KR20150028820A - (meth)acrylate-based copolymer, antimicrobial agent, antimicrobial property-imparting resin composition, and antistatic property-imparting resin composition - Google Patents

Abstract

[식 중, R¹, R², Y, X, W 는 명세서에 정의되는 바와 같다.]
단량체 (2) : 불소 함유 (메트)아크릴레이트
[화학식 2]

[식 중, Rf, R¹, R³, Z 는 명세서에 정의되는 바와 같다.]The present invention provides a (meth) acrylate-based copolymer comprising the following monomer (1) and monomer (2) as copolymer components: monomer (1): trimethylammonium-containing (meth)
[Chemical Formula 1]

Wherein R ¹ , R ² , Y, X and W are as defined in the specification.
Monomer (2): fluorine-containing (meth) acrylate
(2)

Wherein Rf, R ¹ , R ³ , Z are as defined in the specification.

Description

(METH) ACRYLATE-BASED COPOLYMER, ANTIMICROBIAL PROPERTY-IMPATING RESIN COMPOSITION, AND ANTISTATIC PROPERTY-IMPATING RESIN COMPOSITION <br> <br> <br> Patents -

The present invention relates to a novel (meth) acrylate copolymer having properties derived from fluorine and characteristics of a trimethylammonium salt and an antibacterial agent containing the same as an active ingredient.

The present invention also relates to a novel (meth) acrylate-based copolymer which is used in the fields of glass, fiber, metal, resin, film, optical material, paint and the like, To an antimicrobiality-imparting resin composition and an antistatic property-imparting resin composition which are excellent in antimicrobial activity.

In the coating liquid used in the fields of resins, optical materials, paints and the like, it is possible to suppress defects such as streaks, craters, irregularities, grains, and wetting which are generated in the coating step on the member surface, Various materials have been added for the purpose of imparting smoothness.

A compound containing a perfluoroalkenyl group is also used as an additive in the present application, and in particular, it is known that a nonionic surfactant having a perfluoroalkenyl group is useful from the viewpoint of imparting surface smoothness (for example, Patent Document 1).

In addition, a thin display, a PC monitor, a mobile phone, a portable game machine, a car navigation system, and the like are used in various environments and a touch panel is being developed. Especially on the screens of these devices, various contaminants such as sebum, cosmetics, and food waste are attached to the surface of the screen, thereby promoting the propagation of bacteria. In order to remove contamination such as sebum, cosmetics, and food waste, it is wiped with a cloth containing water or a detergent, but it is not easy to wipe off the contamination, and by performing wiping several times, In some cases, traces may occur.

Methods for introducing an antimicrobial agent for the purpose of suppressing the propagation of bacteria have been known and widely used (for example, Patent Documents 2 and 3). Conventionally, various antibacterial agents have been developed to impart antimicrobial properties to desired materials, and organic and inorganic antibacterial agents are known. Examples of the organic antimicrobial agent include a quaternary ammonium salt-based compound such as benzalkonium chloride, a sulfur-containing benzimidazole-based compound such as 2,4-thiazolylbenzimidazole, a bistiocyanate-based compound such as methylenebistiocyanate, Quinolinol-based compounds such as nanolin, alcohol-based compounds such as ethanol, aldehyde-based compounds such as formalin, phenol-based compounds such as cresol, and carboxylic acid-based compounds such as sorbic acid. On the other hand, as an inorganic antimicrobial agent, it is known that metal ions showing antimicrobial activity such as silver, copper and zinc are supported on activated carbon, epothartite, zeolite, tetravalent metal phosphate or the like (Patent Documents 4 to 6).

However, conventional organic antimicrobial agents generally lack heat resistance. Therefore, when they are used in kneading processing for plastics and fibers, problems such as discoloration and foaming may occur, or volatilization or decomposition may occur during processing, I could not show it. Further, in order to impart antimicrobial properties to plastics and resins, a large amount of antimicrobial agents are required, which deteriorates the performance of the original plastic or resin. Further, since the organic antimicrobial agent does not chemically bond with the cured component in the coating liquid, the omission effect is lost from the resin cured film due to the passage of time or external stimulation, and the plastic antibacterial action is exhibited in the film, .

In addition, although conventional inorganic antibacterial agents are excellent in heat resistance and chemical resistance, they are relatively expensive, have difficulty in processing, have a possibility of coloring or discoloration at the time of processing or use, and have poor reproducibility of effects there was. In addition, when an inorganic antimicrobial agent is used, it is difficult to obtain a surface having a clear antimicrobial property.

Japanese Laid-Open Patent Publication No. 2011-057589 Japanese Laid-Open Patent Publication No. 2011-037716 Japanese Laid-Open Patent Publication No. 2011-173816 Japanese Patent Application Laid-Open No. 2007-223917 Japanese Patent Laid-Open No. 2004-262795 Japanese Patent Application Laid-Open No. 2004-217501

It is an object of the present invention to provide a novel (meth) acrylate-based copolymer and an antimicrobial agent which do not impair the performance of a base material.

It is still another object of the present invention to provide an antimicrobial coating composition which does not inhibit the performance of a substrate, and which also has transparency and antistatic property on the surface to which antimicrobial activity is imparted.

An object of the present invention is to provide a novel (meth) acrylate-based copolymer, an antibacterial agent, an antimicrobial property-imparting resin composition and an antistatic property-imparting resin composition.

Section 1.

(Meth) acrylate-based copolymer comprising the following monomer (1) and the monomer (2) as a copolymerization component.

Monomer (1): Trimethylammonium-containing (meth) acrylic monomer

[Chemical Formula 1]

Wherein 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 substituted with a halogen atom, an ether bond (-O-) (-COO- or -O-CO-), an amide bond (-CONH- or -NHCO-) or an aryl group or an arylene group, and Y represents an oxygen atom, (-COO- or -O-CO-), an amide bond (-CONH- or -NHCO-), a sulfonic acid ester bond (-SO ₂ -O- or -O-SO ₂ (-SO-), a sulfonamide bond (-SO ₂ NH- or -NHSO ₂ -), an ether bond (-O-) and a thioether bond (-S-), X represents a halogen atom, W represents H or an alkoxy An aryl group which may have a substituent, a hydroxyl group, a carboxyl group (COOH), an amino group, a mercapto group or an isocyanate group.

