CN104395363A - (meth)acrylate-based copolymer, antimicrobial agent, antimicrobial property-imparting resin composition, and antistatic property-imparting resin composition - Google Patents
(meth)acrylate-based copolymer, antimicrobial agent, antimicrobial property-imparting resin composition, and antistatic property-imparting resin composition Download PDFInfo
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- CN104395363A CN104395363A CN201380032054.XA CN201380032054A CN104395363A CN 104395363 A CN104395363 A CN 104395363A CN 201380032054 A CN201380032054 A CN 201380032054A CN 104395363 A CN104395363 A CN 104395363A
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- 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
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- C08L2201/00—Properties
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Abstract
The present invention provides a (meth)acrylate-based copolymer comprising a monomer (1) and a monomer (2) as copolymerization components. Monomer (1) is a trimethylammonium-containing (meth)acrylic-based monomer (in the formula, R1, R2, Y, X, and W are as defined in the description). Monomer (2) is a fluorine-containing (meth)acrylate (in the formula, Rf, R1, R3, and Z are as defined in the description).
Description
Technical field
The present invention relates to a kind of novel (methyl) acrylate based copolymer and it can be used as the antiseptic-germicide of effective constituent, described multipolymer has the characteristic of characteristic caused by fluorine and leptodactyline concurrently.
In addition, the present invention relates to the resin combination of the endowing antibacterial of anti-microbial activity excellence and give the resin combination of static resistance, can be used in the fields such as glass, fiber, metal, resin, film, optical material, coating, described composition using novel (methyl) acrylate based copolymer of the characteristic of the characteristic that has concurrently caused by fluorine and leptodactyline as effective constituent.
Background technology
In the coating fluid for fields such as resin, optical material, coating, to suppress component surface to produce striped, repulsion, irregular, particle, the defect such as not moistening in coating process, namely give for the purpose of smoothness to coated film surface, various material can be added.
The additive that compound containing perfluorinated alkenyl also can be used as in this purposes uses, and particularly in imparting surface smoothness, the known nonionic system tensio-active agent with perfluorinated alkenyl is useful (such as, patent documentation 1.
In addition, thin display, PC monitor, mobile telephone, portable game machine, auto navigation etc. are used to various environment, advance contact panel.In the fluorescent screen of these equipment, particularly screen surface can adhere to the various dirt such as residue of sebum or makeup, beverage food, can promote the breeding of bacterium.In order to remove the dirt such as residue of sebum or makeup, beverage food, cloth etc. that is moisture or washing composition can be utilized to carry out wiping, but wiping dirt being not easy, sometimes also can make fluorescent screen produces chafe mark because carrying out repeatedly wiping.
For the purpose of anti-bacteria breeding, there will be a known the method importing antiseptic-germicide, be widely used (such as, patent documentation 2 and 3).In the past in order to develop various antiseptic-germicide to material requested endowing antibacterial, the antiseptic-germicide of known organic system and inorganic system.As the antiseptic-germicide of organic system, there will be a known the antiseptic-germicides such as the carboxylic serials such as phenol system compound, Sorbic Acid compound such as aldehyde based compound, the cresols such as alcohol based compound, the formalin such as hydroxyquinoline based compound, the ethanol such as Rhodan ester based compound, oxine such as the sulfur-bearing such as the quaternary ammonium salt based compounds such as benzalkonium chloride, 2,4-thibendoles benzimidazole compound, methylene-bis thiocyanic ester.On the other hand, as the antiseptic-germicide of inorganic system, there will be a known metal ion silver, copper, zinc etc. being shown germ resistance and be carried on gac, phosphatic rock, zeolite, tetravalent metal phosphate etc. and the antiseptic-germicide (patent documentation 4 ~ 6) obtained.
But, because existing organic system antiseptic-germicide generally lacks thermotolerance, therefore, if processed for the kneading to plastics or fiber etc., then there will be the problem such as variable color, foaming, or add generation volatilization in man-hour or decompose, sufficient antibacterial effect can not be played.In addition, in order to the endowing antibacterial such as plastics or resin, need a large amount of antiseptic-germicides, there is the problem performance of plastics or the resin originally had being reduced and so on.And then, because the cure component in organic system antiseptic-germicide and coating fluid does not have Chemical bond, therefore, exist because of the time through or from outside stimulation and cause coming off from resin cured film and effect disappear, the effect of softening agent is demonstrated, problem film toughness being reduced and so in film.
In addition, although the thermotolerance of existing inorganic series antibacterial agent or chemical resistant properties are excellent, exist costly, processing difficulties, the problem such as reproducibility difference of painted or variable color, effect may be occurred when adding man-hour or using.And, when using inorganic series antibacterial agent, being difficult to obtain transparent germ resistance and giving face.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-057589 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-037716 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2011-173816 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2007-223917
Patent documentation 5: Japanese Unexamined Patent Publication 2004-262795
Patent documentation 6: Japanese Unexamined Patent Publication 2004-217501
Summary of the invention
The problem that invention will solve
The object of the invention is to, a kind of novel (methyl) the acrylate based copolymer and the antiseptic-germicide that do not damage substrate performance are provided.
In addition, the object of the invention is to, provide a kind of germ resistance coating composition, it is the germ resistance coating composition not damaging substrate performance, and also has the transparency, static resistance that germ resistance gives face concurrently.
For solving the scheme of problem
The invention provides a kind of novel (methyl) acrylate based copolymer, antiseptic-germicide, the resin combination of endowing antibacterial and the resin combination of imparting static resistance.
<1>.
A kind of (methyl) acrylate based copolymer, it contains following monomer (1), monomer (2) as copolymer composition.
Monomer (1): (methyl) acrylic monomer containing trimethyl ammonium
[chemical formula 1]
[in formula, R
1represent H or CH
3, R
2(this representative examples of saturated aliphatic alkyl can have halogen atom, ehter bond (-O-), thioether bond (-S-), ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-) or aryl, arylidene to the divalent representative examples of saturated aliphatic alkyl of expression carbonatoms 1 ~ 50 as required.), Y is identical or different, represents singly-bound, ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-), sulfonic acid ester bond (-SO
2o-or-O-SO
2-), sulphonamide key (-SO
2nH-or-NHSO
2-), ehter bond (-O-), thioether bond (-S-), X represents halogen atom, and W represents H or alkoxyl group, can have substituent aryl, hydroxyl, carboxyl (COOH), amino, sulfydryl or isocyanate group.]
Monomer (2): fluorine-containing (methyl) acrylate
[chemical formula 2]
[in formula, Rf represents the perfluoroalkyl of carbonatoms 1 ~ 9 or the perfluorinated alkenyl of carbonatoms 2 ~ 9, R
1represent H or CH
3, R
3(this representative examples of saturated aliphatic alkyl can have halogen atom, ehter bond (-O-), thioether bond (-S-), ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-) or aryl, arylidene to the divalent representative examples of saturated aliphatic alkyl of expression carbonatoms 1 ~ 50 as required.), Z represents singly-bound, ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-), sulfonic acid ester bond (-SO
2o-or-O-SO
2-), sulphonamide key (-SO
2nH-or-NHSO
2-), ehter bond (-O-), thioether bond (-S-).]
<2>.
(methyl) acrylate based copolymer according to <1>, wherein, the Rf of described fluorine-containing (methyl) acrylate of formula (2) is the perfluorinated alkenyl of carbonatoms 2 ~ 9.
<3>.
(methyl) acrylate based copolymer according to <1> or <2>, it has reactive functional groups, and containing following monomer (1), monomer (2) and monomer (3) as copolymer composition.
