WO2015083360A1 - 環状ハラミン構造を有する新規共重合体 - Google Patents
環状ハラミン構造を有する新規共重合体 Download PDFInfo
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- WO2015083360A1 WO2015083360A1 PCT/JP2014/005985 JP2014005985W WO2015083360A1 WO 2015083360 A1 WO2015083360 A1 WO 2015083360A1 JP 2014005985 W JP2014005985 W JP 2014005985W WO 2015083360 A1 WO2015083360 A1 WO 2015083360A1
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- 0 C*(C)CC1(*=C1)C(OC(CC1(C)C)CC(C)(C)N1Cl)=O Chemical compound C*(C)CC1(*=C1)C(OC(CC1(C)C)CC(C)(C)N1Cl)=O 0.000 description 2
- UFLXKQBCEYNCDU-UHFFFAOYSA-N CC(C)(C1)NC(C)(C)CC1OC(C(C)=C)=O Chemical compound CC(C)(C1)NC(C)(C)CC1OC(C(C)=C)=O UFLXKQBCEYNCDU-UHFFFAOYSA-N 0.000 description 1
- HEVKFRBDENHXII-UHFFFAOYSA-N CC(C)(CC(CC1(C)C)OC(C(C)=C)=O)N1Cl Chemical compound CC(C)(CC(CC1(C)C)OC(C(C)=C)=O)N1Cl HEVKFRBDENHXII-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-halogen bonds
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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
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- C08F2810/00—Chemical modification of a polymer
- C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
Definitions
- the present invention relates to a copolymer having a repeating unit containing a cyclic halamine structure, and further relates to a resin composition containing the copolymer and its use.
- a polymer having a repeating unit containing a cyclic halamine structure is known to have a reproducible antibacterial effect.
- an antibacterial composition containing a polymer obtained by polymerizing a compound represented by the following formula (III) Is described in Patent Document 1.
- R 1 , R 2 , R 3 , R 4 , and Y are a C1 to C40 alkyl group, a C1 to C40 alkylene group, a C1 to C40 alkenyl group, a C1 to C40 alkynyl group, and a C1 to C40. Allyl group, C1-C30 alkoxy group, C1-C40 alkylcarbonyl group, C1-C40 alkylcarboxyl group, C1-C40 amide group, C1-C40 carboxyl group, or a combination thereof, X is , Cl, Br, H.
- Patent Document 1 also describes that a polymer comprising the compound represented by the above formula (III) is obtained by emulsion polymerization, and that an aqueous dispersion of the polymer can be used by adding it to an aqueous emulsion paint. Yes.
- the present invention has been made in view of the above circumstances, and is a novel copolymer having a cyclic halamine structure. Further, a copolymer capable of obtaining a highly transparent coating film when the coating film is prepared. It is an object to provide a polymer. Another object of the present invention is to provide a curable composition containing the copolymer.
- the present inventors have a repeating unit derived from a (meth) acrylic acid derivative having a specific cyclic halamine structure in the molecule and a repeating unit containing a crosslinkable functional group.
- the copolymer has been found to provide a highly transparent coating film when the coating film is prepared, and the present invention has been completed.
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a hydrogen atom or a saturated or unsaturated alkyl group having 1 to 18 carbon atoms
- R 11 to R 14 each independently represents a hydrogen atom
- a copolymer comprising a repeating unit having a functional functional group
- R 3 represents a hydrogen atom or a methyl group
- X 1 represents an oxygen atom or an optionally substituted nitrogen atom
- P 1 represents a functional group containing a crosslinkable functional group.
- Crosslinkable functional group is epoxy group, oxetanyl group, dioxanyl group, carboxyl group, carbon-carbon double bond unsaturated group, hydroxyl group, amino group having active hydrogen, isocyanate group, isothiocyanate group, cyano group ,
- the present invention also provides: (6) A curable composition comprising the copolymer according to any one of (1) to (5) above, a curable compound, and a polymerization initiator, (7) A coating agent, paint or adhesive comprising the curable composition according to (6) above, (8) A cured product obtained by curing the curable composition according to (6) above, and (9) a copolymer according to any one of (1) to (5) above is mixed with a resin.