Monomer (2): fluorine-containing (meth) acrylate

(2)

Wherein 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 , and R ³ represents a divalent group having 1 to 50 carbon atoms The saturated aliphatic hydrocarbon group may be substituted with a halogen atom, an ether bond (-O-), a thioether bond (-S-), an ester bond (-COO- or -O-CO-), an amide bond (-COOH- or -O-CO-), an amide bond (-CONH- or -NHCO-) or an aryl group or an arylene group), Z is a single bond, an ester bond -), a sulfonic ester bond (-SO ₂ -O- or -O-SO ₂ -), a sulfonamide bond (-SO ₂ NH- or -NHSO ₂ -), an ether bond (-O-), a thioether bond -S-).

Section 2.

The (meth) acrylate-based 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.

Section 3.

The (meth) acrylate-based copolymer according to item 1 or 2, which has a reactive functional group and contains the following monomer (1), the monomer (2) and the monomer (3) as copolymer components.

Monomer (1): Trimethylammonium-containing (meth) acrylic monomer

(3)

Wherein 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 substituted with a halogen atom, an ether bond (-O-) (-COO- or -O-CO-), an amide bond (-CONH- or -NHCO-) or an aryl group or an arylene group, and Y represents an oxygen atom, (-COO- or -O-CO-), an amide bond (-CONH- or -NHCO-), a sulfonic acid ester bond (-SO ₂ -O- or -O-SO ₂ (-SO-), a sulfonamide bond (-SO ₂ NH- or -NHSO ₂ -), an ether bond (-O-) and a thioether bond (-S-), X represents a halogen atom, W represents H or an alkoxy An aryl group which may have a substituent, a hydroxyl group, a carboxyl group (COOH), an amino group, a mercapto group or an isocyanate group.

Monomer (2): fluorine-containing (meth) acrylate

[Chemical Formula 4]

Wherein 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 , and R ³ represents a divalent group having 1 to 50 carbon atoms The saturated aliphatic hydrocarbon group may be substituted with a halogen atom, an ether bond (-O-), a thioether bond (-S-), an ester bond (-COO- or -O-CO-), an amide bond (-COOH- or -O-CO-), an amide bond (-CONH- or -NHCO-) or an aryl group or an arylene group), Z is a single bond, an ester bond -), a sulfonic ester bond (-SO ₂ -O- or -O-SO ₂ -), a sulfonamide bond (-SO ₂ NH- or -NHSO ₂ -), an ether bond (-O-), a thioether bond -S-).

Monomer (3): (meth) acrylic monomer containing reactive site

[Chemical Formula 5]

Wherein R ¹ represents H or CH ₃ and W ¹ represents H or an alkoxy group, an aryl group which may have a substituent, a hydroxyl group, a carboxyl group (COOH), an amino group, a mercapto group, an isocyanate group, An oxetane group, a lactone group, and a phosphoric acid group. R ⁴ represents an alkyl group or a divalent arylene group which may have a substituent or a divalent alkylene oxide group having 2 to 4 carbon atoms and Z represents a single bond, O, NH, NHCO or S.

Section 4.

(Meth) acrylate according to item 1 or 2, wherein the monomer composition of the copolymer is 1 to 90% by weight of the monomer (1) and 1 to 50% by weight of the monomer (2) Lt; / RTI &gt; copolymer.

Item 5.

Wherein the monomer composition of the copolymer is 1 to 90% by weight, the monomer (2) is 1 to 30% by weight, the monomer (3) is 1 to 90% by weight, And (4) the reactive functional group-containing monomer (4) is 0 to 50% by weight, the monomer (4) is a

[Chemical Formula 6]

Wherein R ¹ represents H or CH ₃ , W ² represents H or an alkoxyl group capable of reacting with W ¹ , an aryl group which may have a substituent, a hydroxyl group, a carboxyl group (COOH), an amino group, a mercapto group, An isocyanate group, a glycidyl group, an oxetane group, a lactone group, and a phosphoric acid group. R ⁴ represents an alkyl group or a divalent arylene group which may have a substituent or a divalent alkylene oxide group having 2 to 4 carbon atoms and Z represents a single bond, O, NH, NHCO or S.

(Meth) acryl-based monomer containing a moiety capable of reacting with the monomer (3) represented by the formula

Section 6.

An antimicrobial agent characterized by comprising at least one component selected from the group consisting of a (meth) acrylate copolymer, a salt thereof, and a mixture thereof according to any one of (1) to (5) as an active ingredient.

Item 7.

The antimicrobial resin composition according to any one of (1) to (5), wherein the antimicrobial resin composition contains at least one component selected from the group consisting of a (meth) acrylate-based copolymer, a salt-exchanged product thereof and a mixture thereof.

Section 8.

An antistatic resin composition characterized by containing at least one component selected from the group consisting of the (meth) acrylate-based copolymer, the salt-exchanged product thereof, and the mixture thereof according to any one of items 1 to 5 .

Section 9.

The resin composition according to item 7 or 8, wherein the resin composition is a curable resin composition comprising a curable resin monomer and / or a resin oligomer and a polymerization initiating component.

The resin composition of the present invention is excellent in antimicrobial property, transparency and antistatic property. With this characteristic, the resin composition of the present invention can be used for various kinds of rubber, plastic and the like, molded products such as films and sheets, antibacterial and antistatic properties for various fibers, paper, leather, paint, adhesive, It is possible to give a sex. Further, by controlling the amount of the reactive group in the oligomer, the reaction conditions, the kind of the monomer, etc., it is possible to improve the film strength as a surface modifying agent and design the strength according to the purpose. In addition, the fluorine-containing trimethylammonium oligomer of the present invention may improve the solubility of the fluorinated trimethylammonium oligomer in a solvent when the surface is modified by introducing a hydrocarbon-based substituent or a hydrophilic substituent into the molecule.

In the present specification, (meth) acrylate means acrylate and / or methacrylate.

(Meth) acrylate-based copolymer

The (meth) acrylate-based copolymer in the present invention is a compound containing the monomer (1) and the monomer (2) as a copolymerization component. In order to impart a compound having a reactive functional group to the copolymer, the monomer ), The monomer (2), and the monomer (3) as a copolymerization component may further be added to the monomer (4) having a reactive functional group.

The monomers (1) to (4) are as follows.

Monomer (1): Trimethylammonium-containing (meth) acrylic monomer

Monomer (2): fluorine-containing (meth) acrylate

Monomer (3): (meth) acrylic monomer containing reactive site

Monomer (4): A (meth) acrylic monomer containing a moiety capable of reacting with monomer (3)

Monomer (1): The trimethylammonium-containing (meth) acrylic monomer is characterized by being represented by the following formula.