Monomer (1): (methyl) acrylic monomer containing trimethyl ammonium
[chemical formula 3]
[in formula, R
1represent H or CH
3, R2 represents that (this representative examples of saturated aliphatic alkyl can have halogen atom, ehter bond (-O-), thioether bond (-S-), ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-) or aryl, arylidene as required for the divalent representative examples of saturated aliphatic alkyl of carbonatoms 1 ~ 50.), Y is identical or different, represents singly-bound, ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-), sulfonic acid ester bond (-SO
2o-or-O-SO
2-), sulphonamide key (-SO
2nH-or-NHSO
2-), ehter bond (-O-), thioether bond (-S-), X represents halogen atom, and W represents H or alkoxyl group, can have substituent aryl, hydroxyl, carboxyl (COOH), amino, sulfydryl or isocyanate group.]
Monomer (2): fluorine-containing (methyl) acrylate
[chemical formula 4]
[in formula, Rf represents the perfluoroalkyl of carbonatoms 1 ~ 9 or the perfluorinated alkenyl of carbonatoms 2 ~ 9, R
1represent H or CH
3, R
3(this representative examples of saturated aliphatic alkyl can have halogen atom, ehter bond (-O-), thioether bond (-S-), ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-) or aryl, arylidene to the divalent representative examples of saturated aliphatic alkyl of expression carbonatoms 1 ~ 50 as required.), Z represents singly-bound, ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-), sulfonic acid ester bond (-SO
2o-or-O-SO
2-), sulphonamide key (-SO
2nH-or-NHSO
2-), ehter bond (-O-), thioether bond (-S-).]
Monomer (3): containing can (methyl) acrylic monomer of reactive site
[chemical formula 5]
[in formula, R
1represent H or CH
3, W
1represent H or alkoxyl group, the functional groups such as substituent aryl, hydroxyl, carboxyl (COOH), amino, sulfydryl, isocyanate group, glycidyl, oxetanyl, lactone group, phosphate can be had.R
4represent that alkyl maybe can have the divalent epoxy alkyl of substituent divalent arylidene, carbonatoms 2 ~ 4, Z represents singly-bound, O, NH, NHCO or S.]
<4>.
(methyl) acrylate based copolymer according to <1> or <2>, wherein, using overall for multipolymer as 100 % by weight time, the set of monomers of multipolymer becomes: monomer (1) is 1 ~ 90 % by weight, and (2 is 1 ~ 50 % by weight to monomer.
<5>.
(methyl) acrylate based copolymer according to <3>, wherein, using overall for multipolymer as 100 % by weight time, the set of monomers of multipolymer becomes: monomer (1) is 1 ~ 90 % by weight, monomer (2) is 1 ~ 30 % by weight, monomer (3) is 1 ~ 90 % by weight, and the monomer (4) with reactive functional groups is 0 ~ 50 % by weight, monomer (4) (methyl) acrylic monomer containing the position can reacted with monomer (3) represented by following formula.
[chemical formula 6]
[in formula, R
1represent H or CH
3, W
2represent energy and W
1reaction H or alkoxyl group, the functional groups such as substituent aryl, hydroxyl, carboxyl (COOH), amino, sulfydryl, isocyanate group, glycidyl, oxetanyl, lactone group, phosphate can be had, R
4represent that alkyl maybe can have the divalent epoxy alkyl of substituent divalent arylidene, carbonatoms 2 ~ 4, Z represents singly-bound, O, NH, NHCO or S.]
<6>.
A kind of antiseptic-germicide, it is characterized in that, using more than one the composition in (methyl) acrylate based copolymer, its salt quid pro quo and their mixture that are selected from according to any one of <1> ~ <5> as effective constituent.
<7>.
A kind of antibacterial resin composition, it is characterized in that, containing more than one the composition in (methyl) acrylate based copolymer, its salt quid pro quo and their mixture that are selected from according to any one of <1> ~ <5>.
<8>.
A kind of antistatic resin compositions, it is characterized in that, containing more than one the composition in (methyl) acrylate based copolymer, its salt quid pro quo and their mixture that are selected from according to any one of <1> ~ <5>.
<9>.
Resin combination according to <7> or <8>, wherein, described resin combination is the curable resin composition of resin monomer containing solidified nature and/or resin oligomers, polymerization starter composition.
The effect of invention
The germ resistance of resin combination of the present invention and the transparency, excellent antistatic property.According to this characteristic, resin combination of the present invention can give various rubber, plastic or other material and germ resistance, the static resistance such as the products formed such as film, sheet material formed by them and various fiber, paper, leather, coating, caking agent, lagging material, pointing.In addition, by controlling the kind etc. of the amount of the reactive group in oligopolymer, reaction conditions, monomer, can improve as the film toughness of surface-modifying agent or carrying out Intensity Design according to object.And then, for fluorine-containing trimethyl ammonium oligopolymer of the present invention, by importing hydrocarbon system substituting group, hydrophilic etc. in molecule, solubleness in a solvent when can also improve surface modification.
Embodiment
In this manual, (methyl) acrylate refers to acrylate and/or methacrylic ester.
(methyl) acrylate based copolymer
(methyl) acrylate based copolymer in the present invention is as the compound of copolymer composition containing monomer (1), monomer (2), in order to give the compound with reactive functional groups to above-mentioned multipolymer, also can to the monomer (4) as the further addition of compound of copolymer composition containing monomer (1), monomer (2) and monomer (3) with reactive functional groups.
Monomer (1) ~ (4) are monomers as follows.
Monomer (1): (methyl) acrylic monomer containing trimethyl ammonium
Monomer (2): fluorine-containing (methyl) acrylate
Monomer (3): containing can (methyl) acrylic monomer of reactive site
Monomer (4): (methyl) acrylic monomer containing the position can reacted with monomer (3)
Monomer (1): the feature of (methyl) acrylic monomer containing trimethyl ammonium represents with following formula.
[chemical formula 7]
In formula, R
1represent H or CH
3, R
2(this representative examples of saturated aliphatic alkyl can have halogen atom, ehter bond (-O-), thioether bond (-S-), ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-) or aryl, arylidene to the divalent representative examples of saturated aliphatic alkyl of expression carbonatoms 1 ~ 50 as required.), Y represents singly-bound, ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-), sulfonic acid ester bond (-SO
2o-or-O-SO
2-), sulphonamide key (-SO
2nH-or-NHSO
2-), ehter bond (-O-), thioether bond (-S-), X represents halogen atom, and W represents H or alkoxyl group, can have substituent aryl, the functional group such as hydroxyl, carboxyl (COOH), amino, sulfydryl or isocyanate group.
In addition, monomer (1) can be used alone a kind, also can be mixed with two or more.
Monomer (2): the feature of fluorine-containing (methyl) acrylate represents with following formula.
[chemical formula 8]
In formula, Rf represents the perfluoroalkyl of carbonatoms 1 ~ 9 or the perfluorinated alkenyl of carbonatoms 2 ~ 9.As perfluoroalkyl, can be any one in straight chain, side chain, can enumerate: CF
3-, C
2f
5-, (n-or iso-) C
3f
7-, (N-, iso-, sec-or uncle-) C
4f
9-, CF
3(CF
2)
m-(m is the integer of 4 ~ 8), (CF
3)
2cF (CF
2)
k-(k is the integer of 1 ~ 6) etc.
As perfluorinated alkenyl, preferably illustrate following 3 kinds of groups.
