, having 6 to 8 carbon atoms aryl chloride ions, carbon atoms in the alkyl group Examples thereof include alkyl sulfate halides having 1 to 4 numbers, halogen ions, acetate ions, borate ions, citrate ions, tartrate ions, hydrogen sulfate ions, bisulfite ions, sulfate ions, phosphate ions, etc. However, the present invention is not limited to such examples.
  • Examples of the halogen atom in the halide include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the halogen atom in the halogen ion include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • X - Among the alkyl chloride ions of 1 to 4 carbon atoms, an aryl chloride ions monovalent number dialkyl sulfate ion and carbon 6-8 carbon atoms in the alkyl group 1 to 4 are preferred.
  • the monomer having a group represented by the formula (IV) include methyl chloride salt of N, N-dimethylaminoethyl (meth) acrylate, dimethyl sulfate salt of N, N-dimethylaminoethyl (meth) acrylate, Diethyl sulfate of N, N-dimethylaminoethyl (meth) acrylate, benzyl chloride salt of N, N-dimethylaminoethyl (meth) acrylate, methyl chloride salt of N, N-dimethylaminopropyl (meth) acrylate, N, N N-dimethylaminopropyl (meth) acrylate dimethyl sulfate, N, N-dimethylaminopropyl (meth) acrylate diethyl sulfate, N, N-dimethylaminopropyl (meth) acrylate benzyl chloride salt, N,
  • N, N-dimethylaminoethyl (meth) acrylate methyl chloride salt, N, N-dimethylaminoethyl (meth) acrylate diethyl sulfate salt and the like because they are inexpensive and easily available Is preferred.
  • R 2 as the hydrophilic group, for example, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms having at least one hydroxyl group, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end is used.
  • examples include 20 polyethylene glycol groups, 1 to 10 polypropylene glycol groups having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end, and groups represented by the formula (III).
  • the present invention is not limited to such examples.
  • the group represented by the formula (III) is preferable from the viewpoint of increasing the coating film strength.
  • examples of the hydrophobic group include an alkyl group having 2 to 20 carbon atoms which may have a fluorine atom, and an aryl group having 6 to 20 carbon atoms which may have a fluorine atom.
  • the present invention is not limited to such examples.
  • an alkyl group having 2 to 20 carbon atoms having 3 or more fluorine atoms and an aryl group having 6 to 20 carbon atoms having 3 or more fluorine atoms are preferable.
  • examples of the cationic group include a group represented by the formula (IV), but the present invention is not limited to such examples.
  • examples of the anionic group include a carboxyethenylphenoxide dodecyl group and a carboxyacetylaminoethyl group, but the present invention is not limited to such examples.
  • the lower limit of the number of repeating units represented by formula (I) is preferably 1 or more, more preferably 10 or more.
  • the upper limit of the number of repeating units represented by formula (I) is preferably 1000 or less, more preferably 500 or less.
  • R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, At least one of R 3 , R 4 and R 5 is an alkoxy group having 1 to 4 carbon atoms.
  • the reason why at least one of R 3 , R 4 and R 5 is an alkoxy group having 1 to 4 carbon atoms is to fix the surface modifier to the substrate by chemical bonding.
  • R 3 it is preferable that at least one of the radicals R 4 and R 5 is an alkoxy group having 1 to 4 carbon atoms, R 3, R 4 and at least two groups having a carbon number of R 5 More preferably, it is an alkoxy group having 1 to 4 and more preferably all of R 3 , R 4 and R 5 are alkoxy groups having 1 to 4 carbon atoms.
  • R 4 and R 5 are alkoxy groups having 1 to 4 carbon atoms.
  • the alkyl groups having 1 to 4 carbon atoms a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
  • the alkoxy groups having 1 to 4 carbon atoms a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.
  • R 6 is an alkylene group having 1 to 12 carbon atoms.
  • R 6 an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 6 carbon atoms is more preferable.
  • the alkoxysilyl group represented by the formula (II) is present at least at one end of the (meth) acrylic polymer, but from the viewpoint of sufficiently expressing the properties of the (meth) acrylic polymer, (meth) acrylic It is preferably present only at one end of the polymer.
  • the alkoxysilyl group represented by the formula (II) is present only at one end of the (meth) acrylic polymer, from the viewpoint of sufficiently expressing the properties of the (meth) acrylic polymer at the other end.
  • a group such as a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a residue of a polymerization initiator is preferably present.
  • the (meth) acrylic polymer having a repeating unit represented by the formula (I) and having an alkoxysilyl group represented by the formula (II) at least at one end is, for example, the formula (VII):
  • alkoxysilyl group-containing compound represented by the formula (VII) examples include 1-thiopropyl-3-trimethoxysilane, 1-thiopropyl-3-triethoxysilane, 1-thiopropyl-3-triisopropoxysilane, 1 -Thiopropyl-3-methyldimethoxysilane, 1-thiopropyl-3-methyldiethoxysilane, 1-thiopropyl-3-methyldipropoxysilane, and the like, but the present invention is not limited to such examples. .
  • These alkoxysilyl group-containing compounds may be used alone or in combination of two or more.
  • the amount of the alkoxysilyl group-containing compound represented by the formula (VII) is not particularly limited, but is usually preferably about 0.01 to 10 parts by weight per 100 parts by weight of the total amount of monomers to be subjected to polymerization.
  • Examples of the (meth) acrylic monomer represented by the formula (VIII) include N- (meth) acryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine, N- (meth) acryloylaminoethyl -N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine, methoxytriethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl methacrylate, and the like are included, but the present invention is limited to such examples only. Is not to be done. These (meth) acrylic monomers may be used alone or in combination of two or more.
  • N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine is, for example, disclosed in JP-A-9-95474, JP-A-9-95586, and JP-A-11-222470. Can be easily prepared with high purity.
  • (meth) acrylic monomer represented by the formula (VIII) may be used in combination with other polymerizable monomers as long as the object of the present invention is not inhibited.
  • Examples of other polymerizable monomers include styrene, ⁇ -hydroxystyrene, p-hydroxystyrene, methyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, and N-methyl (meta ) Acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-octyl ( (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone (meth) acrylamide, methyl itaconate, ethyl itaconate, vinyl acetate, vinyl
  • the polymerization initiator may be the same as that used in the first group of the present invention.
  • the amount of the polymerization initiator is not particularly limited, but is usually about 0.01 to 5 parts by weight per 100 parts by weight of the total amount of the monomer including the (meth) acrylic monomer represented by the formula (VIII). It is preferable.
  • Examples of the method for polymerizing the (meth) acrylic monomer represented by the formula (VIII) include a solution polymerization method, but the present invention is not limited to such examples.
  • the monomer is polymerized by a solution polymerization method, for example, the (meth) acrylic monomer represented by the formula (VIII) is dissolved in a solvent, and the resulting solution is stirred to add a polymerization initiator and polymerize. be able to.
  • the solvent may be the same as that used in the first group of the present invention.
  • the amount of the solvent is usually such that the concentration of the monomer in the solution obtained by dissolving the monomer to be polymerized containing the (meth) acrylic monomer represented by the formula (VIII) in the solvent is about 10 to 80% by weight. It is preferable to adjust so that it becomes.
  • the polymerization conditions such as polymerization temperature and polymerization time when polymerizing the (meth) acrylic monomer represented by the formula (VIII) depend on the type of monomer and the amount used, the type of polymerization initiator and the amount used, etc. It is preferable to adjust appropriately.