(7)

Wherein R ¹ represents H or CH ₃ , R ² represents a saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group is optionally substituted with a halogen atom, an ether bond (-O-), a thio (-S-), an ester bond (-COO- or -O-CO-), an amide bond (-CONH- or -NHCO-) or an aryl group or an arylene group, (-COO- or -O-CO-), an amide bond (-CONH- or -NHCO-), a sulfonic acid ester bond (-SO ₂ -O- or -O-SO ₂ -), a sulfonamide bond (-SO ₂ NH- or -NHSO ₂ -), ether bond (-O-), thioether bond (-S-), X represents a halogen atom, W represents H or an alkoxy group, A hydroxyl group, a carboxyl group (COOH), an amino group, a mercapto group, and an isocyanate group.

The monomers (1) may be used singly or in combination of two or more kinds.

Monomer (2): The fluorine-containing (meth) acrylate is characterized by being represented by the following formula.

[Chemical Formula 8]

In the formulas, 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 any of straight chain and branched chain, and may be 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 an integer of _{4 ~ 8), (CF 3} ) 2 CF (CF 2) k - (k is an integer of 1-6) and so on .

As the perfluoroalkenyl group, the following three groups are preferably exemplified.

[Chemical Formula 9]

In the formula (2), R ¹ represents H or CH ₃ , R ³ represents a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group may have a halogen atom, an ether bond (-O- ), An ester bond (-COO- or -O-CO-), an amide bond (-CONH- or -NHCO-) or an aryl group or an arylene group, Z (-COO- or -O-CO-), an amide bond (-CONH- or -NHCO-), a sulfonic acid ester bond (-SO ₂ -O- or -O-SO ₂ -), (-SO ₂ NH- or -NHSO ₂ -), an ether bond (-O-), or a thioether bond (-S-). The saturated aliphatic hydrocarbon group of &quot; bivalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms &quot; may be any of linear, branched or cyclic. For example, 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 more substituents, and the substituent is not particularly limited as long as it does not adversely affect the present invention. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. Examples of the 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 monomers 2 may be used singly or in combination of two or more.

Monomer (3): As the (meth) acrylic monomer containing a reactive site, trimethylammonium and a (meth) acrylic monomer containing no fluorine are shown by the following formulas.

[Chemical formula 10]

Wherein R ¹ represents H or CH ₃ and W ¹ represents H or an alkoxyl group, an aryl group which may have a substituent, a hydroxyl group, a carboxyl group (COOH), an amino group, a mercapto group, an isocyanate group, Cetane group, lactone group, phosphoric acid group and the like.

In the formula, R ⁴ represents 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 (phenylene, naphthylene, etc.) which may have a substituent. The alkylene group of the "divalent alkylene group having 1 to 10 carbon atoms" may be any of linear, branched or cyclic. For example, a methylene group, an ethylene group, a propylene group, a butylene group, a cyclopentylene group, a cyclohexylene group, and an octylene group. These alkylene groups may have a substituent, and the substituent is not particularly limited as long as it does not adversely affect the present invention. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen group, and the like. The alkylene moiety of the "bivalent alkylene oxide group having 2 to 4 carbon atoms" may be either a linear chain or a branched chain, and the repeating unit of the alkylene oxide is preferably about 1 to 20.

Wherein Z represents a single bond, O, NH, NHCO, or S;

The monomers 3 may be used singly or in combination of two or more.

Monomer (4): The (meth) acrylic monomer containing a moiety capable of reacting with the monomer (3) is characterized by being represented by the following formula and includes, for example, an isocyanate group-containing (meth) acrylate, a glycidyl group- (Meth) acrylate, oxetane-containing (meth) acrylate, lactone ring-containing (meth) acrylate, and phosphoric acid group-containing (meth) acrylate.

(11)

Wherein, R ¹ is H or represents a CH _3, W ² is W ¹ and capable of reacting with H or alkoxy group, which may have a substituent, an aryl group, a hydroxyl group, a carboxyl group (COOH), an amino group, a mercapto group, an isocyanate A glycidyl group, an oxetane group, a lactone group, and a phosphoric acid group. W ² is not particularly limited as long as it is a functional group capable of reacting with W ¹ .

In the formula, R ⁴ represents 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 (phenylene, naphthylene, etc.) which may have a substituent. The alkylene group of the "divalent alkylene group having 1 to 10 carbon atoms" may be any of linear, branched or cyclic. For example, a methylene group, an ethylene group, a propylene group, a butylene group, a cyclopentylene group, a cyclohexylene group, and an octylene group. These alkylene groups may have a substituent, and the substituent is not particularly limited as long as it does not adversely affect the present invention. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen group, and the like. The alkylene moiety of the "bivalent alkylene oxide group having 2 to 4 carbon atoms" may be either a linear chain or a branched chain, and the repeating unit of the alkylene oxide is preferably about 1 to 20.

Wherein Z represents a single bond, O, NH, NHCO, or S;

The monomers 4 may be used singly or in a mixture of two or more.

The (meth) acrylate-based copolymer containing the monomer (1) and the monomer (2) as copolymer components is characterized in that it contains 1 to 90% by weight of the monomer (1) and 1 to 50% by weight of the monomer (2) And may further contain monomer (3) and / or monomer (4).

In the (meth) acrylate-based copolymer containing the monomer (1), the monomer (2) and the monomer (3) as a copolymerization component and having a reactive functional group derived from the monomer (4) 1 to 90% by weight of monomer (1), 1 to 30% by weight of monomer (2), 1 to 90% by weight of monomer (3) and 0 to 50% by weight of monomer (4) having reactive functional group. The monomer 4 is not required when the W group of the monomer 1 has a group capable of reacting with the monomer 3 (reactive functional group), that is, when the monomer 1 also serves as the monomer 4. In this case, The monomer (4) may be 0% by weight.

The (meth) acrylate-based copolymer of the present invention is useful as an antimicrobial agent that imparts an excellent antimicrobial effect to various materials and an antistatic agent that imparts an excellent antistatic effect. Examples of the material that can be blended include rubber such as silicone and acrylic, plastic such as vinyl chloride, polyolefin, polyurethane, ABS, polystyrene, vinyl acetate and polycarbonate, phenol, (meth) acrylate, urethane acrylate And the like. The composition of the present invention can be imparted with antimicrobial property and antistatic property by being compounded with the material or coated on the surface of the molded article and the shape of the molded article can be suitably selected from the group consisting of a fiber, Or a block or the like.