[chemical formula 9]
In formula (2), R
1represent H or CH
3, R
3for the divalent representative examples of saturated aliphatic alkyl of carbonatoms 1 ~ 50, (this representative examples of saturated aliphatic alkyl can have halogen atom, ehter bond (-O-), thioether bond (-S-), ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-) or aryl, arylidene as required.), Z represents singly-bound, ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-), sulfonic acid ester bond (-SO
2o-or-O-SO
2-), sulphonamide key (-SO
2nH-or-NHSO
2-), ehter bond (-O-), thioether bond (-S-).As the representative examples of saturated aliphatic alkyl of " the divalent representative examples of saturated aliphatic alkyl of carbonatoms 1 ~ 50 ", can be any one in straight chain, side chain or ring-type.Such as, can enumerate: methylene radical, ethylidene, propylidene, butylidene, cyclopentylidene, cyclohexylidene, octylene etc.In addition, these representative examples of saturated aliphatic alkyl can have one or more substituting groups, as this substituting group, as long as can not bring detrimentally affect to the present invention, are not particularly limited.As this substituting group, such as, can enumerate: the alkyl of carbonatoms 1 ~ 3, the alkoxyl group etc. of carbonatoms 1 ~ 4.As arylidene, such as, can enumerate: phenylene, naphthylidene etc.In addition, this arylidene also can have substituting group, as this substituting group, as long as can not bring detrimentally affect to the present invention, is not particularly limited.
In addition, monomer (2) can be used alone a kind, also can be mixed with two or more.
Monomer (3): containing can (methyl) acrylic monomer of reactive site be not containing trimethyl ammonium and fluorine (methyl) acrylic monomer, the monomer represented with following formula can be enumerated.
[chemical formula 10]
In formula, R
1represent H or CH
3, W
1represent H or alkoxyl group, the functional groups such as substituent aryl, hydroxyl, carboxyl (COOH), amino, sulfydryl, isocyanate group, glycidyl, oxetanyl, lactone group, phosphate can be had.
In formula, R
4the expression divalent alkylidene group of carbonatoms 1 ~ 10, the divalent epoxy alkyl of carbonatoms 2 ~ 4 maybe can have substituent divalent arylidene (phenylene, naphthylidene etc.).As the alkylidene group of " the divalent alkylidene group of carbonatoms 1 ~ 10 ", can be any one in straight chain, side chain or ring-type.Such as, can enumerate: methylene radical, ethylidene, propylidene, butylidene, cyclopentylidene, cyclohexylidene, octylene etc.In addition, these alkylidene groups can have substituting group, as this substituting group, as long as can not bring detrimentally affect to the present invention, are not particularly limited.As this substituting group, such as, can enumerate: the alkyl of carbonatoms 1 ~ 3, the alkoxyl group, halogen etc. of carbonatoms 1 ~ 4.As the alkylene moiety of " the divalent epoxy alkyl of carbonatoms 2 ~ 4 ", can be any one in straight chain, side chain, as the repeating unit of oxirane, be preferably about 1 ~ 20.
In formula, Z represents singly-bound, O, NH, NHCO or S.
In addition, monomer (3) can be used alone a kind, also can be mixed with two or more.
Monomer (3): the feature of (methyl) acrylic monomer containing the position can reacted with monomer (3) represents with following formula, such as, can enumerate: (methyl) acrylate containing isocyanate group, (methyl) acrylate containing glycidyl, (methyl) acrylate etc. containing trimethylene oxide (methyl) acrylate, (methyl) acrylate containing lactonic ring, phosphorous acidic group.
[chemical formula 11]
In formula, R
1represent H or CH
3, W
2represent energy and W
1reaction H or alkoxyl group, the functional groups such as substituent aryl, hydroxyl, carboxyl (COOH), amino, sulfydryl, isocyanate group, glycidyl, oxetanyl, lactone group, phosphate can be had.W
2as long as with W
1the functional group of reaction, is not particularly limited.
In formula, R
4the expression divalent alkylidene group of carbonatoms 1 ~ 10, the divalent epoxy alkyl of carbonatoms 2 ~ 4 maybe can have substituent divalent arylidene (phenylene, naphthylidene etc.).As the alkylidene group of " the divalent alkylidene group of carbonatoms 1 ~ 10 ", can be any one in straight chain, side chain or ring-type.Such as, can enumerate: methylene radical, ethylidene, propylidene, butylidene, cyclopentylidene, cyclohexylidene, octylene etc.In addition, these alkylidene groups can have substituting group, as this substituting group, as long as can not bring detrimentally affect to the present invention, are not particularly limited.As this substituting group, such as, can enumerate: the alkyl of carbonatoms 1 ~ 3, the alkoxyl group, halogen etc. of carbonatoms 1 ~ 4.As the alkylene moiety of " the divalent epoxy alkyl of carbonatoms 2 ~ 4 ", can be any one in straight chain, side chain, as the repeating unit of oxirane, be preferably about 1 ~ 20.
In formula, Z represents singly-bound, O, NH, NHCO or S.
In addition, monomer (4) can be used alone a kind, also can be mixed with two or more.
Containing monomer (1) and monomer (2) as in (methyl) acrylate based copolymer of copolymer composition, containing the monomer (1) of 1 ~ 90 % by weight, the monomer (2) of 1 ~ 50 % by weight, monomer (3) and/or monomer (4) can also be contained further.
Containing monomer (1), monomer (2) and monomer (3) as copolymer composition, there is from the reactive functional groups of monomer (4) (methyl) acrylate based copolymer, the monomer (1) containing 1 ~ 90 % by weight, the monomer (2) of 1 ~ 30 % by weight, the monomer (3) of 1 ~ 90 % by weight and the monomer (4) with reactive functional groups of 0 ~ 50 % by weight.The W group of monomer (1) have can react with monomer (3) group (reactive functional groups), in other words monomer (1) holds a concurrent post monomer (4) time, do not need monomer (4), now, (4 can be 0 % by weight to monomer
The static inhibitor that (methyl) of the present invention acrylate based copolymer is compounded in antistatic effect excellent as the antiseptic-germicide and imparting of giving excellent antibacterial effect in various material is useful.As material that can be compounding, such as, have: the plastics such as the rubber such as silicone, vinylformic acid, vinylchlorid, polyolefine, urethane, ABS, polystyrene, vinyl-acetic ester, polycarbonate; Phenol, resin such as (methyl) acrylate, urethane acrylate etc. etc.For composition of the present invention, by in the material compounding and carry out shaping or be coated on the surface of formed body, to formed body endowing antibacterial and static resistance, for the shape of formed body, can make the different shapes such as fiber, film, sheet material, plate or block by the known method of forming.
In addition, for (methyl) of the present invention acrylate based copolymer, dissolve making it or be suspended in the solution in the liquid solvent such as water or organic solvent, by common coating processes such as spraying, spreader coating, dip-coating, brushing, roller coat, coat the surface of various metal or plastics, pottery, resin etc., can also tunicle be formed.The bacterial reproduction in the article of various material can be stoped thus.Being not particularly limited the concentration of (methyl) acrylate based copolymer in this solution, such as, is 0.1 ~ 90.0 about % by weight, preferably 1 ~ 10 about % by weight.If the concentration of (methyl) acrylate based copolymer in this solution is too low, the quantitative change being then present in (methyl) acrylate based copolymer on surface is few, modified surface through coating or spraying is thinning, becomes the principal element of germ resistance or static resistance reduction.On the other hand, when this excessive concentration, occur that coating is irregular etc. sometimes.The concentration of (methyl) acrylate based copolymer in this solution also can by the impact according to the solubleness of the kind of solvent, the molecular weight of polymkeric substance etc.Relative to the material 100 % by weight wanting endowing antibacterial or static resistance, be 0.1 ~ 20 % by weight by the compounding preferred proportion in various material of (methyl) of the present invention acrylate based copolymer, be more preferably 0.5 ~ 5 % by weight.Above-mentioned (methyl) acrylate based copolymer can be used alone, and also can use as a mixture.
