Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N29/00—Biocides, pest repellants or attractants, or plant growth regulators containing halogenated hydrocarbons
  • A01N29/02—Acyclic compounds or compounds containing halogen attached to an aliphatic side-chain of a cycloaliphatic ring system
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
  • A01N33/02—Amines; Quaternary ammonium compounds
  • A01N33/12—Quaternary ammonium compounds
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
  • A01N37/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
• • 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
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
• • 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
  • C08F220/22—Esters containing halogen
  • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
  • C08L33/12—Homopolymers or copolymers of methyl methacrylate
• • 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
  • C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • 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
  • C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
  • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/04—Antistatic

Definitions

• the present invention relates to a novel (meth) acrylate-based copolymer that has both the characteristics attributable to fluorine and the characteristics of trimethylammonium salt, and an antibacterial agent comprising this as an active ingredient.
• the present invention also relates to a novel (meth) acrylate copolymer used in the fields of glass, fibers, metals, resins, films, optical materials, paints, etc., which has both the properties due to fluorine and the properties of ammonium salts.
• the present invention relates to an antibacterial property-imparting resin composition and an antistatic property-imparting resin composition that are excellent in antibacterial activity.
• Coating liquids used in the fields of resins, optical materials, paints, etc. suppress defects such as streaks, repellency, unevenness, irregularities, and non-wetting that occur during the coating process on the surface of the member.
• Various substances are added for the purpose of imparting smoothness to the film surface.
• a compound containing a perfluoroalkenyl group is also used as an additive in this application, and in particular, a nonionic surfactant having a perfluoroalkenyl group is known to be useful in terms of imparting surface smoothness.
• a nonionic surfactant having a perfluoroalkenyl group is known to be useful in terms of imparting surface smoothness.
• Patent Documents 2 and 3 For the purpose of suppressing the growth of bacteria, methods of introducing antibacterial agents are known and widely used (for example, Patent Documents 2 and 3). Various antibacterial agents have been developed so far to impart antibacterial properties to desired materials, and organic and inorganic antibacterial agents are known.
• Organic antibacterial agents include quaternary ammonium salt compounds such as benzalkonium chloride, sulfur-containing benzimidazole compounds such as 2,4-thiazolylbenzimidazole, bisthiocyanate compounds such as methylenebisthiocyanate, 8- Antibacterial agents such as quinolinol compounds such as quinolinol, alcohol compounds such as ethanol, aldehyde compounds such as formalin, phenol compounds such as cresol, and carboxylic acid compounds such as sorbic acid are known.
• quaternary ammonium salt compounds such as benzalkonium chloride, sulfur-containing benzimidazole compounds such as 2,4-thiazolylbenzimidazole, bisthiocyanate compounds such as methylenebisthiocyanate, 8- Antibacterial agents such as quinolinol compounds such as quinolinol, alcohol compounds such as ethanol, aldehyde compounds such as formalin, phenol compounds such as cresol, and carboxylic acid compounds such as sorbic acid are known.
• an inorganic antibacterial agent one in which metal ions exhibiting antibacterial properties such as silver, copper and zinc are supported on activated carbon, apatite, zeolite, tetravalent metal phosphate or the like is known (Patent Documents 4 to 4). 6).
• inorganic antibacterial agents have excellent heat resistance and chemical resistance, they are relatively expensive, difficult to process, and may be colored or discolored during processing or use. There were problems such as poor reproducibility. In addition, when an inorganic antibacterial agent is used, it is difficult to obtain a transparent antibacterial imparting surface.
• JP 2011-057589 A JP 2011-037716 JP 2011-173816 JP JP2007-223917 JP2004-262795 JP2004-217501
• An object of the present invention is to provide a novel (meth) acrylate copolymer and an antibacterial agent that do not impair the performance of the substrate.
• the present invention also provides an antibacterial coating composition that does not impair the performance of the base material, and also has antibacterial properties imparting transparency and antistatic properties. Objective.
• the present invention provides a novel (meth) acrylate copolymer, antibacterial agent, antibacterial imparting resin composition, and antistatic property imparting resin composition.
• Item 1 A (meth) acrylate copolymer comprising the following monomer (1) and monomer (2) as copolymerization components.
• R 1 represents H or CH 3
• R 2 represents a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group is optionally a halogen atom or an ether bond) (—O—), thioether bond (—S—), ester bond (—COO— or —O—CO—), amide bond (—CONH— or —NHCO—) or aryl group
• arylene group Y is the same or different and is a single bond, ester bond (—COO— or —O—CO—), amide bond (—CONH— or —NHCO—), sulfonate bond (— SO 2 —O— or —O—SO 2 —), sulfonamide bond (—SO 2 NH— or —NHSO 2 —), ether bond (—O—), thioether bond (—S—), and
• X is Halogen field
• W is shown H or an alkoxy group, an optionally substituted
• Rf represents a perfluoroalkyl group having 1 to 9 carbon atoms or a perfluoroalkenyl group having 2 to 9 carbon atoms
• R 1 represents H or CH 3
• R 3 represents 1 to 50 carbon atoms.