The (meth) acrylate-based copolymer of the present invention can be obtained by dissolving or suspending the (meth) acrylate-based copolymer in a liquid medium such as water or an organic solvent by a conventional coating means such as spray coating, coater coating, dipping, , Various metals, plastics, ceramics, resins, and the like to form a coating film, thereby preventing the growth of bacteria in various kinds of materials. The concentration of the (meth) acrylate-based 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. If the concentration of the (meth) acrylate-based copolymer in the solution is too low, the amount of the (meth) acrylate-based copolymer present on the surface becomes small and the modified surface sprayed or sprayed becomes thin, It becomes a factor of deterioration of the prevention. On the other hand, when the concentration is excessively high, coating non-uniformity may occur. The concentration of the (meth) acrylate-based copolymer in the solution is also influenced by the solubility of the solvent, the molecular weight of the polymer, and the like. A preferable proportion of the (meth) acrylate-based copolymer of the present invention to be blended in various materials is 0.1 to 20% by weight, more preferably 0.5 to 5% by weight, per 100% by weight of the material to be imparted with antimicrobial property or antistatic property Weight%. The (meth) acrylate-based copolymer may be used singly or as a mixture.

Specific examples of the application of the material or the molded article to which the (meth) acrylate-based copolymer of the present invention is blended include textile products such as towels, carpets, curtains and clothes, leather products, refrigerators, washing machines, dish dryers, vacuum cleaners, Kitchenware such as telephone products such as car, PC, car navigation, building material such as wallpaper, tile, brick, concrete, screw and joint, daily necessities such as wash basin, broom, hose, slipper, trash can, kitchen of triangular corner net, Supplies, water surroundings, toiletries, various coating materials, paints and adhesives.

Since the (meth) acrylate copolymer of the present invention may have a reactive acrylate group or a methacrylate group in the molecule, the (meth) acrylate copolymer may have an antimicrobial effect or a high antistatic effect Sustainability can be expected.

Further, by controlling the amount of the reactive group in the (meth) acrylate-based copolymer, the reaction conditions, etc., it is possible to improve the film strength as a surface modifying agent and design the strength according to the purpose.

In the antimicrobial activity test method and the antistatic property test method of the present invention, the coating liquid obtained by dissolving the (meth) acrylate-based copolymer of the present invention in an organic solvent is applied to a base material, After removal of the solvent, an antimicrobial or antistatic film can be formed.

The coating method of the coating liquid is not particularly limited, and examples of the coating method include a gravure coating method, a bar coating method, a wire bar coating method, a spin coating coating method, a doctor blade coating method, A slit coat method, and the like.

Antimicrobial resin composition or antistatic resin composition

The antimicrobial component of the antimicrobial resin composition or the antistatic component of the antistatic resin composition in the present invention is a (meth) acrylate-based copolymer containing the monomer (1) and the monomer (2) A compound having a reactive functional group may be further added to the compound. The (meth) acrylate-based copolymer may be used singly or as a mixture.

How to use

The (meth) acrylate-based copolymer can be obtained by copolymerizing a monomer having a polymerizable unsaturated group such as, for example, toluene, xylene, diethyl ether, ethyl acetate, methyl ethyl ketone, acetone, acetonitrile, propionitrile, diethylene glycol monoethyl ether, It can be used as a solution of an organic solvent such as diethyl ether, ethanol, isopropanol, tetrahydrofuran or 1,4-dioxane, or as a solution added to a coating liquid (resin composition) such as a paint.

The (meth) acrylate-based copolymer may be used singly or in combination of two or more kinds. The solvent used in the solution may be used singly or in a mixture of two or more kinds.

The solution containing the (meth) acrylate-based copolymer of the present invention is applied to the surface of a base material such as resin, film, fiber, glass or metal by coating, coating, spraying or the like, Antimicrobial or antistatic properties can be imparted. That is, by evaporating the solvent in the solution, a film containing the (meth) acrylate-based copolymer of the present invention is formed on the surface of the coating film. The film has antimicrobial property, antistatic property, transparency and the like. The drying (evaporation) conditions of the solvent vary depending on the kind and amount of the solvent in the solution, and usually the solvent is dried at room temperature to 200 ° C for about 10 seconds to 10 minutes.

The concentration of the solution of the (meth) acrylate-based copolymer 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 solution of the (meth) acrylate-based copolymer in the solution is too low, the amount of the (meth) acrylate-based copolymer present on the surface becomes small and the surface of the applied film sprayed or sprayed becomes thin, It becomes a factor of antibacterial property or antistatic property. Further, there may arise a problem that the strength of the surface of the coating film is not sufficiently obtained. On the other hand, when the concentration is excessively high, coating non-uniformity may occur. The concentration of the solution of the (meth) acrylate-based copolymer in the solution is also influenced by the solubility of the solvent, the molecular weight of the polymer, and the like.

The antimicrobial and / or antistatic resin composition of the present invention can be obtained by blending a curable component (resin monomer, resin oligomer, polymerization initiating component, etc.) into a curable resin composition (curable antimicrobial and / or antistatic resin Composition). Hereinafter, the antimicrobial and / or antistatic resin composition of the present invention having a curable component may be referred to as a &quot; curable resin composition &quot;. The resin composition of the present invention is preferably a &quot; curable resin composition &quot;.

(Meth) acrylate-based copolymer as an effective component

The curable resin composition contained in the present invention is prepared as a coating liquid for application to a substrate. As the curable resin composition (coating liquid), a (meth) acrylate-based copolymer mainly as an antifouling component, an energy ray-curable resin monomer or resin oligomer mainly functioning as a resin film, a polymerization initiator, do. However, when a solvent-free coating liquid is used, a solvent is not blended, and in the case of radiation curing, a polymerization initiator is not required. Further, other components may be added to the coating liquid as necessary.

The content of the (meth) acrylate-based copolymer in the total amount of the curable resin composition of the present invention (excluding the amount of the solvent component when the solvent component is used) is usually about 0.0006 to 17% by weight Is about 0.007 to 13% by weight, and more preferably about 0.07 to 10% by weight.

The (meth) acrylate-based copolymer of the present invention exhibits a function as an antimicrobial agent in a cured film obtained by polymerization with an energy ray-curable resin monomer and / or a resin oligomer to be described later.

Energy radiation curable resin monomer or resin oligomer component

The curable resin composition of the present invention may contain, in addition to the (meth) acrylate-based copolymer, an energy ray-curable resin monomer and / or a resin oligomer (hereinafter sometimes referred to as a resin monomer or a resin oligomer) ).