  • the atmosphere when the (meth) acrylic monomer represented by the formula (VIII) is polymerized is preferably an inert gas.
  • the inert gas include nitrogen gas and argon gas, but the present invention is not limited to such examples.
  • a polymer having an alkoxysilyl group can be obtained by polymerizing the (meth) acrylic monomer represented by the formula (VIII) and other monomers used as necessary.
  • the viscosity average molecular weight of the polymer having an alkoxysilyl group can be measured using, for example, an Ubbelohde viscometer.
  • the viscosity average molecular weight of the polymer having an alkoxysilyl group is preferably 100 or more, more preferably 500 or more, from the viewpoint of sufficiently expressing the surface modification effect by the surface modifier of the present invention. From the viewpoint of improving the solubility of the polymer having, it is preferably 100,000 or less, more preferably 50,000 or less.
  • the liquid I used in the present invention contains a polymer having an alkoxysilyl group and a silane coupling agent having a thiol group.
  • silane coupling agent having a thiol group examples include a formula (Vb):
  • R 15 , R 16 and R 17 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R 15 , R 16 and R 17 are And at least one group of R 1 represents an alkoxy group having 1 to 4 carbon atoms, and R 18 represents an alkylene group having 1 to 12 carbon atoms.
  • R 1 represents an alkoxy group having 1 to 4 carbon atoms
  • R 18 represents an alkylene group having 1 to 12 carbon atoms.
  • R 15 , R 16 and R 17 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. , R 15 , R 16 and R 17 are each an alkoxy group having 1 to 4 carbon atoms. The reason why at least one of R 15 , R 16 and R 17 is an alkoxy group having 1 to 4 carbon atoms is to fix the surface modifier to the substrate by chemical bonding.
  • R 15 it is preferable that at least one of the radicals R 16 and R 17 is an alkoxy group having 1 to 4 carbon atoms, R 15, at least two groups having a carbon number of R 16 and R 17 More preferably, it is an alkoxy group having 1 to 4, more preferably all of R 15 , R 16 and R 17 are alkoxy groups having 1 to 4 carbon atoms.
  • R 15 , R 16 and R 17 are alkoxy groups having 1 to 4 carbon atoms.
  • the alkyl groups having 1 to 4 carbon atoms a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
  • a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.
  • R 18 is an alkylene group having 1 to 12 carbon atoms.
  • an alkylene group having 1 to 8 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 2 to 6 carbon atoms is still more preferable.
  • the liquid I can be easily prepared by mixing a polymer having an alkoxysilyl group and a silane coupling agent having a thiol group.
  • a solvent can be used as necessary.
  • the solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, and xylene.
  • Alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol
  • ketones such as acetone and methyl ethyl ketone
  • ethers such as diethyl ether and tetrahydrofuran
  • aromatic hydrocarbons such as benzene, toluene, and xylene.
  • Compounds, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such as cyclohexane, and
  • solvents may be used alone or in combination of two or more.
  • the amount of the solvent is not particularly limited, but is usually preferably 300 to 1000 parts by weight, more preferably 500 to 900 parts by weight per 100 parts by weight of the total amount of the polymer having an alkoxysilyl group and the silane coupling agent having a thiol group. If it is about a part.
  • the ratio between the polymer having an alkoxysilyl group and the silane coupling agent having a thiol group is not particularly limited.
  • both the polymer having an alkoxysilyl group and the silane coupling agent having a thiol group are fixed to the substrate.
  • the silane coupling agent having a thiol group binds to the (meth) acrylic monomer contained in the II liquid. Therefore, considering the balance between the properties of the (meth) acrylic monomer and the properties of the polymer having an alkoxysilyl group, the ratio of the polymer having the alkoxysilyl group and the silane coupling agent having a thiol group is appropriately determined.
  • the molar ratio of the polymer having the alkoxysilyl group and the silane coupling agent having a thiol group is preferably 6/4 or more, more preferably 7/3 or more, and in the case of strongly expressing the properties of the (meth) acrylic monomer contained in the II liquid, an alkoxysilyl group
  • the molar ratio of the polymer having a thiol group and the silane coupling agent having a thiol group is preferably 4/6 or less, more preferably 3/7 or less.
  • a polymer having an alkoxysilyl group and a silane having a thiol group is preferably 3/7 to 7/3, more preferably 4/6 to 6/4.
  • Liquid II contains a (meth) acrylic monomer.
  • the (meth) acrylic monomer for example, the formula (Vb):
  • R 19 represents a hydrogen atom or a methyl group
  • R 20 represents a hydrophilic group, a hydrophobic group, a cationic group or an anionic group
  • This (meth) acryl monomer may use only 1 type and may use 2 or more types together.
  • R 19 is a hydrogen atom or a methyl group.
  • R 20 is a hydrophilic group, a hydrophobic group, a cationic group or an anionic group.
  • the (meth) acrylic polymer having an alkoxysilyl group only one type of hydrophilic group, hydrophobic group, cationic group and anionic group may exist, or two or more types exist. It may be.
  • the properties imparted to the substrate by the surface modifier of the present invention can be adjusted by the types of the hydrophilic group, hydrophobic group, cationic group and anionic group.
  • a hydrophilic group when imparting hydrophilicity to the substrate, a hydrophilic group is selected, and when imparting hydrophobicity to the substrate, a hydrophobic group is selected.
  • a hydrophilic group and a hydrophobic group are selected, hydrophilicity and hydrophobicity can be imparted to the (meth) acrylic polymer having an alkoxysilyl group.
  • the surface modifier of the present invention has a hydrophilic property. And hydrophobicity can also be imparted.
  • R 20 is, for example, a hydrogen atom, a hydroxyl group or an alkyl group having 2 to 20 carbon atoms which may have a fluorine atom, an aryl group having 6 to 20 carbon atoms which may have a hydroxyl group or a fluorine atom, An ethylene oxide group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and optionally having a hydroxyl group or a fluorine atom, a hydroxyl group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end Alternatively, an ethylene oxide group which may have a fluorine atom has a polyethylene oxide group having an addition mole number of 2 to 20, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end, a hydroxyl group or a fluorine atom.
  • a propylene oxide group which may have a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and a hydroxyl group or a fluorine atom which may have a fluorine atom.
  • Examples thereof include a polypropylene oxide group having a number of 2 to 20, a group represented by the above formula (III), a group represented by the above formula (IV), and the like, but the present invention is limited only to such examples. It is not something.
  • the hydrophilic group includes, for example, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms having at least one hydroxyl group, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one terminal, Examples include 20 polyethylene glycol groups, 1 to 10 polypropylene glycol groups having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end, and groups represented by the formula (III). However, the present invention is not limited to such examples. Among these groups, the group represented by the formula (III) is preferable from the viewpoint of increasing the coating film strength.
  • examples of the hydrophobic group include an alkyl group having 2 to 20 carbon atoms which may have a fluorine atom, and an aryl group having 6 to 20 carbon atoms which may have a fluorine atom.
  • the present invention is not limited to such examples.
  • an alkyl group having 2 to 20 carbon atoms having 3 or more fluorine atoms and an aryl group having 6 to 20 carbon atoms having 3 or more fluorine atoms are preferable.
  • examples of the cationic group include a group represented by the formula (IV), but the present invention is not limited to such examples.