• a divalent saturated aliphatic hydrocarbon group (the saturated aliphatic hydrocarbon group is optionally a halogen atom, an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO— or —O— CO—), an amide bond (—CONH— or —NHCO—), or an aryl group or an arylene group), and Z is a single bond, an ester bond (—COO— or —O—CO).
• Item 2. The (meth) acrylate copolymer according to Item 1, wherein Rf of the fluorine-containing (meth) acrylate of the formula (2) is a perfluoroalkenyl group having 2 to 9 carbon atoms.
• Item 3. The (meth) acrylate copolymer according to Item 1 or 2, having a reactive functional group, comprising the following monomer (1), monomer (2), and monomer (3) as a copolymerization component: .
• R 1 represents H or CH 3
• R 2 represents a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group is optionally a halogen atom or an ether bond) (—O—), thioether bond (—S—), ester bond (—COO— or —O—CO—), amide bond (—CONH— or —NHCO—) or aryl group
• arylene group Y is the same or different and is a single bond, ester bond (—COO— or —O—CO—), amide bond (—CONH— or —NHCO—), sulfonate bond (— SO 2 —O— or —O—SO 2 —), sulfonamide bond (—SO 2 NH— or —NHSO 2 —), ether bond (—O—), thioether bond (—S—), and
• X is Halogen field
• W is shown H or an alkoxy group, an optionally substituted
• Rf represents a perfluoroalkyl group having 1 to 9 carbon atoms or a perfluoroalkenyl group having 2 to 9 carbon atoms
• R 1 represents H or CH 3
• R 3 represents 1 to 50 carbon atoms.
• a divalent saturated aliphatic hydrocarbon group (the saturated aliphatic hydrocarbon group is optionally a halogen atom, an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO— or —O— CO—), an amide bond (—CONH— or —NHCO—), or an aryl group or an arylene group), and Z is a single bond, an ester bond (—COO— or —O—CO).
• R 1 represents H or CH 3
• W 1 represents H or an alkoxy group, an aryl group optionally having a substituent, a hydroxyl group, a carboxy group (COOH), an amino group, a mercapto group, an isocyanate group.
• a functional group such as a glycidyl group, an oxetane group, a lactone group, or a phosphate group.
• R 4 represents an alkyl group or a divalent arylene group which may have a substituent, a divalent alkylene oxide group having 2 to 4 carbon atoms, and Z represents a single bond, O, NH, NHCO, or S Indicates.
• Item 4 represents an alkyl group or a divalent arylene group which may have a substituent, a divalent alkylene oxide group having 2 to 4 carbon atoms
• Z represents a single bond, O, NH, NHCO, or S Indicates.
• the monomer composition of the copolymer is 100% by weight of the whole copolymer, the monomer (1) is 1 to 90% by weight, the monomer (2) is 1 to 30% by weight, Item 4.
• R 1 represents H or CH 3
• W 2 represents H or an alkoxyl group capable of reacting with W 1 , an aryl group optionally having a substituent, a hydroxyl group, a carboxy group (COOH), an amino group , Functional groups such as mercapto group, isocyanate group, glycidyl group, oxetane group, lactone group, and phosphate group.
• R 4 represents an alkyl group or a divalent arylene group which may have a substituent, a divalent alkylene oxide group having 2 to 4 carbon atoms, and Z represents a single bond, O, NH, NHCO, or S Indicates.
• Item 6 It is a (meth) acrylic-type monomer containing the site
• Item 6. Item 6.
• the antibacterial characterized in that it comprises at least one component selected from the group consisting of the (meth) acrylate copolymer according to any one of items 1 to 5, a salt exchange product thereof, and a mixture thereof as an active ingredient.
• Agent. Item 7.
• An antibacterial resin comprising one or more components selected from the group consisting of the (meth) acrylate copolymer according to any one of items 1 to 5, a salt exchange product thereof, and a mixture thereof. Composition.
• Item 8. Item 6.
• An antistatic property comprising at least one component selected from the group consisting of the (meth) acrylate copolymer according to any one of Items 1 to 5, a salt exchange product thereof, and a mixture thereof.
• Resin composition. Item 9.
• the resin composition of the present invention has excellent antibacterial properties, transparency and antistatic properties. Due to this characteristic, the resin composition of the present invention can be used for various rubbers, plastics, and the like, and molded articles such as films and sheets, and various fibers, paper, leather, paints, adhesives, heat insulating materials, caulking materials, and the like. Antibacterial and antistatic properties can be imparted. Further, by controlling the amount of reactive groups in the oligomer, reaction conditions, monomer type, and the like, it is possible to improve the film strength as a surface modifier and to design the strength according to the purpose. Furthermore, the fluorine-containing trimethylammonium oligomer of the present invention can also improve the solubility in a solvent during surface modification by introducing a hydrocarbon-based substituent, a hydrophilic substituent or the like into the molecule.