- the present invention relates to a method for imparting antibacterial activity to a resin.
- the copolymer of the present invention can provide an antibacterial effect that can be reactivated by a function derived from a repeating unit having a specific cyclic halamine structure in the molecule, and can also be a photo (thermo) curable resin.
- a photo (thermo) curable resin When used as an additive, the transparency of the coating can be ensured, so that it can be used in clear solvent paints or powder paints.
- the copolymer of the present invention includes various additives such as resin additives, curable compositions, coating agents, resin moldings, optical members, optical films, adhesives, paints, military products, medical hygiene products, food packaging materials, and the like. Suitable for various applications.
- the copolymer of the present invention contains a repeating unit represented by the following formula (I) in the molecule and a repeating unit having a crosslinkable functional group. In addition to these repeating units, other repeating units may be contained. (Repeating unit represented by formula (I))
- R 1 represents a hydrogen atom or a methyl group.
- R 2 represents a hydrogen atom or a saturated or unsaturated alkyl group having 1 to 18 carbon atoms.
- the saturated or unsaturated alkyl group having 1 to 18 carbon atoms include an alkyl group having 1 to 18 carbon atoms and 2 to 2 carbon atoms. It represents an 18 alkenyl group or an alkynyl group having 2 to 18 carbon atoms.
- saturated or unsaturated alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl.
- n-pentyl group isopentyl group, s-pentyl group, t-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- An alkyl group having 1 to 18 carbon atoms such as undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group or n-octadecyl group; vinyl group , An allyl group, a 2-butenyl group, an oleyl group, or a linoleyl group, etc., an alkenyl group having 2 to 18 carbon atoms; an acet
- R 11 to R 14 each independently represents a hydrogen atom or an alkyl group. Specifically, specific examples similar to the alkyl group having 1 to 18 carbon atoms of R 2 can be exemplified. However, at least two of R 11 to R 14 represent an alkyl group. Specifically, when R 11 to R 14 are alkyl groups, R 11 to R 13 are alkyl groups and R 14 is a hydrogen atom, R 11 and R 12 are alkyl groups, and R 13 and R 14 are hydrogen atoms. Or R 11 and R 13 are alkyl groups and R 12 and R 14 are hydrogen atoms.
- R 11 to R 14 are more preferably methyl groups.
- R 11 and R 12 , or R 13 and R 14 may combine to form a ring.
- — (CH 2 ) m — (m represents an integer of 2 or more, ), —CH 2 CH 2 C (CH 3 ) 2 CH 2 CH 2 —, —CH (CH 3 ) —CH 2 CH 2 CH (CH 3 ) —, etc., a hydrocarbon chain having 2 to 10 carbon atoms; —CH Carbon having an oxygen atom, a sulfur atom, a carbonyl group or the like, such as 2 CH 2 OCH 2 CH 2 —, —CH 2 CH 2 SCH 2 CH 2 —, or —CH 2 CH 2 C ( ⁇ O) CH 2 CH 2 — Examples thereof include hydrocarbon chains of 2 to 10.
- X represents —O— or —NR 20 —, wherein R 20 represents a hydrogen atom or an alkyl group.
- specific examples of the alkyl group include the same specific examples as those of the alkyl group having 1 to 18 carbon atoms of R 2 , among which —O— is preferable.
- Y represents a halogen atom, and specifically represents a chlorine atom, a bromine atom, a fluorine atom, or an iodine atom.
- n represents 0 or 1.
- Specific examples of the repeating unit represented by the formula (I) include repeating units represented by the following formulas.