  • examples of the anionic group include a carboxyethenylphenoxide dodecyl group and a carboxyacetylaminoethyl group, but the present invention is not limited to such examples.
  • the II liquid may be composed of only a (meth) acrylic monomer, and may contain a catalyst if necessary.
  • the catalyst examples include triethylamine, tributylamine, tripentylamine, N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline and the like, but the present invention is limited only to such examples. is not.
  • triethylamine is preferable because it has a high boiling point and can improve workability.
  • the amount of the catalyst is not particularly limited, but is preferably about 1 to 10 parts by weight per 100 parts by weight of the (meth) acrylic monomer from the viewpoint of increasing the reaction rate.
  • (meth) acrylic monomer may be used in combination with other polymerizable monomers as long as the object of the present invention is not impaired.
  • Examples of other polymerizable monomers include styrene, ⁇ -hydroxystyrene, p-hydroxystyrene, methyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, N-methyl (meta ) Acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-octyl ( (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone (meth) acrylamide, methyl itaconate, ethyl itaconate, vinyl acetate, vinyl prop
  • a solvent when preparing II liquid, a solvent can be used if necessary.
  • the solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, and xylene.
  • alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol
  • ketones such as acetone and methyl ethyl ketone
  • ethers such as diethyl ether and tetrahydrofuran
  • aromatic hydrocarbons such as benzene, toluene, and xylene.
  • Compounds, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such
  • the present invention is limited only to such examples. is not.
  • These solvents may be used alone or in combination of two or more.
  • the amount of the solvent is not particularly limited, but is usually preferably about 30 to 200 parts by weight, more preferably about 50 to 100 parts by weight per 100 parts by weight of the (meth) acrylic monomer.
  • the two-component surface modifier of the present invention is composed of the liquid I and liquid II prepared as described above, and is a combination of liquid I and liquid II.
  • the ratio of liquid I to liquid II is theoretically determined from the reaction between the silane coupling agent having a thiol group contained in liquid I and the (meth) acrylic monomer contained in liquid II. Although it is not necessarily a stoichiometric amount, the silane coupling agent having a thiol group contained in the liquid I and the (meth) acrylic monomer contained in the liquid II.
  • the molar ratio of [the silane coupling agent having a thiol group contained in the liquid I / (meth) acrylic monomer contained in the liquid II] may be adjusted to 4/6 to 6/4. .
  • the two-pack type surface modifier of the present invention is, for example, a liquid (II) applied to a base material, then a liquid II, and a silane coupling agent having a thiol group and the (meth) acrylic contained in the liquid II. By reacting with the monomer, the surface of the substrate can be modified.
  • the two-component surface modifier is used.
  • the liquid I containing a polymer having an alkoxysilyl group and a silane coupling agent having a thiol group was applied to the base material, the liquid I was applied.
  • a liquid II containing a (meth) acrylic monomer is applied to the surface of the substrate, and a silane coupling agent having a thiol group present on the surface of the substrate is reacted with the (meth) acrylic monomer.
  • a substrate having a hydroxyl group on the surface thereof can be suitably used from the viewpoint of chemically fixing the polymer having an alkoxysilyl group and the silane coupling agent having a thiol group to the substrate.
  • the material of the substrate may be the same as that used in the first group of the present invention.
  • the alkoxysilyl group-containing polymer and thiol group-containing silane coupling agent contained in the two-component surface modifier should be more firmly fixed to the substrate having a hydroxyl group on the surface. Therefore, when using a base material having no hydroxyl group on the surface, it is preferable to modify the surface so that the hydroxyl group exists on the surface. In addition, for example, when there are sufficient hydroxyl groups on the surface, such as a substrate made of glass, it is not necessary to modify the surface so that hydroxyl groups are present on the surface. Needless to say.
  • the shape of the substrate is not particularly limited and may be the same as that used in the first group of the present invention.
  • Examples of the method for applying the liquid I to the substrate include a flow coating method, a spray coating method, a dipping method, a brush coating method, and a roll coating method, but the present invention is limited only to such examples. is not.
  • the atmosphere at the time of applying the liquid I to the substrate may be air, and the temperature at the time of application may usually be room temperature or warming.
  • the coating amount of the liquid I when the liquid I is applied to the base material varies depending on the use of the base material and cannot be unconditionally determined.
  • After applying the liquid I to the substrate it is preferable to heat the substrate from the viewpoint of increasing production efficiency. Since the heating temperature of the base material varies depending on the heat-resistant temperature of the base material, etc., it cannot be determined unconditionally. However, it is usually possible to set a temperature within the range of 50 to 150 ° C. that does not adversely affect the base material. preferable.
  • the polymer having an alkoxysilyl group and the silane coupling agent having a thiol group contained in the liquid I can be fixed to the substrate.
  • the II liquid is applied to the surface of the substrate on which the I liquid has been applied.
  • the method for applying the liquid II to the substrate include the flow coating method, the spray coating method, the dipping method, the brush coating method, and the roll coating method, as in the method for applying the liquid I to the substrate.
  • the present invention is not limited to such examples.
  • the temperature of the II solution is preferably adjusted to about 30 to 80 ° C. from the viewpoint of increasing production efficiency.
  • the time for immersing the substrate in the II liquid is not particularly limited, but it is about 30 to 120 minutes from the viewpoint of increasing the reaction rate of the (meth) acrylic monomer contained in the II liquid and increasing the production efficiency. Preferably there is.
  • the silane coupling agent having a thiol group immobilized on the base material by application of the liquid I and the (meth) acrylic monomer bind to each other, so that the liquid I previously immobilized on the base material
  • the property which the polymer which has the alkoxy silyl group contained in and the property which a (meth) acryl monomer has can be provided to a base material.
  • the substrate After completion of the reaction between the (meth) acrylic monomer and the silane coupling agent having a thiol group, the substrate may be washed and dried as necessary.
  • a polymer having an alkoxysilyl group and a (meth) acrylic monomer contained in the liquid I are immobilized on the surface. Therefore, while having the property which the polymer which has an alkoxy silyl group has, and the property which the (meth) acryl monomer fixed to the base material by reacting with the silane coupling agent which has a thiol group can be provided, conventionally It is possible to prevent the liquid from being washed away when water is attached as in the case of using the surfactant.
  • the base material has, for example, desired properties such as hydrophilicity, hydrophobicity, oil repellency, and lipophilicity. Properties can be imparted.
  • the surface hydrophilizing agent of the third group of the present invention has the formula (IX):
  • R 1 is a hydrogen atom or a methyl group
  • R 6 is an alkylene group having 1 to 6 carbon atoms
  • R 3 , R 4 and R 5 are each independently an alkyl group or carbon having 1 to 4 carbon atoms
  • Y represents an oxygen atom or an NH— group
  • X silicon atom-containing monomer represented by formula (X):
  • R 1 , R 6 and Y are the same as above, R 9 and R 10 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 8 is an alkylene having 1 to 4 carbon atoms) Group
  • (Meth) acrylic polymer formed by polymerizing the monomer component containing the nitrogen atom containing monomer represented by these is characterized by the above-mentioned.
  • R 1 is a hydrogen atom or a methyl group.
  • R 6 is an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms. Specific examples of R 6 include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, and a tert-butylene group.
  • the present invention is limited only to such examples. Is not to be done.
  • R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and at least one of R 3 , R 4 and R 5 The group is an alkoxy group having 1 to 4 carbon atoms.