• (meth) acrylate means acrylate and / or methacrylate.
• the (meth) acrylate copolymer in the present invention is a compound containing monomer (1) and monomer (2) as a copolymerization component, and reacts with the copolymer.
• Monomer having reactive functional group to compound containing monomer (1), monomer (2), and monomer (3) as a copolymerization component in order to impart a compound having a functional functional group (4) may be further added.
• Monomers (1) to (4) are as follows.
• Trimethylammonium-containing (meth) acrylic monomer Monomer (2): Fluorine-containing (meth) acrylate Monomer (3): Reactive site-containing (meth) acrylic monomer Monomer ( 4): (Meth) acrylic monomer containing a site capable of reacting with monomer (3)
• Trimethylammonium-containing (meth) acrylic monomer is represented by the following formula:
• R 1 represents H or CH 3
• R 2 represents a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group is optionally a halogen atom, an ether bond ( -O-), thioether bond (-S-), ester bond (-COO- or -O-CO-), amide bond (-CONH- or -NHCO-), aryl group, or arylene group
• Y is a single bond, an ester bond (—COO— or —O—CO—), an amide bond (—CONH— or —NHCO—), a sulfonate ester bond (—SO 2 —O— or —O—SO 2 —), sulfonamide bond (—SO 2 NH— or —NHSO 2 —), ether bond (—O—), thioether bond (—S—),
• X represents a halogen atom
• Rf represents a perfluoroalkyl group having 1 to 9 carbon atoms or a perfluoroalkenyl group having 2 to 9 carbon atoms.
• the perfluoroalkyl group may be either straight-chain, branched-chain, CF 3 -, C 2 F 5 -, (n- or iso-) C 3 F 7 -, (n-, iso-, sec - or tert-) C 4 F 9 -, CF 3 (CF 2) m - (m is 4-8 integer), (CF 3) 2 CF (CF 2) k - (k is an integer of 1-6) Etc.
• the following three groups are preferably exemplified as the perfluoroalkenyl group.
• R 1 represents H or CH 3
• R 3 is a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group is optionally a halogen atom, Has an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO— or —O—CO—), an amide bond (—CONH— or —NHCO—), an aryl group, or an arylene group Z is a single bond, an ester bond (—COO— or —O—CO—), an amide bond (—CONH— or —NHCO—), a sulfonate ester bond (—SO 2 —).
• the saturated aliphatic hydrocarbon group of the “divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms” may be linear, branched or cyclic. Examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a cyclopentylene group, a cyclohexylene group, and an octylene group.
• these saturated aliphatic hydrocarbon groups may have one or a plurality of substituents, and the substituents are not particularly limited as long as they do not adversely affect the present invention.
• substituents include an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.
• arylene group include a phenylene group and a naphthylene group. The arylene group may have a substituent, and the substituent is not particularly limited as long as it does not adversely affect the present invention.
• the monomer (2) may be used alone or in combination of two or more.
• the reactive site-containing (meth) acrylic monomer is a (meth) acrylic monomer that does not contain trimethylammonium and fluorine, and includes those represented by the following formula.
• R 1 represents H or CH 3
• W 1 represents H or an alkoxyl group, an aryl group optionally having a substituent, a hydroxyl group, a carboxy group (COOH), an amino group, a mercapto group, an isocyanate group, Functional groups such as a glycidyl group, an oxetane group, a lactone group, and a phosphate group are shown.
• R 4 is a divalent alkylene group having 1 to 10 carbon atoms, a divalent alkylene oxide group having 2 to 4 carbon atoms, or a divalent arylene group optionally having a substituent (phenylene, naphthylene, etc.) ).
• the alkylene group of the “C 1-10 divalent alkylene group” may be linear, branched or cyclic. Examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a cyclopentylene group, a cyclohexylene group, and an octylene group.
• alkylene groups may have a substituent, and the substituent is not particularly limited as long as it does not adversely affect the present invention.
• substituent include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen group.
• the alkylene part of the “divalent alkylene oxide group having 2 to 4 carbon atoms” may be linear or branched, and the alkylene oxide repeating unit is preferably about 1 to 20.
• Z represents a single bond, O, NH, NHCO, or S.
• the monomer (3) may be used alone or in combination of two or more.
• the (meth) acrylic monomer containing a site capable of reacting with the monomer (3) is represented by the following formula, for example, an isocyanate group-containing (meth) acrylate Glycidyl group-containing (meth) acrylate, oxetane-containing (meth) acrylate, lactone ring-containing (meth) acrylate, phosphoric acid group-containing (meth) acrylate, and the like.
• R 1 represents H or CH 3
• W 2 represents H or an alkoxyl group capable of reacting with W 1
• an aryl group optionally having a substituent, a hydroxyl group, a carboxy group (COOH), an amino group
• Functional groups such as a mercapto group, an isocyanate group, a glycidyl group, an oxetane group, a lactone group, and a phosphate group are shown.