There are the material of (methyl) of the present invention acrylate based copolymer or the concrete purposes of formed body as compounding, have the textile products such as towel, carpet, curtain, clothes; The electronic products such as leather, refrigerator, washing machine, tableware drier, suction cleaner, air-conditioning, TV, phone, computer, auto navigation; The material of construction such as wallpaper, ceramic tile, brick, concrete, screw, seam; The daily use Sundry goodss such as washbowl, broom, flexible pipe, slippers, refuse container; The kitchen tackle such as trilateral kitchen cabinet, waterways; Tank articles for use; Bath articles; Various coating material; Coating and caking agent etc.
For (methyl) of the present invention acrylate based copolymer, owing to can also there is reactive acrylate's base or methacrylate based in molecule, therefore, by utilizing the chemical bond strengthening adaptation of substrate surface, the high persistence of antibacterial effect or antistatic effect can be expected.
In addition, by controlling the amount, reaction conditions etc. of the reactive group be somebody's turn to do in (methyl) acrylate based copolymer, can improve as the film toughness of surface-modifying agent or carrying out Intensity Design according to object.
In germ resistance test method of the present invention and anti-electrostatic test method, (methyl) of the present invention acrylate based copolymer is dissolved in organic solvent and is made masking liquid, this masking liquid is coated base material, after drying removing organic solvent, the film of germ resistance or static resistance can be made.
The coating process of masking liquid is not particularly limited, such as, be coated with by wet type coating, can enumerate such as its mode: intaglio printing mode, excellent painting mode, metal thread bar mode, spin coating mode, scraper mode, dip coating manner, slot coated mode etc.
antibacterial resin composition or antistatic resin compositions
The antimicrobial component of the antibacterial resin composition in the present invention or the antistatic composition of antistatic resin compositions as copolymer composition (methyl) acrylate based copolymer, can have the compound of reactive functional groups containing above-mentioned monomer (1), monomer (2) to the further addition of above-claimed cpd.Above-mentioned (methyl) acrylate based copolymer can be used alone, and also can use as a mixture.
using method
For above-mentioned (methyl) acrylate based copolymer, can with such as toluene, dimethylbenzene, ether, ethyl acetate, methyl ethyl ketone, acetone, acetonitrile, propionitrile, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, ethanol, Virahol, tetrahydrofuran (THF), 1, the form of the solution of the organic solvents such as 4-diox uses, or, can use with the form being added on the solution formed in the coating fluids such as coating (resin combination).
Above-mentioned (methyl) acrylate based copolymer can be used alone a kind, also can be mixed with two or more.In addition, the above-mentioned solvent used in this solution can be used alone a kind, also can be mixed with two or more.
The above-mentioned solution containing (methyl) of the present invention acrylate based copolymer is made to be attached to the substrate surfaces such as such as resin, film, fiber, glass, metal by coating, coating, spraying etc., thus can to film coated surface endowing antibacterial or static resistance.That is, by evaporating the solvent in this solution, the film containing (methyl) of the present invention acrylate based copolymer is formed in film coated surface.This film has germ resistance or static resistance, the transparency etc.Solvent seasoning (evaporation) condition changes according to the kind, amount etc. of the solvent in solution, usually makes it at room temperature ~ 200 DEG C about dry 10 seconds ~ 10 points kinds.
Being not particularly limited the concentration of the solution of (methyl) acrylate based copolymer in this solution, such as, is 0.1 ~ 20.0 about % by weight.If the concentration of the solution of (methyl) acrylate based copolymer in this solution is too low, the quantitative change being then present in (methyl) acrylate based copolymer on surface is few, film coated surface through coating or spraying is thinning, becomes the principal element of germ resistance or static resistance reduction.In addition, the problems such as the film coated surface that cannot obtain sufficient intensity can also be there is.On the other hand, when this excessive concentration, occur that coating is irregular etc. sometimes.The concentration of the solution of (methyl) acrylate based copolymer in this solution also can by the impact according to the solubleness of the kind of solvent, the molecular weight of polymkeric substance etc.
Germ resistance of the present invention and/or antistatic resin compositions can compounding solidified nature compositions (resin monomer, resin oligomers, polymerization starter composition etc.) and make curable resin composition (having germ resistance and/or the antistatic resin compositions of solidified nature).Below, the germ resistance of the present invention and/or antistatic resin compositions with solidified nature composition are recited as " curable resin composition ".Resin combination of the present invention preferably " curable resin composition ".
containing the curable resin composition of (methyl) acrylate based copolymer as effective constituent
Curable resin composition contained by the present invention is prepared for the form of the masking liquid coating base material.In curable resin composition (masking liquid), compounding mainly as playing (methyl) acrylate based copolymer of composition of didirtresistance, the energy ray-curable resin monomer played a role mainly as resin molding or resin oligomers, other polymerization starter, solvents etc.But, when making solvent-free system's masking liquid, being unworthy of miscible agent, when radiation curing, not needing polymerization starter.In addition, other compositions can be added as required in masking liquid.
In curable resin composition total amount of the present invention (when using solvent composition, the amount of removing solvent composition) the content of above-mentioned (methyl) acrylate based copolymer be generally 0.0006 ~ 17 about % by weight, be preferably 0.007 ~ 13 about % by weight, be more preferably 0.07 ~ 10 about % by weight.
(methyl) of the present invention acrylate based copolymer, in the cured film of being polymerized and obtaining with energy ray-curable resin monomer described later and/or resin oligomers, plays the function as germ resistance imparting agent.
energy ray-curable resin monomer or resin oligomers composition
For curable resin composition of the present invention, except containing except (methyl) acrylate based copolymer, can also containing with its reaction and become energy ray-curable resin monomer and/or the resin oligomers (hereinafter sometimes referred to resin monomer, resin oligomers) of resin cured film.
For such resin monomer and resin oligomers, as long as form the material of cured film with (methyl) acrylic ester copolymer reaction, be not particularly limited, resin monomer and/or the resin oligomers of the energy ray-curable being generally used for hard coat film or antireflection film can be used arbitrarily.
As this resin monomer and resin oligomers, such as, can enumerate: acrylic acid series, polyurethane series, epoxy, the silicone-based isoreactivity compounds such as various acrylate or acroleic acid polyurethane, preferably use acrylic resin.Particularly in order to make resin composition of the present invention use with film form, preferably use there are 2 officials can the resin monomer of above reactive functional groups and/or resin oligomers.
As have 2 officials can above reactive functional groups resin monomer, resin oligomers, such as, can enumerate: tristane dihydroxymethyl diacrylate, Bisphenol F EO modified diacrylate, dihydroxyphenyl propane EO modified diacrylate, isocyanuric acid EO modified diacrylate, polypropyleneglycol diacrylate, polyethyleneglycol diacrylate, Viscoat 295, trimethylolpropane trimethacrylate, TriMethylolPropane(TMP) PO modified triacrylate, glycerine PO addition triacrylate, TriMethylolPropane(TMP) EO modified triacrylate, TriMethylolPropane(TMP) EO modification trimethacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid EO modified triacrylate, 6-caprolactone modification isocyanuric acid three (acryloyl-oxyethyl) ester, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, ditrimethylolpropane tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, various urethane acrylate oligomer (the Nippon Synthetic Chemical Industry Co., Ltd's purple light series, Negami Chemical Ind Co., Ltd. Art Resin series etc.) etc., but be not particularly limited to these.This resin monomer, resin oligomers can use a kind, also can with arbitrary proportion compounding two or more use.