  • the reason why at least one of R 3 , R 4 and R 5 is an alkoxy group having 1 to 4 carbon atoms is to firmly fix the surface hydrophilizing agent of the present invention to the substrate. Accordingly, at least one group of R 3 , R 4 and R 5 is an alkoxy group having 1 to 4 carbon atoms, but at least two groups of R 3 , R 4 and R 5 have 1 to 4 carbon atoms.
  • R 3 , R 4 and R 5 are more preferably alkoxy groups having 1 to 4 carbon atoms.
  • alkyl groups having 1 to 4 carbon atoms a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
  • alkoxy groups having 1 to 4 carbon atoms a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.
  • Y is an oxygen atom or an NH— group.
  • Examples of the silicon atom-containing monomer represented by the formula (IX) include ⁇ - (meth) acryloyloxypropyltrimethoxysilane, ⁇ - (meth) acryloyloxypropyltriethoxysilane, ⁇ - (meth) acryloyloxypropyltrimethoxysilane. Examples include isopropoxysilane, ⁇ - (meth) acryloyloxypropylmethyldimethoxysilane, ⁇ - (meth) acryloyloxypropylmethyldiethoxysilane, and ⁇ - (meth) acryloyloxypropylmethyldipropoxysilane. However, the present invention is not limited to such examples. These silicon atom-containing monomers may be used alone or in combination of two or more.
  • (meth) acryl means “acryl” and / or “methacryl”.
  • R 1 , R 6 and Y may be the same as described above. More specifically, R 1 is a hydrogen atom or a methyl group.
  • R 6 is an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms. Specific examples of R 6 include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, tert-butylene group and the like.
  • Y is an oxygen atom or an NH— group.
  • R 8 is an alkylene group having 1 to 4 carbon atoms.
  • alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, and a tert-butylene group. It is not limited only to such illustration.
  • R 9 and R 10 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
  • alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. It is not limited to illustration only.
  • Examples of the nitrogen atom-containing monomer represented by the formula (X) include N- (meth) acryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine, N- (meth) acryloylaminoethyl- Examples include N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine, but the present invention is not limited to such examples.
  • These nitrogen atom-containing monomers may be used alone or in combination of two or more.
  • the nitrogen atom-containing monomer represented by the formula (X) may be a hydrate.
  • N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine is, for example, disclosed in JP-A-9-95474, JP-A-9-95586, and JP-A-11-222470. Can be easily prepared with high purity.
  • the weight ratio of the silicon atom-containing monomer represented by the formula (IX) and the nitrogen atom-containing monomer represented by the formula (X) improves adhesion to the substrate. From the viewpoint, it is preferably 3/97 or more, more preferably 5/95 or more, and from the viewpoint of enhancing the hydrophilicity of the coating film comprising the surface hydrophilizing agent, preferably 95/5 or less, more preferably 85/15 or less, More preferably, it is 75/25 or less.
  • the monomer composition used in the present invention contains a silicon atom-containing monomer represented by the formula (IX) and a nitrogen atom-containing monomer represented by the formula (X).
  • a monomer copolymerizable with the silicon atom-containing monomer represented by (IX) and the nitrogen atom-containing monomer represented by the formula (X) may be contained.
  • Representative examples of the copolymerizable monomer include monomers having a carbon-carbon unsaturated double bond.
  • Examples of the monomer copolymerizable with the silicon atom-containing monomer represented by the formula (IX) and the nitrogen atom-containing monomer represented by the formula (X) include, for example, a styrene monomer, a carboxylic acid ester monomer, an amide monomer, and the like. Examples of such a monomer having a carbon-carbon unsaturated double bond include, but are not limited to, the present invention. These copolymerizable monomers may be used alone or in combination of two or more.
  • styrene monomer When a styrene monomer is contained in the monomer component, there is an advantage that the heat resistance of the surface hydrophilizing agent of the present invention can be improved.
  • the styrenic monomer include styrene, ⁇ -methylstyrene, ⁇ -hydroxystyrene, p-hydroxystyrene, and the like, but the present invention is not limited to such examples. These styrene monomers may be used alone or in combination of two or more.
  • carboxylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) Tert-butyl acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, (meth) ) Ethyl carbitol acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxy
  • the hydrolysis resistance of the surface hydrophilizing agent of the present invention can be improved.
  • the amide monomer include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N -Acrylamide monomers such as tert-butyl (meth) acrylamide, N-octyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, diacetone (meth) acrylamide, (Meth) acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam and the like can be mentioned, but the present invention is not limited to such examples. These amide monomers may be used alone
  • the amount of the silicon atom-containing monomer represented by the formula (IX) and the monomer copolymerizable with the nitrogen atom-containing monomer represented by the formula (X) is the amount of the silicon atom-containing monomer represented by the formula (IX) and the formula (IX).
  • X is preferably 100 parts by weight or less, that is, 0 to 100 parts by weight, more preferably 50 parts by weight or less, from the viewpoint of improving hydrophilicity per 100 parts by weight of the total amount of the nitrogen atom-containing monomer represented by X).
  • the amount is preferably 10 parts by weight or less, and the amount varies depending on the type of the copolymerizable monomer, but preferably 0 from the viewpoint of sufficiently expressing the properties imparted by using the copolymerizable monomer. .3 parts by weight or more, more preferably 1 part by weight or more, still more preferably 3 parts by weight or more.
  • polymerization initiator When polymerizing the monomer component, it is preferable to use a polymerization initiator.
  • the polymerization initiator include azobisisobutyronitrile, azoisobutyronitrile, methyl azoisobutyrate, azobisdimethylvaleronitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, benzophenone derivatives, phosphine oxide derivatives, benzoketones Derivatives, phenylthioether derivatives, azide derivatives, diazo derivatives, disulfide derivatives and the like can be mentioned, but the present invention is not limited to such examples.
  • These polymerization initiators may be used alone or in combination of two or more.
  • the amount of the polymerization initiator is not particularly limited, but it is usually preferably about 0.01 to 10 parts by weight per 100 parts by weight of the monomer component.
  • a chain transfer agent may be used when the monomer component is polymerized.
  • Chain transfer agents can usually be used by mixing with monomer components.
  • examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, dodecyl mercaptan, and thioglycerol, and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. It is not limited. These chain transfer agents may be used alone or in combination of two or more.
  • the amount of the chain transfer agent is not particularly limited, but is usually about 0.01 to 10 parts by weight per 100 parts by weight of the monomer component.
  • Examples of the method for polymerizing the monomer component include a solution polymerization method and the like, but the present invention is not limited to such examples.
  • the monomer component is polymerized by a solution polymerization method, for example, the monomer component can be dissolved in a solvent, and the polymerization initiator can be added to the resultant solution while stirring to polymerize.
  • the solvent examples include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol and propylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene.
  • Alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol and propylene glycol
  • ketones such as acetone and methyl ethyl ketone
  • ethers such as diethyl ether and tetrahydrofuran
  • aromatic hydrocarbons such as benzene, toluene and xylene.
  • Compounds, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such as cyclohexane, and acetic acid esters such as methyl acetate and
  • the amount of the solvent is usually preferably adjusted so that the concentration of the monomer component in the solution obtained by dissolving the monomer component in the solvent is about 10 to 80% by weight.
  • the polymerization conditions such as the polymerization temperature and polymerization time for polymerizing the monomer component are preferably adjusted as appropriate according to the composition of the monomer component, the type and amount of the polymerization initiator, and the like.