- the repeating unit having a crosslinkable functional group of the present invention is a repeating unit capable of forming a copolymer in combination with the repeating unit represented by the formula (I), and includes a crosslinking unit in the repeating unit. If it has a functional functional part, it will not restrict
- the crosslinkable functional group reacts and bonds with a plurality of functional groups contained in the crosslinker, or self-condenses with the crosslinkable functional groups to bond the chain polymer chains to each other. Any functional group that can form a three-dimensional structure is not particularly limited.
- epoxy group oxetanyl group, dioxanyl group, carboxyl group, carbon-carbon double bond unsaturated group, hydroxyl group, amino group having active hydrogen, isocyanate group, isothiocyanate group, cyano group, mercapto group, Examples thereof include an azide group, a propargyl group, a benzocyclobutenyl group, and a crosslinkable silyl group.
- the repeating unit is not particularly limited as long as it is a repeating unit derived from a monomer having a double bond capable of undergoing a polymerization reaction with a (meth) acrylic acid derivative, and specifically, a repeating unit represented by the following formula: It can be illustrated.
- R 30 represents a hydrogen atom or a methyl group
- a represents a divalent linking group
- a and A 1 each independently represent a site containing a crosslinkable functional group
- l represents 0 or 1
- q and q1 each independently represents an integer of 1 to 5.
- a repeating unit derived from a (meth) acrylic acid derivative is preferable. More specifically, examples of the repeating unit having a crosslinkable functional group include repeating units represented by the following formulae.
- the molecular weight of the polymer of the present invention is not particularly limited, but the weight average molecular weight (Mw) measured using gel permeation chromatography (converted to standard material styrene) (hereinafter abbreviated as GPC) is 1,000 to 50, Is preferably in the range of 1,000 to 30,000, more preferably in the range of 2,000 to 10,000.
- the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured using GPC is preferably in the range of 1.01 to 10.0, and 1.01 to 5.00. 1.01 to 3.00, 1.01 to 2.00, and more preferably 1.01 to 1.50.
- the structure of the polymer of this invention can take all structures, such as a random type, a block type, a star type, a hyperbranch type, and a graft type.
- a random structure in which a repeating unit represented by the formula (I) and a repeating unit having a crosslinkable functional group are arbitrarily bonded to the main chain, and a repeating unit represented by the formula (I) on the main chain A block structure in which a block having a repeating unit having a repeating unit having a crosslinkable functional group is bonded, a repeating unit having a repeating unit represented by the formula (I) in the main chain and having a crosslinkable functional group in the side chain
- a star type structure including a repeating unit represented by the formula (I) in the core and a repeating unit having a crosslinkable functional group in the arm.
- the repeating unit having a group)) is not particularly limited, but is preferably in the range of 95/5 to 5/95, 90/10 to 20/80, 80/20 to 30/70, more preferably 60/40 to 40/60. The range of is preferable.
- the copolymer of the present invention may contain other repeating units in addition to the repeating unit represented by formula (I) and the repeating unit having a crosslinkable functional group.
- Such a repeating unit is not particularly limited as long as the repeating unit can form a copolymer with the repeating unit represented by the formula (I) and the repeating unit having a crosslinkable functional group.
- styrene examples thereof include repeating units derived from ⁇ -methylstyrene, 4-chlorostyrene, methyl (meth) acrylate, n-butyl (meth) acrylate, benzyl (meth) acrylate, and the like.
- the method for producing the copolymer of the present invention is not particularly limited as long as it is a method capable of introducing the repeating unit represented by the formula (I) and the repeating unit having a crosslinkable functional group in the molecule. Specifically, a method of polymerizing a monomer that can be induced in each repeating unit, a method of introducing a predetermined functional group by a polymer reaction, or the like can be exemplified.
- R 1 , R 2 , R 11 to R 14 , and n represent the same meaning as in formula (I), and Y 1 represents a hydrogen atom, a halogen atom, or a protecting group.