As the energy line making resin monomer, resin oligomers solidify, radiation, electron beam, ultraviolet, visible rays etc. can be enumerated.Because in the solidification by radiation, electron beam, electromagnetic energy is high, therefore, can by means of only polymerizability double-bond polymerization.When using ultraviolet, visible rays as energy source, preferred compounding polymerization starter composition described later.
In curable resin composition total amount of the present invention (when using solvent composition, the amount of removing solvent composition) this resin monomer and the content of resin oligomers be generally 55 ~ 99.9 about % by weight, be preferably 60 ~ 99.5 about % by weight, be more preferably 70 ~ 99 about % by weight.
In addition, for the usage ratio of this resin monomer and resin oligomers and (methyl) acrylate based copolymer, relative to resin monomer and resin oligomers 100 % by weight, usually use above-mentioned (methyl) acrylate based copolymer 0.001 ~ 18 about % by weight, preferably 0.01 ~ 15 about % by weight, more preferably 0.1 ~ 10 about % by weight.
polymerization starter composition
In curable resin composition of the present invention, except containing except above-mentioned (methyl) acrylate based copolymer, resin monomer and/or resin oligomers, polymerization starter composition can also be contained as required.
Polymerization starter composition can use known polymerization starter, such as, can use Photoepolymerizationinitiater initiater.
As Photoepolymerizationinitiater initiater, there will be a known Photoepolymerizationinitiater initiater miscellaneous, suitably select as required.Such as, can enumerate: 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-ketone, benzophenone, 1-[4-(2-hydroxyl-oxethyl-phenyl)-2-hydroxy-2-methyl-1-propane-1-ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinopropane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone, two (2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-pentyl phosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl] phenyl }-2-methyl-propan-1-ketone, 1-[4-(thiophenyl) phenyl]-1,2-octanedione 2-(O-benzoyl oxime), [9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] ethyl ketone 1-(O-acetyl oxime), 2,2-two (2-chloro-phenyl-)-4,4,5,5-tetraphenyl-1,2-bisglyoxaline, 2,2-diethoxy acetophenone, benzophenone, O-benzoyl methyl benzoate, two (dimethylamino) benzophenone of 4,4-, dibenzyl ketone, Fluorenone, 2-hydroxy-2-methyl Propiophenone, thioxanthone, benzyl dimethyl ketal, benzyl methoxyl group acetal, benzoin, anthraquinone, anthrone, dibenzosuberone, two (dimethylamino) phenyl styryl ketone of 4,4-, P-dimethylamino cinnamylidene indone, 2-(P-dimethylamino phenyl vinylidene)-different naphthothiazoles, 3,3-carbonyl-bis-(7-diethyl amino coumarin), 3-phenyl-5-benzoyl sulfenyl-tetrazolium etc.
When using polymerization starter composition, can be used alone a kind, also can coordinate arbitrarily two or more to use.During relative to polymerizing resin composition (total amount of (methyl) acrylate based copolymer, above-mentioned resin monomer and/or resin oligomers) 100 % by weight, the addition of polymerization starter composition is generally 0.1 ~ 50 about % by weight, is preferably 0.5 ~ 40 about % by weight, is more preferably 1 ~ 30 % by weight.
solvent composition
Curable resin composition of the present invention does not need containing solvent composition, but also can contain solvent composition as required.As solvent composition, use existing known solvent composition, such as, can enumerate: the alcohol systems such as methyl alcohol, ethanol, Virahol; The ketone such as acetone, methyl ethyl ketone system; The ester such as ethyl acetate, butylacetate etc.These solvent compositions can use a kind, also can mix two or more to use with arbitrary proportion.
When using solvent composition, relative to polymerizing resin composition (total amount of above-mentioned (methyl) acrylate based copolymer, above-mentioned resin monomer and/or resin oligomers) 100 weight parts, about the consumption of the solvent composition in curable resin composition of the present invention is generally 25 ~ 5000 weight parts, preferably about 40 ~ 2000 weight parts, more preferably 60 ~ 1000 weight parts.
other compositions
For curable resin composition of the present invention, in order in cured film designed shape of the surface or the function of giving desired by other, can compounding particulate, filler etc. as required.
the making method of cured film
In the present invention, curable resin composition of the present invention is made masking liquid, this masking liquid is coated base material, then carry out rayed etc., can cured film be made thus.
As the order for obtaining cured film of the present invention, make above-mentioned (methyl) acrylate based copolymer, resin monomer and/or resin oligomers and polymerization starter composition, solvent composition, particulate, filler etc. as required with suitably compounding than mixed dissolution, prepare curable resin composition of the present invention with the form of masking liquid.Then, coat on base material in the mode becoming certain thickness by masking liquid, by the removing such as warm air drying, vacuum-drying solvent composition, then, illumination radiation line, electron beam, ultraviolet, visible rays Isoenergetical line, can obtain cured film thus.
The coating process of masking liquid is not particularly limited, such as, be coated with by wet type coating, can enumerate such as its mode: intaglio printing mode, excellent painting mode, metal thread bar mode, spin coating mode, scraper mode, dip coating manner, slot coated mode etc.
As the base material making cured film, as long as can cured film be supported, be not particularly limited, such as, when using as the hard coat towards optical applications, preferably there is the sheet material of the transparency.As the material of transparent sheet material, glass, plastics etc. can be enumerated, particularly preferably plastics sheet.As plastics, can thermoplastic resin, thermosetting resin etc. be used, such as, can enumerate: the polyolefin resin such as polyethylene, polypropylene; The vibrin such as polyethylene terephthalate; The celluosic resin such as tri acetyl cellulose, butyl cellulose; Polystyrene resin, urethane resin, polyvinyl alcohol, polyvinyl chloride, acrylic resin, polycarbonate resin, polyacrylonitrile, cyclic olefin polymer, polyethersulfone etc.These sheet materials can carry out the easy bonding process such as adhesive treatment, corona treatment, Cement Composite Treated by Plasma, flame treating as required.
For the thickness of cured film of the present invention, be not particularly limited, suitably select according to purposes.Usually about can making 100nm ~ 30 μm.
germ resistance test method and anti-electrostatic test method
Evaluate the antimicrbial power of the test film made in following embodiment 1 ~ 12 by the following method.Tested bacterium uses intestinal bacteria (IFO3301), to make bacterium number for 10
2the mode of left and right prepares diluent.Then, at the diluent of the upper dropping 200 μ L of test film (5cm is square), and make it be close on low nutrition nutrient agar, cultivate 24 hours at 35 DEG C.Thereafter, ordinary nutrient agar substratum is implemented the transplanting of test film, cultivate 24 hours at 35 DEG C.Confirm the growth conditions of the bacterium after cultivating.The result that the germ resistance obtained as mentioned above is tested is shown in following table 4.
Evaluate the static resistance of the test film made in following embodiment 1 ~ 12 by the following method.
The expanded beads of 1/4 capacity is only dropped in transparent cylindrical container.Then, test film (5cm is square) is pasted on the inside of cylindrical container.Cylinder is made to be after air-tight state, by expanded beads up-down vibration 50 times.Thereafter, the state of expanded beads when confirming to make it standing.The result of anti-electrostatic test is shown in following table 4.