  • the atmosphere when the monomer component is polymerized is preferably an inert gas.
  • the inert gas include nitrogen gas and argon gas, but the present invention is not limited to such examples.
  • a (meth) acrylic polymer can be obtained by polymerizing the monomer component as described above.
  • the viscosity average molecular weight of the (meth) acrylic polymer is preferably 100 or more, more preferably 500 or more, from the viewpoint of sufficiently expressing the surface hydrophilizing effect, and the dissolution of the (meth) acrylic polymer having an alkoxysilyl group From the viewpoint of enhancing the properties, it is preferably 100,000 or less, more preferably 50,000 or less.
  • the viscosity average molecular weight of the (meth) acrylic polymer can be measured, for example, by gel permeation chromatography.
  • the surface hydrophilizing agent of the present invention contains the (meth) acrylic polymer, but contains other polymers, solvents, various additives, and the like within the range that does not impede the purpose of the present invention. Also good.
  • the solvent may be the same as the solvent used when the monomer component is polymerized.
  • the solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; aromatic carbonization such as benzene, toluene, and xylene.
  • Examples include hydrogen compounds, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such as cyclohexane, and acetate esters such as methyl acetate and ethyl acetate.
  • these solvents may be used alone or in combination of two or more.
  • the amount of the solvent is not particularly limited, but is usually adjusted so that the concentration of the (meth) acrylic polymer in the solution obtained by dissolving the (meth) acrylic polymer in the solvent is about 10 to 80% by weight. It is preferable.
  • the surface hydrophilized substrate of the present invention can be obtained by forming a film comprising a surface hydrophilizing agent on the substrate surface.
  • the material of the substrate may be the same as that used in the first group of the present invention.
  • a substrate having a hydroxyl group on the surface thereof is preferable.
  • the surface is hydrophilized so that the hydroxyl group exists on the surface. It is preferable.
  • a hydroxyl group is sufficiently present on the surface of a substrate made of glass or the like, it is not necessary to make the surface hydrophilic so that a hydroxyl group exists on the surface. Needless to say.
  • the shape of the substrate may be the same as that used in the first group of the present invention.
  • the method for applying the surface hydrophilizing agent of the present invention to the substrate may be the same as that used in the first group of the present invention.
  • the atmosphere when the surface hydrophilizing agent of the present invention is applied to the substrate may be air, and the temperature during application may usually be room temperature or warming.
  • the coating amount of the surface hydrophilizing agent of the present invention when the surface hydrophilizing agent of the present invention is applied to the base material varies depending on the use of the base material and cannot be determined unconditionally. It is preferable to adjust appropriately.
  • After applying the surface hydrophilizing agent of the present invention to the substrate it is preferable to heat the substrate from the viewpoint of increasing production efficiency.
  • the heating temperature for heating the base material varies depending on the heat-resistant temperature of the base material and cannot be determined unconditionally. However, a temperature suitable for the base material is usually within the range of 50 to 150 ° C. It is preferable to select.
  • the surface hydrophilized substrate of the present invention is produced by coating the monomer component on the substrate surface, polymerizing the monomer component by applying light or heating, and forming a film. You can also
  • the thickness (thickness after drying) of the coating film formed on the surface of the surface hydrophilized substrate of the present invention cannot be determined unconditionally because it varies depending on the type and application of the surface hydrophilized substrate. However, it is usually preferable to be about 10 nm to 10 ⁇ m.
  • the surface hydrophilized substrate of the present invention can be obtained by forming a film comprising the surface hydrophilizing agent of the present invention on the surface of the substrate.
  • the hydrophilic property of the (meth) acrylic polymer has Can be imparted to the substrate, and can be prevented from being washed away when moisture adheres, as in the case of using a conventional surfactant.
  • the present invention will be described in more detail based on examples. However, the present invention is not limited to such examples.
  • the first group of the present invention to the third group of the present invention are independent in each group. Therefore, the example numbers such as “Example 1” described in each group are independent among the groups.
  • Example 1 N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added to a 500 mL Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. : GLBT], 32.31 g, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803) and ethanol (146.20 g) were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.
  • the obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 182.76 g of ethanol to obtain a (meth) acrylic polymer solution having an alkoxysilyl group.
  • Example 2 N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added to a 500 mL Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. : GLBT] 35.00 g, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803) and ethanol 153.10 g were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.
  • the resulting polymer solution was cooled to 30 ° C. in a water bath and diluted with 191.37 g of ethanol to obtain a (meth) acrylic polymer solution having an alkoxysilyl group.
  • This (meth) acrylic polymer solution having an alkoxysilyl group was used as a surface modifier.
  • Example 3 N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added to a 500 mL Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. : GLBT] 35.00 g, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803) and ethanol 130.02 g were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.
  • the obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 178.78 g of ethanol to obtain a (meth) acrylic polymer solution having an alkoxysilyl group.
  • Example 4 In a 500 mL colben equipped with a nitrogen gas inlet tube, a condenser and a stirrer, 30.00 g of methoxytriethylene glycol acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V-MTG], 3-mercaptopropyltrimethoxysilane [Product name: KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.] 1.44 g and ethanol 125.68 g were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.
  • methoxytriethylene glycol acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V-MTG
  • 3-mercaptopropyltrimethoxysilane Product name: KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.
  • the obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 157.10 g of ethanol to obtain a (meth) acrylic polymer solution having an alkoxysilyl group.
  • Example 5 To a 500 mL Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer, 2,2,2-trifluoroethyl methacrylate (Osaka Organic Chemical Co., Ltd., product number: V-3FM) 35.00 g, 3- Mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803) 2.35 g and ethanol 149.39 g were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.
  • 2,2,2-trifluoroethyl methacrylate Osaka Organic Chemical Co., Ltd., product number: V-3FM
  • 3- Mercaptopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803
  • the obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 186.74 g of ethanol to obtain a (meth) acrylic polymer solution having an alkoxysilyl group.
  • Example 6 To a 500 mL Kolben equipped with a nitrogen gas inlet tube, a condenser, and a stirrer, 12.00 g of 2- (perfluorohexyl) ethyl methacrylate [manufactured by Daikin Industries, Ltd., product number: M-1620], 3-mercaptopropyltri 0.29 g of methoxysilane [trade name: KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.] and 49.15 g of 2,2,2-trifluoroethanol were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.
  • the obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 61.44 g of 2,2,2-trifluoroethanol to obtain a (meth) acrylic polymer solution having an alkoxysilyl group.
  • Examples 7-12 The surface modifier obtained in Examples 1 to 6 was flow-coated on a glass plate (length: 100 mm, width: 100 mm, thickness: 1 mm), and excess surface modifier was removed by washing with ethanol. Then, this glass plate was put in a warm air dryer, and a surface-modified base material was obtained by performing warm air drying at a temperature of 120 ° C. for 30 minutes.
  • the thickness of the film made of the surface modifying agent formed on the surface modified substrate was measured using a stylus type step gauge [manufactured by KLA-Tencor Co., Ltd., product number: P-10].
  • the surface modifier was flow-coated on a glass plate, dried with hot air at 120 ° C. for 30 minutes, and then steam at 90 ° C. was applied to the glass plate flow-coated with the surface modifier. Exposure for 5 minutes. By visually observing the antifogging property of this glass plate, it evaluated based on the following evaluation criteria.