Such a resin monomer and a resin oligomer are not particularly limited as long as they react with the (meth) acrylate-based copolymer to form a cured film. Usually, the resin monomer and the resin oligomer used in the hard coat film or the antireflective coating film And / or resin oligomers may optionally be used.

Examples of the resin monomer and the resin oligomer include reactive compounds such as acrylate, urethane, epoxy, and silicone such as various acrylates and acryl urethane, and acrylic resins are preferably used. Particularly, since 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 more reactive functional group.

Examples of the resin monomer and resin oligomer having a bifunctional or more reactive functional group include tricyclodecane dimethylol diacrylate, bisphenol F EO-modified diacrylate, bisphenol A EO-modified diacrylate, isocyanuric acid EO-modified di Acrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylpropane PO modified triacrylate, glycerin PO-added triacrylate, trimethylolpropane EO Modified triacrylate, isocyanuric acid EO-modified triacrylate,? -Caprolactone-modified tris (acryloxyethyl) isocyanurate , Pentaerythritol triacrylate, penta Ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, various urethane acrylate oligomers (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., manufactured by Negami Kogyo Co., Ltd.) Art Resin Series, etc.), but the present invention is not limited thereto. The resin monomer and the resin oligomer may be used singly, but two or more kinds thereof may be used in an arbitrary ratio.

Examples of the energy ray for curing the resin monomer and the resin oligomer include radiation, electron beam, ultraviolet ray, and visible ray. In the curing by radiation or electron beam, since the energy of the electromagnetic wave is high, the polymerization can be carried out only by the polymerizable double bond. When an ultraviolet ray or a visible ray is used as an energy source, it is preferable to blend a polymerization initiator component to be described later.

The content of the resin monomer and the resin oligomer in the total amount of the curable resin composition of the present invention (excluding the amount of the solvent component when the solvent component is used) is usually about 55 to 99.9% by weight, preferably about 60 To 99.5% by weight, and more preferably about 70 to 99% by weight.

The ratio of the resin monomer and the resin oligomer to the (meth) acrylate-based copolymer is usually 0.001 to 18% by weight, based on 100% by weight of the resin monomer and the resin oligomer, of the (meth) , Preferably about 0.01 to 15% by weight, and more preferably about 0.1 to 10% by weight.

The polymerization initiator component

The curable resin composition of the present invention may contain a polymerization initiator component, if necessary, in addition to the (meth) acrylate-based copolymer, the resin monomer and / or the resin oligomer.

As the polymerization initiator component, conventionally known ones may be used, and for example, a photopolymerization initiator may be used.

A variety of photopolymerization initiators are known and may be appropriately selected and used. For example, there may be mentioned 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy- 2-methyl-1-propan-1-one, 2-methyl-1- [4- (methyl (2, 6-dimethoxybenzoyl) - &lt; / RTI &gt; (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-hydroxy-1- {4- [4- (2-hydroxy- (Phenylthio) -, 2- (O-benzoyloxime)], 2- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (0-acetyloxime), 2,2- , 4,5,5-tetraphenyl-1,2-biimidazole, 2,2-diethoxyacetophenone, benzophenone, methyl O-benzoylbenzoate, 4,4-bis (dimethylamino) Benzophenone, benzene, anthraquinone, anthrone, dibenzosuberone, dibenzoylmethane, dibenzoylketone, dibenzoylketone, fluorenone, 2-hydroxy-2-methylpropiophenone, thioxanthone, benzyldimethylketol, benzylmethoxyethyl acetal, (3-carbonyl) -bis (7-di (isopropylamino) phenyl) -isonaphthol, 4,4-bis (dimethylamino) chalcone, P- Ethyl amino coumarin), 3-phenyl-5-benzoylthio-tetrazole and the like.

When a polymerization initiator component is used, one type may be used alone, or two or more types may be arbitrarily used. The addition amount of the polymerization initiator component is usually about 0.1 to 50% by weight, preferably about 0.1 to 50% by weight based on 100% by weight of the polymerizable resin component ((meth) acrylate copolymer, the resin monomer and / 0.5 to 40% by weight, and more preferably about 1 to 30% by weight.

Solvent component

The curable resin composition of the present invention does not need to contain a solvent component, but may contain a solvent component if necessary. As the solvent component, conventionally known solvent components may be used. For example, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, . These solvent components may be used singly or in combination of two or more thereof in any desired ratio.

When the solvent component is used, the amount of the solvent component used in the curable resin composition of the present invention is preferably 100 parts by weight of the polymerizable resin component (the total amount of the (meth) acrylate copolymer, the resin monomer and / or the resin oligomer) Usually about 25 to 5,000 parts by weight, preferably about 40 to 2,000 parts by weight, and more preferably about 60 to 1,000 parts by weight.

Other components

The curable resin composition of the present invention may be blended with fine particles, fillers and the like as necessary in order to form a shape on the surface of the cured film or to impart other desired functions.

Method of making cured film

In the present invention, the curable resin composition of the present invention may be used as a coating liquid, and the coating liquid may be applied to a base material, followed by irradiation with light or the like to form a cured film.

As a procedure for obtaining the cured film of the present invention, the polymerization initiator component, the solvent component, the fine particles, the filler and the like may be added in a suitable mixing ratio (if necessary) in the order of (meth) acrylate copolymer, resin monomer and / To prepare a curable resin composition of the present invention as a coating solution. Subsequently, a cured film can be obtained by applying a coating liquid on a substrate so as to have a constant film thickness, removing solvent components by hot air drying or vacuum drying, and irradiating energy lines such as radiation, electron beam, ultraviolet ray and visible ray.

The coating method of the coating liquid is not particularly limited, and examples of the coating method include a gravure coating method, a bar coating method, a wire bar coating method, a spin coating coating method, a doctor blade coating method, A slit coat method, and the like.

The substrate on which the cured film is formed is not particularly limited as long as it can support the cured film. For example, in the case of being used as a hard coat for optical use, a sheet having transparency is preferable. As a material of the transparent sheet, glass, plastic and the like can be mentioned, and a plastic sheet is particularly preferable. As the plastic, a thermoplastic resin, a thermosetting resin or the like can be used. Examples of the plastic include a polyolefin resin such as polyethylene and polypropylene, a polyester resin such as polyethylene terephthalate, a cellulose resin such as triacetylcellulose and butylcellulose, a polystyrene resin, Polyurethane resin, polyvinyl alcohol, polyvinyl chloride, acrylic resin, polycarbonate resin, polyacrylonitrile, cycloolefin polymer, and polyethersulfone. These sheets may be subjected to an adhesion facilitating treatment such as a binder treatment, a corona treatment, a plasma treatment, a frame treatment or the like, if necessary.