Embodiment
By following embodiment, content of the present invention is described, but content of the present invention carries out limited explanation not by embodiment.
synthesis example 1
In the there-necked flask (3L) having dropping funnel, add HEMA 234.3g (1.8mol), triethylamine 218.6g (2.16mol), acetonitrile 1000g.Hexafluoropropylene trimer 973.0g (2.16mol) is added, with within about 60 minutes, under agitation slowly dripping in the solution in flask in dropping funnel.After dropping terminates, at room temperature continue further to carry out stirring 3 hours.
Adding 1N hydrochloric acid 2200g in the reactive mixture makes reaction stop, and then, after in the beaker of this reaction mixture immigration 5L, carries out 3 carrying out washing treatment with 1L water.Solution after washing process is under reduced pressure dewatered, obtains the fluorinated acrylate 937.8g (yield 93%) represented with following formula (A-1) thus.By the fluorinated acrylate (A-1) that obtains
1the data of H-NMR are shown in table 1.
[chemical formula 12]
RfOCH
2CH
2OC(＝O)C(CH
3)＝CH
2(A-1)
[in formula, Rf is the group represented with following general formula.]
[chemical formula 13]
[table 1]
Fluorinated acrylate
1h-NMR data
synthesis example 2
In the there-necked flask (100mL) having prolong, add fluorinated acrylate (A-1) 2.80g (5mmol) of synthesis in synthesis example 1, Osaka organic synthesis industry DMAMC processed (B-1) 24.3g (100mmol), methyl ethyl ketone 54.3g, 2-propyl alcohol 54.3g, 2,2 '-azo two (2 Methylpropionic acid) dimethyl ester 0.24g (1.1mmol).In reaction soln, import nitrogen, carry out nitrogen replacement in reaction vessel.After nitrogen replacement, stirring reaction solution starts reaction while reaction soln to be heated to 80 DEG C.Thereafter, continue to carry out stirring 14 hours at 80 DEG C.With
1the distinctive peak of each acrylate of H-NMR disappears and confirms that reaction terminates.Distillation, except desolventizing, obtains target (methyl) acrylate based copolymer quantitatively.
[chemical formula 14]
synthesis example 3
By the order identical with synthesis example 2, the ratio of change monomer (A-1), (B-1) implements synthesis.Monomer ratio is as shown in table 3.
synthesis example 4
In the there-necked flask (3L) having addition funnel, add HEMA 234.3g (1.8mol), triethylamine 218.6g (2.16mol), acetonitrile 1000g.The fluorine-containing acyl chlorides 1264.68g (2.16mol) shown in following general formula (7) is added, with within about 60 minutes, under agitation slowly dripping in the solution in flask in dropping funnel.After dropping terminates, at room temperature continue further to carry out stirring 3 hours.
Adding 1N hydrochloric acid 2200g in the reactive mixture makes reaction stop, and then, after in the beaker of this reaction mixture immigration 5L, carries out 3 carrying out washing treatment with 1L water.Solution after washing process is under reduced pressure dewatered, obtains the fluorinated acrylate 1138.3g (yield 93%) represented with following formula (A-1) thus.By the fluorinated acrylate (A-2) that obtains
1the data of H-NMR are shown in table 2.
[chemical formula 15]
RfO-C
6H
4-C(＝O)Cl (7)
[chemical formula 16]
RfC-C
6H
4-C(＝O)O-CH
2CH
2OC(＝O)C(CH
3)＝CH
2(A-2)
[in formula, Rf is for the group represented by following general formula.]
[chemical formula 17]
[table 2]
Fluorinated acrylate
1h-NMR data
synthesis example 5
By the order identical with synthesis example 2, with fluorinated acrylate (A-2:RfO-Ph-C (=O) O-CH
2cH
2oC (=O) C (CH
3)=CH
2) substituted monomer (A-1) implement synthesis.Monomer ratio is as shown in table 3.
synthesis example 6
By the order identical with synthesis example 2A, with straight chain fluorinated acrylate (A-3:CF
3(CF
2)
5cH
2cH
2oC (=O) CH=CH
2) substituted monomer (A-1) implement synthesis.Monomer ratio is as shown in table 3.
synthesis example 7
By the order identical with synthesis example 2, implement synthesis with Osaka organic synthesis industry DMCMA processed (B-2) substituted monomer (B-1).Monomer ratio is as shown in table 3.
[chemical formula 18]
synthesis example 8
By the order identical with synthesis example 2, implement synthesis with emerging people DMAPAA-Q (B-3) substituted monomer (B-1).Monomer ratio is as shown in table 3.
[chemical formula 19]
synthesis example 9
By the order identical with synthesis example 2, implement synthesis with day oil BLEMMER QA (B-4) substituted monomer (B-1) processed.Monomer ratio is as shown in table 3.
[chemical formula 20]
synthesis example 10
By the order identical with synthesis example 2, with monomer (A-1), monomer (B-1), implement synthesis as the day oil PME-100 processed of monomer (C-1).Monomer ratio is as shown in table 3.
The structure of day oil PME-100 processed is as follows.
[chemical formula 21]
synthesis example 11
By the order identical with synthesis example 2, the ratio of change monomer (A-1), monomer (B-1), monomer (C-1) implements synthesis.Monomer ratio is as shown in table 3.
synthesis example 12
By the order identical with synthesis example 2, the ratio of change monomer (A-1), monomer (B-1), monomer (C-1) implements synthesis.Monomer ratio is as shown in table 3.
synthesis example 13
By the order identical with synthesis example 2, implement synthesis with day oil AE-90 processed as monomer (C-2) substituted monomer (C-1).Monomer ratio is as shown in table 3.
The structure of day oil AE-90 processed (C-2) is as follows.
[chemical formula 22]
synthesis example 14
By the order identical with synthesis example 2, use monomer (A-1) and monomer (A-3) simultaneously, and change ratio to implement synthesis.Monomer ratio is as shown in table 3.
[table 3]
The monomer ratio of (methyl) acrylate based copolymer
germ resistance test method
The antimicrbial power of the test film made in Evaluation operation example 1 ~ 12 by the following method.Tested bacterium uses intestinal bacteria (IFO3301), to make bacterium number for 10
2the mode of left and right prepares diluent.Then, exist
examinationtest the diluent of the upper dropping 200 μ L of sheet (5cm is square), and make it be close on low nutrition nutrient agar, cultivate 24 hours at 35 DEG C.Thereafter, ordinary nutrient agar substratum is implemented the transplanting of test film, cultivate 24 hours at 35 DEG C.Confirm the growth conditions of the bacterium after cultivating.The result that the germ resistance obtained as mentioned above is tested is shown in following table 4.
embodiment 1 ~ 12
Use (methyl) acrylate based copolymer 2 quality % methanol solution product described in synthesis example 2 ~ 3, synthesis example 5 ~ 14, coat PET film.Then, at 80 DEG C, make its dry 10 minutes.Use dried (methyl) acrylate based copolymer coated film as test film, implement germ resistance test.Its measurement result is shown in table 4.
comparative example 1
Use the PET film of not adding antiseptic-germicide as test film, implement germ resistance test.Its measurement result is shown in table 4.
comparative example 2
Be used as the 2 quality % methyl alcohol dispersion soln product of the NOVARON AG 300 of inorganic series antibacterial agent, coat PET film.Then, at 80 DEG C, make its dry 10 minutes.Use dried antimicrobial composition coated film as test film, implement germ resistance test.Its measurement result is shown in table 4.
comparative example 3
2 quality % methanol solution product of the fluorochemical monomer using synthesis example 1 to record, coat PET film.Then, at 80 DEG C, make its dry 10 minutes.Use the conduct of dried fluorochemical monomer coated film
examinationtest sheet, implement germ resistance test.Its measurement result is shown in table 4.
comparative example 4
2 quality % methanol solution product of the fluorochemical monomer using synthesis example 4 to record, coat PET film.Then, at 80 DEG C, make its dry 10 minutes.Use dried fluorochemical monomer coated film as test film, implement germ resistance test.Its measurement result is shown in table 4.
the evaluation (table 4,5) of germ resistance
(1) germ resistance
Judgement criteria: ◎=asepsis growth
Zero=colony number 1 ~ 50
△=colony number is more than 50, but can see antibacterial effect compared with not adding.