  • example number described in the column of “type of glass plate” in Table 1 indicates that the physical properties were examined using a glass plate on which the surface modifier obtained by the example number was flow-coated. Means.
  • Example 7 instead of the glass plate modified with the surface modifier, a glass plate not modified with the surface modifier was used, and the contact angle with water and antifogging were carried out in the same manner as in Example 7. I examined the sex. The results are shown in Table 1.
  • Comparative Example 2 A 1% sodium laurate aqueous solution is flow-coated on a glass plate, the glass plate is placed in a hot air dryer, and then heated at 120 ° C. for 30 minutes to dry the substrate treated with the surfactant. Obtained. The physical properties of the obtained substrate were examined in the same manner as in Example 7. The results are shown in Table 1.
  • Comparative Example 3 A 1% sodium myristate aqueous solution is flow-coated on a glass plate, and the glass plate is placed in a warm air dryer and dried with warm air at a temperature of 120 ° C. for 30 minutes, whereby a substrate treated with a surfactant is obtained. Obtained. The physical properties of the obtained substrate were examined in the same manner as in Example 7. The results are shown in Table 1.
  • Comparative Example 4 A 1% sodium palmitate aqueous solution is flow-coated on a glass plate, and the glass plate is placed in a warm air dryer and dried with warm air at a temperature of 120 ° C. for 30 minutes. Obtained. The physical properties of the obtained substrate were examined in the same manner as in Example 7. The results are shown in Table 1.
  • the comparative example number described in the column of “type of glass plate” in Table 1 indicates that the physical properties were examined using a glass plate on which the surface modifier obtained by the comparative example number was flow-coated. Means.
  • FIG. 1 (a) and (b) are photographs, which substitute for a drawing, showing the results of examining the antifogging property using the surface modified substrate obtained in Example 7 and the glass plate of Comparative Example 1, respectively. .
  • Example 13 A resin plate made of ABS resin (length: 80 mm, width: 25 mm, thickness: 1.5 mm) was used as the substrate. The resin plate was placed in a vacuum container and degassed, and then trimethoxysilane vapor (vapor pressure: about 400 Pa) was introduced, and silica was deposited on the resin plate for 3 hours.
  • trimethoxysilane vapor vapor pressure: about 400 Pa
  • Example 1 After the surface modifier obtained in Example 1 is flow-coated on the resin plate on which silica is vapor-deposited and the excess surface modifier is removed by washing with ethanol, the resin plate is heated with hot air.
  • the surface-modified base material was obtained by putting in a dryer and performing warm air drying at a temperature of 80 ° C. for 1 hour.
  • the surface modified substrate obtained above was exposed to 90 ° C. water vapor for 5 minutes.
  • the anti-fogging property of the surface-modified base material was visually observed, no occurrence of fogging was observed on the surface of the modified base material. From this, it is understood that the surface modifier of the present invention can be fixed on the surface of the resin base material by depositing silica on the surface of the resin base material.
  • Example of the second group of the present invention Production Example 1 N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added to a 500 mL Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. : GLBT], 32.31 g, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803) and ethanol (146.20 g) were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.
  • the obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 182.76 g of ethanol to obtain a polymer solution having an alkoxysilyl group.
  • the viscosity average molecular weight was determined by measuring the viscosity of the resulting polymer solution having an alkoxysilyl group at 25 ° C. with an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26]. As a result, the viscosity average molecular weight was 15000.
  • N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added to a 500 mL Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. : GLBT] 35.00 g, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803) and ethanol 153.10 g were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.
  • the obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 191.37 g of ethanol to obtain a polymer solution having an alkoxysilyl group.
  • the viscosity average molecular weight was determined by measuring the viscosity of the resulting polymer solution having an alkoxysilyl group at 25 ° C. with an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26]. As a result, the viscosity average molecular weight was 3000.
  • N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added to a 500 mL Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. : GLBT] 35.00 g, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803) and ethanol 130.02 g were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.
  • the obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 178.78 g of ethanol to obtain a polymer solution having an alkoxysilyl group.
  • the viscosity average molecular weight was determined by measuring the viscosity of the resulting polymer solution having an alkoxysilyl group at 25 ° C. with an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26]. As a result, the viscosity average molecular weight was 5000.
  • the obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 157.10 g of ethanol to obtain a polymer solution having an alkoxysilyl group.
  • the viscosity average molecular weight was determined by measuring the viscosity of the resulting polymer solution having an alkoxysilyl group at 25 ° C. with an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26]. As a result, the viscosity average molecular weight was 5000.
  • the obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 186.74 g of ethanol to obtain a polymer solution having an alkoxysilyl group.
  • the viscosity average molecular weight was determined by measuring the viscosity of the resulting polymer solution having an alkoxysilyl group at 25 ° C. with an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26]. As a result, the viscosity average molecular weight was 4000.
  • the obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 61.44 g of 2,2,2-trifluoroethanol to obtain a polymer solution having an alkoxysilyl group.
  • the viscosity average molecular weight was determined by measuring the viscosity of the resulting polymer solution having an alkoxysilyl group at 25 ° C. with an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26]. As a result, the viscosity average molecular weight was 10,000.
  • Example 1 In a 100 mL vial, 4.50 g of the polymer solution having an alkoxysilyl group obtained in Production Example 1, 3-mercaptopropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803] 15 g and 55.35 g of ethanol were added and mixed by thorough stirring. Thereafter, 0.01 g of 0.1N hydrochloric acid was added to the vial and mixed by sufficiently stirring to prepare a liquid I.
  • a two-pack type surface modifier composed of the liquid I and liquid II was prepared.
  • 5 mL of the I solution obtained above was flow-coated on a glass plate (length: 100 mm, width: 100 mm, thickness: 1 mm), and the excess I solution was removed by washing with ethanol.
  • the glass plate was placed in a warm air dryer and dried with warm air at 120 ° C. for 30 minutes to obtain a substrate modified with a polymer having an alkoxysilyl group.
  • the substrate treated with the polymer having an alkoxysilyl group obtained above was immersed in 10 mL of a II solution heated to 60 ° C. for 60 minutes. After that, it was taken out from this II solution, and the glass plate was washed with acetone to remove excess II solution, and the acetone remaining on the substrate was dried with an air gun to be modified with a surface modifier. A substrate was obtained.
  • Example 2 In a 100 mL vial, 3.00 g of the polymer solution having an alkoxysilyl group obtained in Production Example 1, 3-mercaptopropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803] 30 g and 56.70 g ethanol were added and mixed by thorough stirring. Thereafter, 0.01 g of 0.1N hydrochloric acid was added to the vial and mixed by sufficiently stirring to prepare a liquid I.
  • a two-pack type surface modifier composed of the liquid I and liquid II was prepared.
  • 5 mL of the I solution obtained above was flow-coated on a glass plate (length: 100 mm, width: 100 mm, thickness: 1 mm), and the excess I solution was removed by washing with ethanol.
  • the glass plate was put in a warm air dryer and dried with warm air at a temperature of 120 ° C. for 30 minutes to obtain a substrate treated with a polymer having an alkoxysilyl group.
  • the substrate treated with the polymer having an alkoxysilyl group obtained above was immersed in 10 mL of a II solution heated to 60 ° C. for 60 minutes. After that, it was taken out from this II solution, and the glass plate was washed with acetone to remove excess II solution, and the acetone remaining on the substrate was dried with an air gun to be modified with a surface modifier. A substrate was obtained.