• W 2 is not particularly limited as long as it is a functional group that reacts with W 1 .
• R 4 is a divalent alkylene group having 1 to 10 carbon atoms, a divalent alkylene oxide group having 2 to 4 carbon atoms, or a divalent arylene group optionally having a substituent (phenylene, naphthylene, etc.) ).
• the alkylene group of the “C 1-10 divalent alkylene group” may be linear, branched or cyclic. Examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a cyclopentylene group, a cyclohexylene group, and an octylene group.
• alkylene groups may have a substituent, and the substituent is not particularly limited as long as it does not adversely affect the present invention.
• substituent include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen group.
• the alkylene part of the “divalent alkylene oxide group having 2 to 4 carbon atoms” may be linear or branched, and the alkylene oxide repeating unit is preferably about 1 to 20.
• Z represents a single bond, O, NH, NHCO, or S.
• the monomer (4) may be used alone or in combination of two or more.
• the monomer (1) is 1 to 90% by weight and the monomer (2) is 1 It may contain ⁇ 50% by weight, and may further contain monomer (3) and / or monomer (4).
• the monomer (1) is 1 to 90% by weight
• the monomer (2) is 1 to 30% by weight
• the monomer (3) is 1 to 90% by weight
• the monomer (4) is contained in an amount of 0 to 50% by weight.
• the W group of the monomer (1) has a group (reactive functional group) capable of reacting with the monomer (3), in other words, when the monomer (1) also serves as the monomer (4)
• the monomer (4) is not necessary, and in this case, the monomer (4) may be 0% by weight.
• the (meth) acrylate copolymer of the present invention is useful as an antibacterial agent that imparts an excellent antibacterial effect when blended with various materials and an antistatic agent that imparts an excellent antistatic effect.
• materials that can be blended include rubbers such as silicone and acrylic, plastics such as vinyl chloride, polyolefin, polyurethane, ABS, polystyrene, vinyl acetate, and polycarbonate, resins such as phenol, (meth) acrylate, and urethane acrylate. is there.
• the composition of the present invention can be blended with the material and molded, or by coating the surface of the molded body, it can impart antibacterial and antistatic properties to the molded body.
• Various shapes such as a fiber, a film, a sheet, a plate or a block can be formed by a known molding method.
• the (meth) acrylate copolymer of the present invention is dissolved or suspended in a liquid medium such as water or an organic solvent, and is usually used for spray coating, coater coating, dipping, brush coating, roll coating, etc.
• the coating means can be applied to the surface of various metals, plastics, ceramics, resins, etc. to form a film, and thus the growth of bacteria in articles of various materials can be prevented.
• concentration of the (meth) acrylate copolymer in the solution is not particularly limited, but may be, for example, about 0.1 to 90.0% by weight, preferably about 1 to 10% by weight.
• concentration of the (meth) acrylate copolymer in the solution is too low, the amount of the (meth) acrylate copolymer present on the surface decreases, and the coated or sprayed modified surface becomes thin, It becomes a factor of antibacterial property or antistatic property fall. On the other hand, if the concentration is too high, uneven coating may occur.
• concentration of the (meth) acrylate copolymer in the solution is also affected by the solubility depending on the type of solvent and the molecular weight of the polymer.
• a preferred ratio of the (meth) acrylate copolymer of the present invention blended in various materials is 0.1 to 20% by weight, more preferably 100% by weight, per 100% by weight of the material to be imparted with antibacterial or antistatic properties. Is 0.5 to 5% by weight.
• the (meth) acrylate copolymer can be used alone or as a mixture.
• Specific uses of the material or molded product containing the (meth) acrylate copolymer of the present invention include textiles such as towels, carpets, curtains, clothing, leather, refrigerators, washing machines, dish dryers, and vacuum cleaners.
• Electrical appliances such as air conditioners, TVs, telephones, personal computers, car navigation systems, wallpaper, tiles, bricks, concrete, screws, joints and other building materials, washbasins, brooms, hoses, slippers, trash cans and other household goods, triangles
• kitchen items such as corners, drains, water supplies, toiletries, various coating materials, paints, and adhesives.
• the (meth) acrylate copolymer of the present invention can also have a reactive acrylate group or a methacrylate group in the molecule, an antibacterial effect or an antistatic effect by strengthening adhesion using a chemical bond to the substrate surface High sustainability can be expected.
• the (meth) acrylate copolymer of the present invention is used as a coating solution dissolved in an organic solvent, the coating solution is applied to a substrate, and dried. After removing the organic solvent, an antibacterial or antistatic film can be obtained.
• the coating method of the coating liquid is not particularly limited, but for example, it is applied by wet coating, and as its method, for example, gravure method, bar coating method, wire bar method, spin coating method, doctor blade method, dip coating method, slit coating method Etc.