The thickness of the cured film of the present invention is not particularly limited and may be appropriately selected depending on the application. Normally, it may be about 100 nm to 30 탆.

Antibacterial test method and antistatic property test method

The antibacterial activity of the test pieces prepared in the following Examples 1 to 12 was evaluated by the following method. Escherichia coli (IFO3301) was used as a test subject, and a diluted solution was prepared so that the number of bacteria was around 10 ² . Subsequently, 200 占 퐇 of diluted solution was dropped onto a test piece (5 cm in length and breadth), adhered to a low-nutrient agar medium, and cultured at 35 占 폚 for 24 hours. Subsequently, the test pieces were transferred to an ordinary agar agar medium and cultured at 35 DEG C for 24 hours. And the growth state of the microorganism after the culture was confirmed. The results of the antibacterial test thus obtained are shown in Table 4 below.

The antistatic properties of the test pieces prepared in the following Examples 1 to 12 were evaluated by the following methods.

One-fourth of the volume of the foamed beads was put into a transparent normal container. Next, a test piece (5 cm in length and breadth) was usually pasted to the inside of the container. After the container was sealed, the foamed beads were shaken up and down 50 times. Thereafter, the state of the foamed beads at the time of still stopping was confirmed. The results of the antistatic property test are shown in Table 4 below.

Example

The content of the present invention will be described by the following examples, but the content of the present invention is not limited to the examples.

Synthesis Example 1

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 three-necked flask (3 L) equipped with a dropping funnel. 973.0 g (2.16 mol) of hexafluoropropene trimmer was added to the dropping funnel, and the solution was slowly added dropwise to the solution in the flask over about 60 minutes while stirring. After completion of the dropwise addition, stirring at room temperature was continued for further 3 hours.

2200 g of 1 N hydrochloric acid was added to the reaction mixture to stop the reaction, and then the reaction mixture was transferred into a 5 L beaker, followed by washing three times with 1 L of water. The solution after the water washing treatment was dehydrated under reduced pressure to obtain 937.8 g (yield: 93%) of the fluorinated acrylate represented by the following formula (A-1). Table 1 shows the data of ¹ H-NMR of the obtained fluorinated acrylate (A-1).

[Chemical Formula 12]

Wherein Rf is a group represented by the following general formula:

[Chemical Formula 13]

Synthesis Example 2

2.80 g (5 mmol) of the fluorinated acrylate (A-1) synthesized in Synthesis Example 1 and 24.3 g (5 mmol) of DMAMC (B-1) manufactured by Osaka Organic Synthesis Industry Co. were charged in a three-necked flask 54.3 g of methyl ethyl ketone, 54.3 g of 2-propanol and 0.24 g (1.1 mmol) of dimethyl 2,2'-azobis (2-methylpropionic acid). Nitrogen gas was introduced into the reaction solution, and the interior of the reaction vessel was replaced with nitrogen. After replacing nitrogen, the reaction solution was heated to 80 DEG C while stirring the reaction solution to initiate the reaction. Then stirring was continued at 80 캜 for 14 hours. The termination of the reaction was confirmed by disappearance of each acrylate-specific peak in ¹ H-NMR. The solvent was distilled off to obtain a desired (meth) acrylate-based copolymer quantitatively.

[Chemical Formula 14]

Synthesis Example 3

Synthesis was carried out by changing the ratios of the monomers (A-1) and (B-1) in the same manner as in Synthesis Example 2. The monomer ratios are shown in Table 3.

Synthesis Example 4

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 three-necked flask (3 L) equipped with a dropping funnel. 1264.68 g (2.16 mol) of the fluorinated acid chloride represented by the following general formula (7) was added to the dropping funnel, and the solution was slowly added dropwise to the solution in the flask over about 60 minutes while stirring. After completion of the dropwise addition, stirring at room temperature was continued for further 3 hours.

2200 g of 1 N hydrochloric acid was added to the reaction mixture to stop the reaction, and then the reaction mixture was transferred into a 5 L beaker, followed by washing three times with 1 L of water. The solution after the water washing treatment was dehydrated under reduced pressure to obtain 1138.3 g (yield: 93%) of the fluorinated acrylate represented by the following formula (A-1). Table 1 shows the data of ¹ H-NMR of the obtained fluorinated acrylate (A-2).

[Chemical Formula 15]

[Chemical Formula 16]

Wherein Rf is a group represented by the following general formula:

[Chemical Formula 17]

Synthesis Example 5

The same procedure as in Synthesis Example 2, the monomer (A-1) a fluorinated acrylate (A-2 instead of: RfO-Ph-C (= O) O-CH 2 CH 2 OC (= O) C (CH 3) = CH ₂ ). The monomer ratios are shown in Table 3.

Synthesis Example 6

(A-3: CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OC (= O) CH = CH ₂ ) was used instead of the monomer (A-1) And the synthesis was carried out. The monomer ratios are shown in Table 3.

Synthesis Example 7

Synthesis was carried out in the same manner as in Synthesis Example 2 except that DMCMA (B-2) manufactured by Osaka Organic Synthesis Industry was used instead of the monomer (B-1). The monomer ratios are shown in Table 3.

[Chemical Formula 18]

Synthesis Example 8

Synthesis was carried out in the same manner as in Synthesis Example 2 except that DMAPAA-Q (B-3) produced by COZINE was used instead of the monomer (B-1). The monomer ratios are shown in Table 3.

[Chemical Formula 19]

Synthesis Example 9

Synthesis was carried out in the same manner as in Synthesis Example 2, except that the monomer (B-1) was replaced with a neem oil-producing blumer QA (B-4). The monomer ratios are shown in Table 3.

[Chemical Formula 20]

Synthesis Example 10

Synthesis was carried out in the same manner as in Synthesis Example 2 using monomeric (A-1), monomer (B-1) and monomeric (C-1) The monomer ratios are shown in Table 3.

The structure of PME-100 produced by the healing process is shown below.

[Chemical Formula 21]

Synthesis Example 11

Synthesis was carried out by changing the ratios of the monomer (A-1), the monomer (B-1) and the monomer (C-1) in the same procedure as in Synthesis Example 2. The monomer ratios are shown in Table 3.