  • Example 3 In a 100 mL vial, 1.50 g of the polymer solution having an alkoxysilyl group obtained in Production Example 1, 3-mercaptopropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803] 45 g and 58.05 g ethanol were added and mixed by thorough stirring. Thereafter, 0.01 g of 0.1N hydrochloric acid was added to the vial and mixed by sufficiently stirring to prepare a liquid I.
  • a two-pack type surface modifier composed of the liquid I and liquid II was prepared.
  • 10 mL of the I solution obtained above was flow-coated on a glass plate (length: 100 mm, width: 100 mm, thickness: 1 mm), and the excess I solution was removed by washing with ethanol.
  • the glass plate was put in a warm air dryer and dried with warm air at a temperature of 120 ° C. for 30 minutes to obtain a substrate treated with a polymer having an alkoxysilyl group.
  • the substrate treated with the polymer having an alkoxysilyl group obtained above was immersed in 10 mL of a II solution heated to 60 ° C. for 60 minutes. After that, it was taken out from this II solution, and the glass plate was washed with acetone to remove excess II solution, and the acetone remaining on the substrate was dried with an air gun to be modified with a surface modifier. A substrate was obtained.
  • Example 4 In a 100 mL vial, 0.60 g of the polymer solution having an alkoxysilyl group obtained in Production Example 1, 3-mercaptopropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803] 54 g and 58.86 g of ethanol were added and mixed by thorough stirring. Thereafter, 0.01 g of 0.1N hydrochloric acid was added to the vial and mixed by sufficiently stirring to prepare a liquid I.
  • a two-pack type surface modifier composed of the liquid I and liquid II was prepared.
  • 5 mL of the I solution obtained above was flow-coated on a glass plate (length: 100 mm, width: 100 mm, thickness: 1 mm), and the excess I solution was removed by washing with ethanol.
  • the glass plate was put in a warm air dryer and dried with warm air at a temperature of 120 ° C. for 30 minutes to obtain a substrate treated with a polymer having an alkoxysilyl group.
  • the substrate treated with the polymer having an alkoxysilyl group obtained above was immersed in 10 mL of a II solution heated to 60 ° C. for 60 minutes. After that, it was taken out from this II solution, and the glass plate was washed with acetone to remove excess II solution, and the acetone remaining on the substrate was dried with an air gun to be modified with a surface modifier. A substrate was obtained.
  • Example 5 In a 100 mL vial, 0.30 g of the polymer solution having an alkoxysilyl group obtained in Production Example 1, 3-mercaptopropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803] 57 g and 59.13 g ethanol were added and mixed by thorough stirring. Thereafter, 0.01 g of 0.1N hydrochloric acid was added to the vial and mixed by sufficiently stirring to prepare a liquid I.
  • a two-pack type surface modifier composed of the liquid I and liquid II was prepared.
  • 5 mL of the I solution obtained above was flow-coated on a glass plate (length: 100 mm, width: 100 mm, thickness: 1 mm), and the excess I solution was removed by washing with ethanol.
  • the glass plate was put in a warm air dryer and dried with warm air at a temperature of 120 ° C. for 30 minutes to obtain a substrate treated with a polymer having an alkoxysilyl group.
  • the substrate treated with the polymer having an alkoxysilyl group obtained above was immersed in 10 mL of a II solution heated to 60 ° C. for 60 minutes. After that, it was taken out from this II solution, and the glass plate was washed with acetone to remove excess II solution, and the acetone remaining on the substrate was dried with an air gun to be modified with a surface modifier. A substrate was obtained.
  • Example 6 In a 100 mL vial, 0.06 g of the polymer solution having an alkoxysilyl group obtained in Production Example 1, 3-mercaptopropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803] 59 g and 59.35 g ethanol were added and mixed by thorough stirring. Thereafter, 0.01 g of 0.1N hydrochloric acid was added to the vial and mixed by sufficiently stirring to prepare a liquid I.
  • a two-pack type surface modifier composed of the liquid I and liquid II was prepared.
  • 5 mL of the I solution obtained above was flow-coated on a glass plate (length: 100 mm, width: 100 mm, thickness: 1 mm), and the excess I solution was removed by washing with ethanol.
  • the glass plate was placed in a warm air dryer and dried with warm air at 120 ° C. for 30 minutes to obtain a substrate treated with a polymer having an alkoxysilyl group.
  • the substrate treated with the polymer having an alkoxysilyl group obtained above was immersed in 10 mL of a II solution heated to 60 ° C. for 60 minutes. After that, it was taken out from this II solution, and the glass plate was washed with acetone to remove excess II solution, and the acetone remaining on the substrate was dried with an air gun to be modified with a surface modifier. A substrate was obtained.
  • Comparative Example 1 A 1% sodium laurate aqueous solution was flow-coated on a glass plate, and this glass plate was placed in a warm air dryer and dried with warm air at a temperature of 120 ° C. for 30 minutes to be treated with a conventional surfactant. A substrate was obtained.
  • Comparative Example 2 A 1% sodium myristate aqueous solution was flow-coated on a glass plate, and this glass plate was placed in a warm air dryer and dried with warm air at a temperature of 120 ° C. for 30 minutes to be treated with a conventional surfactant. A substrate was obtained.
  • Comparative Example 3 A 1% sodium palmitate aqueous solution was flow-coated on a glass plate, and this glass plate was placed in a warm air dryer and dried with warm air at a temperature of 120 ° C. for 30 minutes to be treated with a conventional surfactant. A substrate was obtained.
  • the thickness of the film made of the surface modifier or surfactant formed on the surface of the substrate modified with the surface modifier and the substrate treated with the surfactant is measured with a stylus-type step gauge (KLA Tencor Corporation, product number: P-10] was used for measurement.
  • the contact angle with water or n-decane of the substrate modified with the surface modifier and the substrate treated with the surfactant in the above “contact angle with water or n-decane” is 25 ° C. in the atmosphere. After measurement using a contact angle meter (manufactured by Elma Co., Ltd.), the substrate modified with the surface modifier and the substrate treated with the surfactant are immersed in water heated to 80 ° C. for 5 hours. did.
  • each substrate was taken out from the water, washed with water, the water adhering to the substrate was dried with an air gun, and the contact angle with water was measured in the atmosphere at 25 ° C.
  • the water resistance was evaluated by calculating the difference between the contact angle between the substrate water after the water resistance test and the contact angle between the substrate water before the water resistance test and the absolute value of the obtained difference. Note that the smaller the absolute value, the better the water resistance of the substrate.
  • the surface-modified substrate has a low contact angle with water, but has a high contact angle with n-decane, so that hydrophilicity and oil repellency are imparted.
  • hydrophilicity and oil repellency can be simultaneously imparted to the substrate by using the two-component surface modifier of the present invention.
  • the surface-modified substrate has both water repellency and oil repellency because the contact angle with water and the contact angle with n-decane are both high. I know that there is. From this, it can be seen that if the two-component surface modifier of the present invention is used, water repellency and oil repellency can be simultaneously imparted to the substrate.
  • the use of the two-component surface modifier of the present invention simultaneously imparts water-related properties such as hydrophilicity and water repellency and properties related to oily components such as lipophilicity and oil repellency to the substrate.
  • the surface-modified substrate obtained in each example is excellent in water resistance even when immersed in water heated to 80 ° C. for 5 hours. It can be seen that the polymer having an alkoxysilyl group contained is firmly fixed to the substrate, and the (meth) acrylic monomer is firmly fixed to the substrate via a silane coupling agent having a thiol group. .