• the antibacterial component of the antibacterial resin composition or the antistatic component of the antistatic resin composition is the monomer (1) or monomer (2).
• a (meth) acrylate copolymer containing as a copolymer component, and a compound having a reactive functional group may be further added to the compound.
• the (meth) acrylate copolymer can be used alone or as a mixture.
• the (meth) acrylate copolymer is, for example, toluene, xylene, diethyl ether, ethyl acetate, methyl ethyl ketone, acetone, acetonitrile, propionitrile, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, ethanol, isopropanol, tetrahydrofuran, It can be used as a solution of an organic solvent such as 1,4-dioxane or as a solution added to a coating liquid (resin composition) such as a paint.
• a coating liquid such as a paint.
• the (meth) acrylate copolymer may be used alone or in combination of two or more.
• the said solvent used for this solution may be used individually by 1 type, and 2 or more types may be mixed and used for it.
• the solution containing the (meth) acrylate copolymer of the present invention is applied to the surface of a coating film by coating, coating, spraying, etc. on the surface of a substrate such as a resin, film, fiber, glass, or metal.
• Antibacterial or antistatic properties can be imparted. That is, when the solvent in the solution evaporates, a film containing the (meth) acrylate copolymer of the present invention is formed on the coating film surface.
• the film has antibacterial or antistatic properties, transparency, and the like.
• the drying (evaporation) conditions of the solvent vary depending on the type and amount of the solvent in the solution, but are usually dried at room temperature to 200 ° C. for about 10 seconds to 10 minutes.
• the concentration of the (meth) acrylate copolymer solution in the solution is not particularly limited, but may be, for example, about 0.1 to 20.0% by weight. If the concentration of the (meth) acrylate copolymer solution in the solution is too low, the amount of (meth) acrylate copolymer present on the surface decreases, and the coated or sprayed coating surface becomes thin. Or cause a decrease in antibacterial or antistatic properties. Moreover, problems such as insufficient strength of the coating film surface may occur. On the other hand, if the concentration is too high, uneven coating may occur. The concentration of the (meth) acrylate copolymer solution in the solution is also affected by the solubility depending on the type of solvent and the molecular weight of the polymer.
• the antibacterial and / or antistatic resin composition of the present invention contains a curable component (resin monomer, resin oligomer, polymerization initiation component, etc.) and a curable resin composition (an antibacterial agent of the present invention having curability). And / or antistatic resin composition).
• a curable resin composition a curable resin composition having a curable component
• the resin composition of the present invention is preferably a “curable resin composition”.
• Curable resin composition containing (meth) acrylate copolymer as active ingredient is prepared as a coating liquid for application to a substrate.
• a (meth) acrylate copolymer, an energy ray curable resin monomer or resin oligomer that mainly functions as a resin film, and the like A polymerization initiator, a solvent and the like are blended.
• no solvent is blended in the case of a solvent-free coating solution, and no polymerization initiator is required in the case of radiation curing.
• the content of the (meth) acrylate copolymer in the total amount of the curable resin composition of the present invention is usually 0.0006 to 17% by weight.
• the amount is preferably about 0.007 to 13% by weight, more preferably about 0.07 to 10% by weight.
• the (meth) acrylate copolymer of the present invention exhibits a function as an antibacterial property-imparting agent in a cured film obtained by polymerization with an energy ray curable resin monomer and / or a resin oligomer described later.
• the curable resin composition of the present invention comprises, in addition to the (meth) acrylate copolymer, an energy ray curable resin monomer that reacts with this to form a resin cured film, and / or Or a resin oligomer (henceforth a resin monomer and a resin oligomer) may be included.
• Such resin monomers and resin oligomers are not particularly limited as long as they form a cured film by reacting with a (meth) acrylate-based copolymer, and are usually used for energy used in hard coat films and antireflection coat films.
• a linear curable resin monomer and / or resin oligomer can be optionally used.
• the resin monomer and resin oligomer examples include acrylic, urethane, epoxy, and silicone reactive compounds such as various acrylates and acrylic urethanes, and acrylic resins are preferably used.
• the resin composition of the present invention is cured and used in the form of a film, it is preferable to use a resin monomer and / or a resin oligomer having a bifunctional or higher functional group.
• resin monomers and resin oligomers having a bifunctional or higher reactive functional group examples include tricyclodecane dimethylol diacrylate, bisphenol F EO-modified diacrylate, bisphenol A EO-modified diacrylate, isocyanuric acid EO-modified diacrylate, and polypropylene.
• Glycol diacrylate polyethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane PO-modified triacrylate, glycerin PO-added triacrylate, trimethylolpropane EO-modified triacrylate, trimethylolpropane EO-modified trimethacrylate , Isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified triacrylate, ⁇ - Prolactone-modified tris (acryloxyethyl) isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, various urethane acrylate oligomers Shigumi series manufactured by company, Art
• Examples of energy rays for curing resin monomers and resin oligomers include radiation, electron beams, ultraviolet rays, and visible rays. Since the energy of electromagnetic waves is high in curing with radiation and electron beam, polymerization is possible only with a polymerizable double bond. When ultraviolet rays and visible rays are used as energy sources, it is preferable to blend a polymerization initiator component described later.