Synthesis Example 12

Synthesis was carried out by changing the ratios of the monomer (A-1), the monomer (B-1) and the monomer (C-1) in the same procedure as in Synthesis Example 2. The monomer ratios are shown in Table 3.

Synthesis Example 13

Synthesis was carried out in the same manner as in Synthesis Example 2 except that AE-90, manufactured by Nisshin Oils, was used as the monomer (C-2) instead of the monomer (C-1). The monomer ratios are shown in Table 3.

The structure of the heath-care preparation AE-90 (C-2) is shown below.

[Chemical Formula 22]

Synthesis Example 14

Synthesis was carried out by using monomer (A-1) and monomer (A-3) in combination in the same procedure as in Synthesis Example 2 and changing the ratio. The monomer ratios are shown in Table 3.

Antimicrobial Test Method

The antibacterial activity of the test pieces prepared in Examples 1 to 12 was evaluated by the following methods. Escherichia coli (IFO3301) was used as a test subject, and a diluted solution was prepared so that the number of bacteria was around 10 ² . Subsequently, 200 占 퐇 of diluted solution was dropped onto a test piece (5 cm in length and breadth), adhered to a low-nutrient agar medium, and cultured at 35 占 폚 for 24 hours. Subsequently, the test pieces were transferred to an ordinary agar agar medium and cultured at 35 DEG C for 24 hours. And the growth state of the microorganism after the culture was confirmed. The results of the antibacterial test thus obtained are shown in Table 4 below.

Examples 1 to 12

A 2 mass% methanol solution of the (meth) acrylate copolymer described in Synthesis Examples 2 to 3 and Synthesis Examples 5 to 14 was applied to a PET film. Thereafter, it was dried at 80 DEG C for 10 minutes. An antimicrobial property test was conducted using the dried (meth) acrylate-based copolymer coating film as a test piece. The measurement results are shown in Table 4.

Comparative Example 1

An antimicrobial property test was conducted using a PET film having no antimicrobial agent as a test piece. The measurement results are shown in Table 4.

Comparative Example 2

Was applied to a PET film using a 2 mass% methanol dispersion solution of Novaron AG300 as an inorganic antimicrobial agent. Thereafter, it was dried at 80 DEG C for 10 minutes. The antibacterial agent composition coating film after drying was used as a test piece to carry out an antibacterial activity test. The measurement results are shown in Table 4.

Comparative Example 3

Was applied to a PET film using the 2 mass% methanol solution of the fluorine-containing monomer described in Synthesis Example 1. Thereafter, it was dried at 80 DEG C for 10 minutes. The antibacterial property test was carried out using the dried fluorinated monomer coating film as a test piece. The measurement results are shown in Table 4.

Comparative Example 4

Was applied to a PET film using the 2 mass% methanol solution of the fluorinated monomer described in Synthetic Example 4. Thereafter, it was dried at 80 DEG C for 10 minutes. The antibacterial property test was carried out using the dried fluorinated monomer coating film as a test piece. The measurement results are shown in Table 4.

Evaluation of antimicrobial activity (Tables 4 and 5)

(1) Antimicrobial activity

Evaluation criteria: ◎ = No growth of bacteria

○ = Number of colonies 1 ~ 50

? = The number of colonies is 50 or more, but the antibacterial effect can be seen

× = Less than or equal to that of unincorporated PET film, no antibacterial effect

(2) Transparency

The transparency of the test piece was visually observed.

Evaluation Criteria: Transparent = ○

In cloudiness = ×

As can be seen from Table 4, the antimicrobial composition of the present invention has excellent antimicrobial activity and excellent transparency.

Examples 13 to 24

0.04 parts by mass (50% by mass solution) of the (meth) acrylate-based copolymer described in Synthesis Examples 2, 3 and 5 to 14 and 20 parts by mass of the phenolic resin were added to methyl ethyl ketone, ) Was coated with a bar coater (No. 8). Thereafter, it was dried at 80 DEG C for 3 minutes. Thereafter, the coating film was cured by using a UV irradiation apparatus. The antimicrobial property-imparting resin composition after curing was cut into antimicrobial properties and antistatic properties by using it as a test piece for antibacterial test. Table 5 shows the results of the antimicrobial activity test and the antistatic property test.

Comparative Example 5

A test piece was prepared in the same manner as in Example 13 with no antimicrobial agent added and subjected to an antibacterial test. The measurement results are shown in Table 5.

Comparative Example 6

A test piece was prepared in the same manner as in Example 13 using NovaRon AG300 as an inorganic antimicrobial agent in an amount of 5% by weight based on the resin, and the antimicrobial activity test was carried out. The measurement results are shown in Table 5.

Comparative Example 7

A test piece was prepared in the same manner as in Example 13, using the fluorine-containing monomer described in Synthesis Example 1 as an antimicrobial agent in an amount of 5% by weight based on the resin, and then subjected to an antibacterial test. The measurement results are shown in Table 5.

Comparative Example 8

A test piece was prepared in the same manner as in Example 13, using the fluorine-containing monomer described in Synthesis Example 4 as an antimicrobial agent in an amount of 5% by weight based on the resin, and subjected to an antibacterial test. The measurement results are shown in Table 5.

Comparative Example 9

A test piece was prepared in the same manner as in Example 13, using the monomer (B-1) as an antimicrobial agent in an amount of 5% by weight with respect to the resin, and subjected to an antibacterial test. The measurement results are shown in Table 5.

Comparative Example 10

A test piece was prepared in the same manner as in Example 13, using the monomer (B-1) as an antimicrobial agent in an amount of 20% by weight with respect to the resin, and subjected to an antibacterial test. The measurement results are shown in Table 5.

* Evaluation of antistatic property

       Evaluation criteria: ◎ = no adhesion of foam beads

○ = number of foam beads attached 1 ~ 10

△ = number of attached foam beads 10 to 30

× = 30 or more of the number of foamed beads, no antistatic effect can be obtained

* Coating film hardness

According to JIS K 5600-5-4, a pencil core was stuck at an angle of about 45 ° with respect to the test board surface, and the test board was pressed at a load of 750 g at a uniform speed at a uniform speed of about 10 mm. The hardness symbol of the hardest pencil that did not break the coating was the film hardness.

As can be seen from Table 5, the resin composition of the present invention is excellent in antimicrobial activity, excellent in transparency and antistatic property.