  • Example 1 N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 25.0 g, ⁇ -methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) 30.6 g and ethyl alcohol 500.3 g were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.
  • GLBT ⁇ -methacryloyloxypropyltrimethoxysilane
  • Example 2 N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT], 25.0 g, ⁇ -methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503), and 17.7 g of ethyl alcohol and 327.7 g of ethyl alcohol were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.
  • GLBT 25.0 g
  • ⁇ -methacryloyloxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.,
  • Example 3 N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT], 30.0 g, ⁇ -methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) and 30 g of ethyl alcohol were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.
  • Example 4 N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 25.0 g, ⁇ -methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) 4.4 g, butyl methacrylate 7.6 g and ethyl alcohol 333.5 g Added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.
  • GLBT ⁇ -methacryloyloxypropyltrimethoxysilane
  • Example 5 N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 25.0 g, ⁇ -methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) 4.4 g, styrene 5.6 g and ethyl alcohol 315.2 g were added. did. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.
  • GLBT ⁇ -methacryloyloxypropyltrimethoxysilane
  • Example 6 N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 25.0 g, ⁇ -methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 4.4 g, tert-butyl methacrylamide 7.6 g and ethyl alcohol 333 0.0 g was added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.
  • GLBT 25.0 g
  • ⁇ -methacryloyloxypropyltrimethoxysilane manufactured by Shin-Etsu
  • Example 7 N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 25.0 g, ⁇ -methacryloyloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-502) 30.6 g and ethyl alcohol 500.3 g were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.
  • GLBT ⁇ -methacryloyloxypropylmethyldimethoxysilane
  • Example 8 N-methacryloylaminoethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. 25.0 g, ⁇ -methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) and 30.3 g of ethyl alcohol were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.
  • ⁇ -methacryloyloxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503
  • Comparative Example 3 A 1 L-volume Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer was mixed with 21.5 g of methacrylic acid, ⁇ -methacryloyloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.). 5 g and 450.0 g of ethyl alcohol were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.
  • Comparative Example 4 1L-volume Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer, 21.5 g of butyl methacrylate, ⁇ -methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) 5 g and 450.0 g of ethyl alcohol were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.
  • a wiping cloth (Nippon Paper Crecia Co., Ltd., trade name: Kimwipe S-200) was rubbed 3000 times with a load of 100 g on a surface-hydrophilized substrate, and then water droplets were dropped on the surface to give a contact angle with water of 25 ° C. And was evaluated based on the following evaluation criteria. (Evaluation criteria) ⁇ : Contact angle with water is less than 10 degrees ⁇ : Contact angle with water is 10 degrees or more
  • the thickness of the film made of the surface hydrophilizing agent formed on the surface hydrophilizing substrate was measured using a stylus type step gauge [manufactured by KLA-Tencor Co., Ltd., product number: P-10].
  • the surface hydrophilizing agent obtained in each example can impart hydrophilicity to the substrate.
  • the surface hydrophilizing agent obtained in each example imparts a hydrophilic film excellent in friction resistance, water resistance and solvent resistance to the substrate, as is clear in comparison with Comparative Examples 1 to 4. From this, it can be seen that a hydrophilic coating that is difficult to be detached from the substrate can be formed even when it is in contact with water.
  • the surface modifying agent of the first group of the present invention can be applied to a substrate made of various materials such as glass, metal, organic matter, etc., it can impart desired properties to its surface. It is expected to be applied to a technology for hydrophilizing the surface of a silicone resin used for artificial organs and the like, and a technology for preventing adhesion of proteins, cells, and the like.
  • the surface modifier of the first group of the present invention can easily hydrophilize the surfaces of automobile glass, mirrors, etc., it can be used to protect mirrors, glass surfaces of solar cell panels, residential window glass, etc. It is also useful when adding haze, self-cleaning function, etc., or preventing adhesion of dust and dirt due to antistatic of liquid crystal displays and the like.
  • the second group of two-part surface modifiers of the present invention are made of various materials such as glass, metal, organic matter, etc., and are applied to a surface having a hydroxyl group or the like on the surface, thereby forming a desired surface on the surface. Since the property can be imparted, it is expected to be applied to a technology for hydrophilizing the surface of a silicone resin used in advanced medical instruments, artificial organs, and the like, and a technology for preventing adhesion of proteins, cells, and the like. In addition, the second group two-component surface modifier of the present invention can easily hydrophilize the surfaces of automobile glass, mirrors and the like, and is fixed to those surfaces. As an antistatic agent to add anti-fogging properties and self-cleaning function to the glass surface of panels and residential window glass, and to prevent dust and dirt from adhering to liquid crystal displays due to charging. Is also useful.
  • the surface hydrophilizing agent of the third group of the present invention can impart hydrophilicity to the surface of the base material by applying it to the base material made of various materials such as glass, metal, organic matter, etc. It is expected to be applied to a technology for hydrophilizing the surface of a silicone resin used for instruments, artificial organs, and the like, and a technology for preventing adhesion of proteins, cells, and the like. Furthermore, the surface hydrophilizing agent of the present invention is expected to improve food hygiene because it is difficult for bacteria and bacteria to adhere to the surface when applied to food packaging materials.
  • the surface hydrophilizing agent of the third group of the present invention can easily hydrophilize the surfaces of automobile glass, mirrors, etc., so that it can be applied to mirrors, glass surfaces of solar battery panels, window glass of houses, etc. It is also useful when adding haze, self-cleaning function, etc., or preventing adhesion of dust and dirt due to antistatic of liquid crystal displays and the like. Furthermore, the surface hydrophilizing agent of the third group of the present invention is expected to contribute to fuel efficiency reduction of the ship because it imparts hydrophilicity to the ship bottom when applied to the surface of the ship bottom.

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Abstract

La présente invention concerne : un modificateur de surface présentant deux propriétés opposées comme le caractère hydrophile et le caractère lipophile, et le caractère hydrophile et l'oléophobicité, et qui peut être fixé sur une matière de base ; un procédé de production du modificateur de surface ; et une matière de base présentant une surface modifiée par le modificateur de surface. La présente invention concerne spécifiquement : un modificateur de surface comprenant un polymère acrylique ou méthacrylique portant un groupement alkoxysilyle ; un modificateur de surface en deux parties qui comprend une préparation liquide (I) constituée d'un polymère portant un groupement alkoxysilyle et d'un agent de couplage de type silane portant un groupement thiol, et une préparation liquide (II) comprenant un monomère acrylique ou méthacrylique ; et un agent conférant un caractère hydrophile à une surface caractérisé en ce qu'il comprend un polymère acrylique ou méthacrylique produit par la polymérisation d'un composant monomère constitué d'un monomère comportant des atomes de silicium et d'un monomère comportant des atomes d'azote.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011219637A (ja) * 2010-04-09 2011-11-04 Osaka Organic Chem Ind Ltd ２液型表面改質剤
WO2014084219A1 (fr) * 2012-11-29 2014-06-05 大阪有機化学工業株式会社 Agent de revêtement hydrophile
JP2016071338A (ja) * 2014-10-01 2016-05-09 伊藤光学工業株式会社 光学要素及びその製造方法
WO2016136399A1 (fr) * 2015-02-28 2016-09-01 大阪有機化学工業株式会社 Agent hydrophobe/oléophobe
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