- Y 1 is a hydrogen atom
- a halogen atom is introduced by a halogenating agent after polymerization
- the desired repeating unit can be obtained by deprotection and halogenation by a halogenating agent after polymerization. it can.
- Specific examples of the monomer represented by the formula (III) include the following compounds.
- a monomer that can be derived into a repeating unit having a crosslinkable functional group and can be polymerized specifically includes an epoxy group, an oxetanyl group, a carboxyl group, a carbon-carbon double bond unsaturated group, a hydroxyl group, and active hydrogen.
- examples thereof include (meth) acrylic acid ester derivatives or (meth) acrylic acid amide derivatives having a crosslinkable functional group selected from an amino group, an isocyanate group, a crosslinkable silyl group, and the like. More specifically, the following polymerizable monomers can be exemplified, and these can be used alone or in admixture of two or more.
- polymerizable monomer used for forming the repeating unit having an epoxy group examples include glycidyl (meth) acrylate, glycidyl ⁇ -n-propyl (meth) acrylate, (meth) acrylic acid-3, Examples include compounds containing an alicyclic epoxy skeleton such as 4-epoxybutyl or (meth) acrylic acid-3,4-epoxycyclohexylmethyl, and glycidyl (meth) acrylate is particularly preferred.
- polymerizable monomer used to form a repeating unit having an oxetanyl group examples include 3-((meth) acryloyloxymethyl) oxetane and 3-((meth) acryloyloxymethyl) -3-ethyloxetane. Or 3-((meth) acryloyloxymethyl) -2-methyloxetane and the like, among which 3-((meth) acryloyloxymethyl) oxetane is preferable.
- polymerizable monomer used to form a repeating unit having a carboxyl group examples include (meth) acrylic acid. Moreover, it can also be set as a carboxyl group by superposing
- polymerizable monomer used to form a repeating unit having a carbon-carbon double bond unsaturated group examples include allyl (meth) acrylate and vinyl (meth) acrylate. Among them, allyl (meth) acrylate is preferable.
- polymerizable monomer used to form a repeating unit having a hydroxyl group examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylic acid.
- 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate
- (meth) acrylic acid Illustrate 3-hydroxypropyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, or dipentaerythritol hexa (meth) acrylate Can do.
- polymerizable monomer used to form a repeating unit having an amino group having active hydrogen examples include dimethylaminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylamide, and (meth) acrylamide. Or N-methylolacrylamide and the like.
- polymerizable monomer used for forming the repeating unit having an isocyanate group examples include isocyanate ethyl (meth) acrylate, m-isopropenyl- ( ⁇ ) ⁇ -dimethylbenzyl isocyanate (meth) acrylate, and isophorone diisocyanate.
- the polymerizable monomer used to form a repeating unit having a crosslinkable silyl group specifically, ⁇ - (meth) acryloxypropyltrimethoxysilane, ⁇ - (meth) acryloxypropylmethyldimethoxysilane, or Examples thereof include ⁇ - (meth) acryloxypropyltriethoxysilane.
- the above-mentioned crosslinkable functional group can be used after being protected with a protecting group if necessary, and removing the protecting group if necessary.
- the polymerization method of the above-described monomer is not particularly limited, and a polymerization method such as an anionic polymerization method, a radical polymerization method, a group transfer polymerization method, a suspension polymerization method, etc. can be used, among which a living anion polymerization method, a chain transfer agent. It is preferable to use controlled polymerization such as a living radical polymerization method. Furthermore, the living anion polymerization method is preferable because the molecular weight and structure of the copolymer may be controlled and a monomer having a crosslinkable functional group may be copolymerized as it is.
- a polymerization method such as an anionic polymerization method, a radical polymerization method, a group transfer polymerization method, a suspension polymerization method, etc.
- controlled polymerization such as a living radical polymerization method.