• the content of the resin monomer and resin oligomer in the total amount of the curable resin composition of the present invention is usually about 55 to 99.9% by weight, preferably Is about 60 to 99.5% by weight, more preferably about 70 to 99% by weight.
• the resin monomer / resin oligomer and the (meth) acrylate copolymer are used in an amount of 0.001 to 18 for the (meth) acrylate copolymer with respect to 100% by weight of the resin monomer / resin oligomer.
• About 0.1% by weight, preferably about 0.01 to 15% by weight, more preferably about 0.1 to 10% by weight may be used.
• the curable resin composition of the present invention may contain a polymerization initiator component as necessary. good.
• a conventionally well-known thing can be used for a polymerization initiator component,
• a photoinitiator can be used.
• photopolymerization initiators are known and may be selected as appropriate.
• the addition amount of the polymerization initiator component is usually 0.1 to 50% by weight with respect to 100% by weight of the polymerizable resin component (total amount of the (meth) acrylate copolymer, the resin monomer and / or the resin oligomer). About 0.5 to 40% by weight, more preferably about 1 to 30% by weight.
• Solvent component The curable resin composition of the present invention need not contain a solvent component, but may contain a solvent component as necessary.
• solvent component conventionally known solvent components may be used, and examples thereof include alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate. These solvent components can be used alone or in combination of two or more at any ratio.
• the amount of the solvent component used in the curable resin composition of the present invention is the total amount of the polymerizable resin component (the (meth) acrylate copolymer, the resin monomer and / or the resin oligomer). ) It is usually about 25 to 5000 parts by weight, preferably about 40 to 2000 parts by weight, more preferably about 60 to 1000 parts by weight per 100 parts by weight.
• the curable resin composition of the present invention may be blended with fine particles, fillers and the like as necessary in order to provide a shape on the surface of the cured film and to impart other desired functions. .
• the curable resin composition of the present invention is used as a coating liquid, and after the coating liquid is applied to a substrate, a cured film can be formed by light irradiation or the like.
• the (meth) acrylate copolymer, the resin monomer and / or the resin oligomer, and, if necessary, a polymerization initiator component, a solvent component, fine particles, a filler, etc. are mixed and dissolved at an appropriate blending ratio to prepare the curable resin composition of the present invention as a coating liquid.
• the coating liquid is applied on the substrate so as to have a certain film thickness, and after removing the solvent component by hot air drying, vacuum drying, etc., irradiation with energy rays such as radiation, electron beams, ultraviolet rays, and visible rays is performed.
• energy rays such as radiation, electron beams, ultraviolet rays, and visible rays is performed.
• the coating method of the coating liquid is not particularly limited, but for example, it is applied by wet coating, and as its method, for example, gravure method, bar coating method, wire bar method, spin coating method, doctor blade method, dip coating method, slit coating method Etc.
• the substrate for producing the cured film is not particularly limited as long as the cured film can be supported, but for example, a transparent sheet is desirable when used as a hard coat for optical applications.
• a transparent sheet is desirable when used as a hard coat for optical applications.
• the material for the transparent sheet include glass and plastic, and a plastic sheet is particularly preferable.
• thermoplastic resins, thermosetting resins and the like can be used, for example, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, cellulose resins such as triacetyl cellulose and butyl cellulose, polystyrene resins, polyurethane resins, Examples thereof include polyvinyl alcohol, polyvinyl chloride, acrylic resin, polycarbonate resin, polyacrylonitrile, cycloolefin polymer, and polyethersulfone. These sheets may be subjected to an easy attachment process such as a binder process, a corona process, a plasma process, or a flame process, if necessary.
• polyolefin resins such as polyethylene and polypropylene
• polyester resins such as polyethylene terephthalate
• cellulose resins such as triacetyl cellulose and butyl cellulose
• polystyrene resins polyurethane resins
• polyurethane resins examples thereof
• the thickness of the cured film of the present invention is not particularly limited, and may be appropriately selected depending on the application. Usually, it can be about 100 nm to 30 ⁇ m.
• the antibacterial activity of the test pieces prepared in Examples 1 to 12 below was evaluated by the following method.
• the test bacteria using Escherichia coli (IFO3301) was prepared dilutions so that the number of bacteria becomes 10 2 back and forth.
• 200 ⁇ L of a diluted solution was dropped onto the test piece (5 cm square), closely contacted with a low nutrient agar medium, and cultured at 35 ° C. for 24 hours. Thereafter, the test piece was replanted in a normal nutrient agar medium and cultured at 35 ° C. for 24 hours. The growth state of the bacteria after the culture was confirmed.