×=with do not add PET film on an equal basis below, can't see antibacterial effect.
(2) transparency
By the transparency of visual observation test film.
Judgement criteria: transparent=zero
Have muddiness=×
[table 4]
| Test film | Germ resistance | The transparency |
| Embodiment 1 | ◎ | ○ |
| Embodiment 2 | ◎ | ○ |
| Embodiment 3 | ◎ | ○ |
| Embodiment 4 | ○ | ○ |
| Embodiment 5 | ◎ | ○ |
| Embodiment 6 | ◎ | ○ |
| Embodiment 7 | ◎ | ○ |
| Embodiment 8 | ◎ | ○ |
| Embodiment 9 | ◎ | ○ |
| Embodiment 10 | ○ | ○ |
| Embodiment 11 | ◎ | ○ |
| Embodiment 12 | ◎ | ○ |
| Comparative example 1 | × | ○ |
| Comparative example 2 | ○ | × |
| Comparative example 3 | × | ○ |
| Comparative example 4 | × | ○ |
As shown in Table 4, the germ resistance of anti-bacterial composition of the present invention is excellent, the transparency is also excellent.
embodiment 13 ~ 24
(methyl) acrylate based copolymer 0.04 mass parts (50 quality % solution product) record synthesis example 2,3 and 5 ~ 14 and phenol resin 20 mass parts add in methyl ethyl ketone, implement coating process in PET film (100 μm thick) upper bar coater (NO.8).Then, at 80 DEG C, make its dry 3 minutes.Thereafter, UV irradiating unit is used to make curing of coating.The resin combination cutting the endowing antibacterial after solidification is used as the test film of germ resistance test, implements germ resistance test and anti-electrostatic test.Its germ resistance test-results and anti-electrostatic test result are shown in table 5.
comparative example 5
When not adding antiseptic-germicide by the sequentially built test film identical with embodiment 13, implement germ resistance test.Its measurement result is shown in table 5.
comparative example 6
Use is the NOVARON AG300 as inorganic series antibacterial agent of 5 % by weight relative to resin, by the sequentially built test film identical with embodiment 13, implements germ resistance test.Its measurement result is shown in table 5.
comparative example 7
The fluorochemical monomer that the synthesis example 1 that use is 5 % by weight relative to resin is recorded, as antiseptic-germicide, by the sequentially built test film identical with embodiment 13, implements germ resistance test.Its measurement result is shown in table 5.
comparative example 8
The fluorochemical monomer that the synthesis example 4 that use is 5 % by weight relative to resin is recorded, as antiseptic-germicide, by the sequentially built test film identical with embodiment 13, implements germ resistance test.Its measurement result is shown in table 5.
comparative example 9
Use relative to resin be the monomer (B-1) of 5 % by weight as antiseptic-germicide, by the sequentially built test film identical with embodiment 13, implement germ resistance test.Its measurement result is shown in table 5.
comparative example 10
Use relative to resin be the monomer (B-1) of 20 % by weight as antiseptic-germicide, by the sequentially built test film identical with embodiment 13, implement germ resistance test.Its measurement result is shown in table 5.
* the evaluation of static resistance
Judgement criteria: ◎=adhere to without expanded beads
The attachment number of zero=expanded beads is 1 ~ 10
The attachment number of △=expanded beads is 10 ~ 30
The attachment number of ×=expanded beads is more than 30, can't see antistatic effect
* hardness of film
With JIS K 5600-5-4 for standard, make pencil-lead bump test coated plate face along the angle being about 45 ° relative to test coated plate face, with 750g load pressing test coated plate face, at the uniform velocity forwards move about more than 10mm on one side.Film be there is no the hardness mark of the hardest damaged pencil as hardness of film.
[table 5]
| Addition % | Germ resistance | The transparency | Static resistance | Hardness of film | ||
| Embodiment 13 | Synthesis example 2 | 5 | ◎ | ○ | ◎ | H |
| Embodiment 14 | Synthesis example 3 | 5 | ◎ | ○ | ○ | 2H |
| Embodiment 15 | Synthesis example 5 | 5 | ◎ | ○ | ◎ | 2H |
| Embodiment 16 | Synthesis example 6 | 5 | ◎ | ○ | ◎ | 2H |
| Embodiment 17 | Synthesis example 7 | 5 | ◎ | ○ | ○ | 2H |
| Embodiment 18 | Synthesis example 8 | 5 | ◎ | ○ | ◎ | 2H |
| Embodiment 19 | Synthesis example 9 | 5 | ◎ | ○ | ◎ | 2H |
| Embodiment 20 | Synthesis example 10 | 5 | ◎ | ○ | ◎ | 2H |
| Embodiment 21 | Synthesis example 11 | 5 | ◎ | ○ | ◎ | 2H |
| Embodiment 22 | Synthesis example 12 | 5 | ◎ | ○ | ○ | 2H |
| Embodiment 23 | Synthesis example 13 | 5 | ◎ | ○ | ○ | 3H |
| Embodiment 24 | Synthesis example 14 | 5 | ◎ | ○ | ◎ | 2H |
| Comparative example 5 | - | × | ○ | × | 2H | |
| Comparative example 6 | 5 | ○ | × | × | 2H | |
| Comparative example 7 | 5 | × | ○ | × | 2H | |
| Comparative example 8 | 5 | × | ○ | × | 2H | |
| Comparative example 9 | 5 | × | ○ | ◎ | 2H | |
| Comparative example 10 | 20 | ○ | ○ | ◎ | HB |
As shown in Table 5, the germ resistance of resin combination of the present invention is excellent, and the transparency, static resistance are also excellent.
Even if change resin, also can suppressing striped or repulsion by adding additive, can germ resistance be shown by adding (methyl) acrylate based copolymer.In addition, use inorganic series antibacterial agent can lose the transparency of resin combination, but when (methyl) acrylic copolymer of synthesis example 2 ~ 9 and 11, anti-microbial property and transparency excellence.
The possibility that industry utilizes
According to (methyl) of the present invention acrylate based copolymer as being useful for the germ resistance imparting agent in the fields such as such as glass, fiber, metal, resin, film, optical material, coating and static resistance imparting agent, as can give substrate surface germ resistance, the transparency, static resistance compound be useful.