Even if the resin is changed, it is possible to suppress streaking or cratering by adding an additive, and antimicrobiality is expressed by adding a (meth) acrylate-based copolymer. In addition, the transparency of the resin composition is lost in the use of the inorganic antimicrobial agent, but the (meth) acrylate-based copolymer of Synthesis Examples 2 to 9 and 11 is excellent in antibacterial performance and transparency.

Industrial availability

The (meth) acrylate-based copolymer according to the present invention is useful as an antimicrobial property-imparting agent and antistatic property-imparting agent used in the fields of, for example, glass, fiber, metal, resin, film, optical material, And is useful as a compound capable of imparting antimicrobial properties, transparency and antistatic properties to the surface of a substrate.

Claims (9)

(Meth) acrylate-based copolymer comprising the following monomer (1) and the monomer (2) as a copolymerization component.
Monomer (1): Trimethylammonium-containing (meth) acrylic monomer
[Chemical Formula 1]

Wherein 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 substituted with a halogen atom, an ether bond (-O-) (-S-), an ester bond (-COO- or -O-CO-), an amide bond (-CONH- or -NHCO-) or an aryl group or an arylene group, Y is the same (-COO- or -O-CO-), an amide bond (-CONH- or -NHCO-), a sulfonic acid ester bond (-SO ₂ -O- or -O-SO ₂ - ), sulfonamide bond (-SO ₂ NH- or -NHSO ₂ -), ether bond (-O-), represents a thioether bond (-S-), X represents a halogen atom, W is H or alkoxy group , An aryl group which may have a substituent, a hydroxyl group, a carboxyl group (COOH), an amino group, a mercapto group or an isocyanate group.
Monomer (2): fluorine-containing (meth) acrylate
(2)

Wherein 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 , and R ³ represents a divalent group having 1 to 50 carbon atoms The saturated aliphatic hydrocarbon group may be substituted with a halogen atom, an ether bond (-O-), a thioether bond (-S-), an ester bond (-COO- or -O-CO-), an amide bond (-COOH- 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 (-SO ₂ -O- or -O-SO ₂ -), a sulfonamide bond (-SO ₂ NH- or -NHSO ₂ -), an ether bond (-O-), a thioether bond (- S-). The method according to claim 1,
(Meth) acrylate copolymer wherein Rf of the fluorine-containing (meth) acrylate of the formula (2) is a perfluoroalkenyl group having 2 to 9 carbon atoms. 3. The method according to claim 1 or 2,
(Meth) acrylate-based copolymer having a reactive functional group, which comprises the following monomer (1), monomer (2), and monomer (3) as a copolymerization component.
Monomer (1): Trimethylammonium-containing (meth) acrylic monomer
(3)

Wherein 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 substituted with a halogen atom, an ether bond (-O-) (-S-), an ester bond (-COO- or -O-CO-), an amide bond (-CONH- or -NHCO-) or an aryl group or an arylene group, Y is the same (-COO- or -O-CO-), an amide bond (-CONH- or -NHCO-), a sulfonic acid ester bond (-SO ₂ -O- or -O-SO ₂ - ), sulfonamide bond (-SO ₂ NH- or -NHSO ₂ -), ether bond (-O-), represents a thioether bond (-S-), X represents a halogen atom, W is H or alkoxy group , An aryl group which may have a substituent, a hydroxyl group, a carboxyl group (COOH), an amino group, a mercapto group or an isocyanate group.
Monomer (2): fluorine-containing (meth) acrylate
[Chemical Formula 4]

Wherein 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 , and R ³ represents a divalent group having 1 to 50 carbon atoms The saturated aliphatic hydrocarbon group may be substituted with a halogen atom, an ether bond (-O-), a thioether bond (-S-), an ester bond (-COO- or -O-CO-), an amide bond (-COOH- or -O-CO-), an amide bond (-CONH- or -NHCO-) or an aryl group or an arylene group), Z is a single bond, an ester bond -), a sulfonic ester bond (-SO ₂ -O- or -O-SO ₂ -), a sulfonamide bond (-SO ₂ NH- or -NHSO ₂ -), an ether bond (-O-), a thioether bond -S-).
Monomer (3): (meth) acrylic monomer containing reactive site
[Chemical Formula 5]

Wherein R ¹ represents H or CH ₃ and W ¹ represents H or an alkoxy group, an aryl group which may have a substituent, a hydroxyl group, a carboxyl group (COOH), an amino group, a mercapto group, an isocyanate group, An oxetane group, a lactone group, and a phosphoric acid group. R ⁴ represents an alkyl group or a divalent arylene group which may have a substituent or a divalent alkylene oxide group having 2 to 4 carbon atoms and Z represents a single bond, O, NH, NHCO or S. 3. The method according to claim 1 or 2,
Wherein the monomer composition of the copolymer is 1 to 90% by weight of the monomer (1) and 1 to 50% by weight of the monomer (2) when the entire copolymer is 100% by weight. The method of claim 3,
1 to 90% by weight of the monomer (1), 1 to 30% by weight of the monomer (2), 1 to 90% by weight of the monomer (3) And (4) a reactive functional group-containing monomer (4) in an amount of 0 to 50% by weight, wherein the monomer (4)
[Chemical Formula 6]

Wherein R ¹ represents H or CH ₃ , W ² represents H or an alkoxyl group capable of reacting with W ¹ , an aryl group which may have a substituent, a hydroxyl group, a carboxyl group (COOH), an amino group, a mercapto group, An isocyanate group, a glycidyl group, an oxetane group, a lactone group, and a phosphoric acid group. R ⁴ represents an alkyl group or a divalent arylene group which may have a substituent or a divalent alkylene oxide group having 2 to 4 carbon atoms and Z represents a single bond, O, NH, NHCO or S.
(Meth) acryl-based monomer containing a moiety capable of reacting with the monomer (3) represented by the formula (Meth) acrylate copolymer according to any one of claims 1 to 5, a salt-exchanged product thereof, and a mixture thereof, as an active ingredient Antimicrobial agent. An antimicrobial resin composition comprising at least one component selected from the group consisting of a (meth) acrylate-based copolymer according to any one of claims 1 to 5, a salt-exchanged product thereof, and a mixture thereof Composition. An antistatic composition, which comprises at least one component selected from the group consisting of the (meth) acrylate-based copolymer according to any one of claims 1 to 5, a salt-exchanged product thereof, Resin composition. 9. The method according to claim 7 or 8,
Wherein the resin composition is a curable resin composition comprising a curable resin monomer and / or a resin oligomer and a polymerization initiating component.