• the antibacterial test results obtained as described above are shown in Table 4 below.
• test pieces prepared in Examples 1 to 12 below were evaluated by the following method.
• the foamed beads were put into a transparent cylindrical container by a quarter of the capacity. Subsequently, the test piece (5 cm square) was affixed inside the cylindrical container. After the tube was sealed, the expanded beads were shaken 50 times up and down. Thereafter, the state of the expanded beads when allowed to stand was confirmed.
• Table 4 The results of the antistatic property test are shown in Table 4 below.
• Synthesis example 1 In a three-necked flask (3 L) equipped with a dropping funnel, 234.3 g (1.8 mol) of 2-hydroxyethyl methacrylate, 218.6 g (2.16 mol) of triethylamine, and 1000 g of acetonitrile were placed. The dropping funnel was charged with 973.0 g (2.16 mol) of hexafluoropropene trimer and gradually dropped into the solution in the flask over about 60 minutes with stirring. After completion of the dropwise addition, stirring was continued for another 3 hours at room temperature.
• Rf is a group represented by the following general formula.
• Synthesis example 2 In a three-necked flask (100 mL) equipped with a cooling tube, 2.80 g (5 mmol) of the fluorinated acrylate (A-1) synthesized in Synthesis Example 1 and 24.3 g of DMAMC (B-1) manufactured by Osaka Organic Synthesis Industry (100 mmol), methyl ethyl ketone 54.3 g, 2-propanol 54.3 g, and 2,2′-azobis (2-methylpropionic acid) dimethyl 0.24 g (1.1 mmol) were added. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 80 ° C. while stirring the reaction solution to start the reaction.
• Synthesis example 3 Synthesis was performed in the same procedure as in Synthesis Example 2 with the ratios of monomers (A-1) and (B-1) changed. The monomer ratio is as shown in Table 3.
• Synthesis example 4 In a three-necked flask (3 L) equipped with a dropping funnel, 234.3 g (1.8 mol) of 2-hydroxyethyl methacrylate, 218.6 g (2.16 mol) of triethylamine, and 1000 g of acetonitrile were placed. In a dropping funnel, 1264.68 g (2.16 mol) of a fluorinated acid chloride represented by the following general formula (7) was placed, and gradually dropped into the solution in the flask over about 60 minutes with stirring. After completion of the dropwise addition, stirring was continued for another 3 hours at room temperature.
• the reaction mixture was added with 2200 g of 1N hydrochloric acid to stop the reaction, and then the reaction mixture was transferred into a 5 L beaker, followed by washing with 1 L of water three times.
• the solution after the water washing treatment was dehydrated under reduced pressure to obtain 1138.3 g (yield 93%) of a fluorinated acrylate represented by the following formula (A-1).
• Table 2 shows the 1 H-NMR data of the resulting fluorinated acrylate (A-2).
• Rf is a group represented by the following general formula.
• the monomer ratio is as shown in Table 3.
• Synthesis Example 6 In the same procedure as in Synthesis Example 2A, instead of the monomer (A-1), a linear fluorine-containing acrylate (A-3: CF 3 (CF 2 ) 5 CH 2 CH 2 OC ( ⁇ O) CH ⁇ CH 2 ) was used for the synthesis.
• the monomer ratio is as shown in Table 3.
• Synthesis example 7 In the same procedure as in Synthesis Example 2, synthesis was performed using DMCMA (B-2) manufactured by Osaka Organic Synthesis Industry instead of monomer (B-1). The monomer ratio is as shown in Table 3.
• Synthesis example 8 In the same procedure as in Synthesis Example 2, synthesis was performed using DMAPAA-Q (B-3) manufactured by Kojin in place of monomer (B-1). The monomer ratio is as shown in Table 3.
• Synthesis Example 9 Synthesis was carried out in the same procedure as in Synthesis Example 2 using NOF's Bremer QA (B-4) instead of monomer (B-1). The monomer ratio is as shown in Table 3.
• Synthesis Example 10 Synthesis was carried out in the same procedure as in Synthesis Example 2, using NOF PME-100 as monomer (A-1), monomer (B-1), and monomer (C-1). The monomer ratio is as shown in Table 3. The structure of NOF PME-100 is shown below.
• Synthesis Example 11 Synthesis was carried out in the same procedure as in Synthesis Example 2 with the ratio of monomer (A-1), monomer (B-1), and monomer (C-1) changed.
• the monomer ratio is as shown in Table 3.
• Synthesis Example 12 Synthesis was carried out in the same procedure as in Synthesis Example 2 with the ratio of monomer (A-1), monomer (B-1), and monomer (C-1) changed.
• the monomer ratio is as shown in Table 3.
• Synthesis Example 13 In the same procedure as in Synthesis Example 2, synthesis was carried out using NOF AE-90 as monomer (C-2) instead of monomer (C-1). The monomer ratio is as shown in Table 3. The structure of NOF AE-90 (C-2) is shown below.