Claims (9)
1. (methyl) acrylate based copolymer, it contains following monomer (1), monomer (2) as copolymer composition,
Monomer (1): (methyl) acrylic monomer containing trimethyl ammonium,
[chemical formula 1]
In formula, R
1represent H or CH
3, R
2represent the divalent representative examples of saturated aliphatic alkyl of carbonatoms 1 ~ 50, this representative examples of saturated aliphatic alkyl can have halogen atom, ehter bond (-O-), thioether bond (-S-), ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-) or aryl, arylidene as required, Y is identical or different, represents singly-bound, ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-), sulfonic acid ester bond (-SO
2o-or-O-SO
2-), sulphonamide key (-SO
2nH-or-NHSO
2-), ehter bond (-O-), thioether bond (-S-), X represents halogen atom, and W represents H or alkoxyl group, can have substituent aryl, hydroxyl, carboxyl (COOH), amino, sulfydryl or isocyanate group;
Monomer (2): fluorine-containing (methyl) acrylate,
[chemical formula 2]
In formula, Rf represents the perfluoroalkyl of carbonatoms 1 ~ 9 or the perfluorinated alkenyl of carbonatoms 2 ~ 9, R
1represent H or CH
3, R
3represent the divalent representative examples of saturated aliphatic alkyl of carbonatoms 1 ~ 50, this representative examples of saturated aliphatic alkyl can have halogen atom, ehter bond (-O-), thioether bond (-S-), ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-) or aryl, arylidene as required, and Z represents singly-bound, ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-), sulfonic acid ester bond (-SO
2o-or-O-SO
2-), sulphonamide key (-SO
2nH-or-NHSO
2-), ehter bond (-O-), thioether bond (-S-).
2. (methyl) acrylate based copolymer according to claim 1, wherein, the Rf of described fluorine-containing (methyl) acrylate of formula (2) is the perfluorinated alkenyl of carbonatoms 2 ~ 9.
3. (methyl) acrylate based copolymer according to claim 1 and 2, it has reactive functional groups, and containing following monomer (1), monomer (2) and monomer (3) as copolymer composition,
Monomer (1): (methyl) acrylic monomer containing trimethyl ammonium,
[chemical formula 3]
In formula, R
1represent H or CH
3, R
2represent the divalent representative examples of saturated aliphatic alkyl of carbonatoms 1 ~ 50, this representative examples of saturated aliphatic alkyl can have halogen atom, ehter bond (-O-), thioether bond (-S-), ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-) or aryl, arylidene as required, Y is identical or different, represents singly-bound, ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-), sulfonic acid ester bond (-SO
2o-or-O-SO
2-), sulphonamide key (-SO
2nH-or-NHSO
2-), ehter bond (-O-), thioether bond (-S-), X represents halogen atom, and W represents H or alkoxyl group, can have substituent aryl, hydroxyl, carboxyl (COOH), amino, sulfydryl or isocyanate group;
Monomer (2): fluorine-containing (methyl) acrylate,
[chemical formula 4]
In formula, Rf represents the perfluoroalkyl of carbonatoms 1 ~ 9 or the perfluorinated alkenyl of carbonatoms 2 ~ 9, R
1represent H or CH
3, R
3represent the divalent representative examples of saturated aliphatic alkyl of carbonatoms 1 ~ 50, this representative examples of saturated aliphatic alkyl can have halogen atom, ehter bond (-O-), thioether bond (-S-), ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-) or aryl, arylidene as required, and Z represents singly-bound, ester bond (-COO-or-O-CO-), amido linkage (-CONH-or-NHCO-), sulfonic acid ester bond (-SO
2o-or-O-SO
2-), sulphonamide key (-SO
2nH-or-NHSO
2-), ehter bond (-O-), thioether bond (-S-);
Monomer (3): containing can (methyl) acrylic monomer of reactive site,
[chemical formula 5]
In formula, R
1represent H or CH
3, W
1represent H or alkoxyl group, the functional groups such as substituent aryl, hydroxyl, carboxyl (COOH), amino, sulfydryl, isocyanate group, glycidyl, oxetanyl, lactone group, phosphate can be had, R
4represent that alkyl maybe can have the divalent epoxy alkyl of substituent divalent arylidene, carbonatoms 2 ~ 4, Z represents singly-bound, O, NH, NHCO or S.
4. (methyl) acrylate based copolymer according to claim 1 and 2, wherein, using overall for multipolymer as 100 % by weight time, the set of monomers of multipolymer becomes: monomer (1) is 1 ~ 90 % by weight, and monomer (2) is 1 ~ 50 % by weight.
5. (methyl) acrylate based copolymer according to claim 3, wherein, using overall for multipolymer as 100 % by weight time, the set of monomers of multipolymer becomes: monomer (1) is 1 ~ 90 % by weight, monomer (2) is 1 ~ 30 % by weight, monomer (3) is 1 ~ 90 % by weight, and the monomer (4) with reactive functional groups is 0 ~ 50 % by weight, monomer (4) (methyl) acrylic monomer containing the position can reacted with monomer (3) represented by following formula
[chemical formula 6]
In formula, R
1represent H or CH
3, W
2represent energy and W
1reaction H or alkoxyl group, the functional groups such as substituent aryl, hydroxyl, carboxyl (COOH), amino, sulfydryl, isocyanate group, glycidyl, oxetanyl, lactone group, phosphate can be had, R
4represent that alkyl maybe can have the divalent epoxy alkyl of substituent divalent arylidene, carbonatoms 2 ~ 4, Z represents singly-bound, O, NH, NHCO or S.
6. an antiseptic-germicide, is characterized in that, using more than one the composition in (methyl) acrylate based copolymer, its salt quid pro quo and their mixture that are selected from according to any one of Claims 1 to 5 as effective constituent.
7. an antibacterial resin composition, is characterized in that, containing more than one the composition in (methyl) acrylate based copolymer, its salt quid pro quo and their mixture that are selected from according to any one of Claims 1 to 5.
8. an antistatic resin compositions, is characterized in that, containing more than one the composition in (methyl) acrylate based copolymer, its salt quid pro quo and their mixture that are selected from according to any one of Claims 1 to 5.
9. the resin combination according to claim 7 or 8, wherein, described resin combination is the curable resin composition of resin monomer containing solidified nature and/or resin oligomers, polymerization starter composition.
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| JP2012147437 | 2012-06-29 | ||
| JP2012147453 | 2012-06-29 | ||
| JP2012-147437 | 2012-06-29 | ||
| PCT/JP2013/067607 WO2014003095A1 (en) | 2012-06-29 | 2013-06-27 | (meth)acrylate-based copolymer, antimicrobial agent, antimicrobial property-imparting resin composition, and antistatic property-imparting resin composition |
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| KR (1) | KR101730274B1 (en) |
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| CN110446736A (en) * | 2017-03-17 | 2019-11-12 | 三菱化学株式会社 | Polyurethane (methyl) acrylate polymer |
| CN114921089A (en) * | 2022-03-16 | 2022-08-19 | 江苏恒峰线缆有限公司 | Preparation method of composite additive for irradiation cross-linked polyethylene insulating material |
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| WO2017057571A1 (en) * | 2015-09-30 | 2017-04-06 | 株式会社日本触媒 | Antibacterial agent |
| JP7039121B2 (en) * | 2016-05-31 | 2022-03-22 | 株式会社日本触媒 | Antiseptic antibacterial agent for cosmetics |
| CN111019237A (en) * | 2019-12-27 | 2020-04-17 | 田朝义 | Antistatic plastic master batch for automotive interior |
| CN111471169B (en) * | 2020-06-15 | 2022-12-06 | 扬州富威尔复合材料有限公司 | Antibacterial polyester chip and preparation method thereof |
| CN116836624B (en) * | 2023-08-08 | 2024-04-26 | 苏州格润科特新材料有限公司 | Ultraviolet light curing antibacterial agent, coating agent for leather and application of coating agent |
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| JPWO2014003095A1 (en) | 2016-06-02 |
| KR20150028820A (en) | 2015-03-16 |
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