• Synthesis Example 14 In the same procedure as in Synthesis Example 2, the monomer (A-1) and the monomer (A-3) were used in combination, and the ratio was changed to carry out the synthesis.
• the monomer ratio is as shown in Table 3.
• Antibacterial test method The antibacterial activity of the test pieces prepared in Examples 1 to 12 was evaluated by the following method.
• the test bacteria using Escherichia coli (IFO3301) was prepared dilutions so that the number of bacteria becomes 10 2 back and forth.
• 200 ⁇ L of a diluted solution was dropped onto the test piece (5 cm square), closely contacted with a low nutrient agar medium, and cultured at 35 ° C. for 24 hours. Thereafter, the test piece was replanted in a normal nutrient agar medium and cultured at 35 ° C. for 24 hours. The growth state of the bacteria after the culture was confirmed.
• Table 4 The antibacterial test results obtained as described above are shown in Table 4 below.
• Comparative Example 1 An antibacterial test was carried out using a PET film to which no antibacterial agent was added as a test piece. The measurement results are shown in Table 4.
• Comparative Example 2 A 2% by weight methanol dispersion solution of NOVALON AG300 was used as an inorganic antibacterial agent and applied to a PET film. Then, it was dried at 80 ° C. for 10 minutes. An antibacterial test was carried out using the dried antibacterial composition-coated film as a test piece. The measurement results are shown in Table 4.
• Comparative Example 3 A 2 mass% methanol solution product of the fluorine-containing monomer described in Synthesis Example 1 was used and applied to a PET film. Then, it was dried at 80 ° C. for 10 minutes. An antibacterial test was conducted using the dried fluorine-containing monomer-coated film as a test piece. The measurement results are shown in Table 4.
• Comparative Example 4 A 2 mass% methanol solution product of the fluorine-containing monomer described in Synthesis Example 4 was used and applied to a PET film. Then, it was dried at 80 ° C. for 10 minutes. An antibacterial test was conducted using the dried fluorine-containing monomer-coated film as a test piece. The measurement results are shown in Table 4.
• the antibacterial composition of the present invention has excellent antibacterial properties and excellent transparency.
• Examples 13-24 0.04 parts by mass (50% by mass solution product) of the (meth) acrylate copolymer described in Synthesis Examples 2, 3 and 5 to 14 and 20 parts by mass of a phenolic resin were added to methyl ethyl ketone, and a PET film (100 ⁇ m thick). ) was coated using a bar coater (No. 8). Then, it was dried at 80 ° C. for 3 minutes. Then, the coating film was hardened using UV irradiation apparatus. The cured antibacterial property-imparting resin composition was cut out and used as a test piece for an antibacterial property test, and an antibacterial property test and an antistatic property test were performed. The antibacterial test results and antistatic test results are shown in Table 5.
• Comparative Example 5 A test piece was prepared in the same procedure as in Example 13 with no antibacterial agent added, and an antibacterial test was conducted. The measurement results are shown in Table 5.
• Comparative Example 6 Using 5% by weight of Novalon AG300 as an inorganic antibacterial agent with respect to the resin, a test piece was prepared in the same procedure as in Example 13, and an antibacterial test was conducted. The measurement results are shown in Table 5.
• Comparative Example 7 Using the fluorine-containing monomer described in Synthesis Example 1 as an antibacterial agent in an amount of 5% by weight based on the resin, a test piece was prepared in the same procedure as in Example 13, and an antibacterial test was performed. The measurement results are shown in Table 5.
• Comparative Example 8 Using the fluorine-containing monomer described in Synthesis Example 4 as an antibacterial agent in an amount of 5% by weight based on the resin, a test piece was prepared in the same procedure as in Example 13, and an antibacterial test was performed. The measurement results are shown in Table 5.
• Comparative Example 9 Using 5% by weight of the monomer (B-1) as an antibacterial agent, a test piece was prepared in the same procedure as in Example 13, and an antibacterial test was conducted. The measurement results are shown in Table 5.
• Comparative Example 10 Using 20% by weight of the monomer (B-1) as an antibacterial agent, a test piece was prepared in the same procedure as in Example 13, and an antibacterial test was conducted. The measurement results are shown in Table 5.
• Coat hardness According to JIS K 5600-5-4, a pencil core is applied at an angle of about 45 ° to the test coating plate surface, and pressed against the test coating plate surface at a load of 750 g, with a uniform forward speed of about 10 mm. I moved more. The hardness symbol of the hardest pencil that did not tear the coating film was defined as the coating film hardness.
• the resin composition of the present invention is excellent in antibacterial properties, transparency and antistatic properties.
• the (meth) acrylate copolymer according to the present invention is useful as an antibacterial property-imparting agent and antistatic property-imparting agent used in the fields of glass, fibers, metals, resins, films, optical materials, paints and the like. It is useful as a compound that can impart antibacterial properties, transparency, and antistatic properties to the substrate surface.

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