- the living anion polymerization method is preferable because the molecular weight and structure of the copolymer may be controlled and a
- polymerization initiator used in the living anion polymerization method include carbon anion species derived from organic alkali metal, organic alkaline earth metal, 1,1-diphenylethylene or stilbene. More specifically, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, ethyl sodium, lithium biphenyl, lithium naphthalene, sodium naphthalene, potassium naphthalene, ⁇ -methylstyrene naphthalene dianion, 1,1 Examples include -diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, 1,4-dilithio-2-butene, 1,6-dilithiohexane, polystyryl lithium, cumyl potassium, cumyl cesium, and the like. These polymerization initiators may be used alone or in combination of two or more.
- the polymerization temperature is usually preferably ⁇ 80 ° C. to 40 ° C., more preferably ⁇ 60 ° C. to 0 ° C.
- the reaction is usually completed in 5 minutes to 1 hour.
- the solvent used in the living anion polymerization is not particularly limited as long as it is a solvent compatible with the polymerizable monomer, oligomer or polymer, and specifically, ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, trioxane and the like.
- ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, trioxane and the like.
- Nonpolar solvents or low polarity solvents such as compounds, aliphatic, aromatic or alicyclic hydrocarbon compounds such as hexane and toluene can be exemplified, and these solvents can be used alone or in combination of two or more. It can be used as a mixed solvent.
- the N—H bond is halogenated after polymerization using a monomer having a cyclic amine structure represented by the following formula (IV).
- the method can be further exemplified.
- R 1 , R 2 , R 11 to R 14 , X, and n represent the same meaning as in formula (III).
- a method for converting a cyclic amine moiety to an N-halogenated cyclic amine is not particularly limited, and specific examples thereof include a method of treating a copolymer having a cyclic amine moiety with a halogenating agent. it can.
- halogenating agents include halogens such as chlorine, bromine, iodine, and fluorine, sodium dihaloisocyanurate, sodium hypohalite, N-halosuccinimide, 1,3-dihalohydantoin, and hypohalous acid. Calcium can be exemplified.
- halo represents chlorine, bromine, fluorine or iodine.
- the halamine structure may be reduced to an NH structure, the halamine structure can be regenerated by treating with the above halogenating agent.
- the method for introducing a crosslinkable functional group include a method for introducing a crosslinkable functional group by functional group conversion after polymerization. Specifically, a method of introducing an epoxy group or a hydroxyl group by oxidizing a double bond site, a method of introducing a crosslinkable silyl group by adding hydroxysilane to the double bond, etc. Can do.
- the curable composition of the present invention contains a curable compound and a polymerization initiator in addition to the above copolymer.
- the curing reaction can be performed by heating or light irradiation.
- the heating method is not particularly limited, and a conventionally known heating method such as a heater can be used.
- Specific examples of the light used for the light irradiation include ultraviolet rays, visible light, X-rays, and electron beams, but ultraviolet rays can be preferably exemplified. Since ultraviolet rays have high energy, the curing reaction can be accelerated by irradiating the curable composition with ultraviolet rays, the curing rate of the curable composition can be increased, and the unreacted curable composition in the cured product. The amount of objects can be reduced.
- the visible light source include incandescent bulbs and fluorescent lamps.
- ultraviolet light sources include electrode-type metal halide lamps, xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless excimer lamps, metal halide lamps, and the like.
- the wavelength range is not particularly limited, but is preferably 150 nm to 400 nm, more preferably 200 nm to 380 nm.
- the atmosphere for irradiation with ultraviolet rays is preferably an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere with a reduced oxygen concentration, but a normal air atmosphere is also possible, and the irradiation atmosphere temperature is usually 10 to 200 ° C.
- the cured state can be measured using a Fourier transform infrared spectrophotometer or a photochemical reaction calorimeter
- the curing conditions for completely curing the cured product (light irradiation time, light intensity, etc., heating temperature, etc.) , Heating time, etc.) can be selected as appropriate.
- a curable compound is a compound or resin having a functional group that undergoes a polymerization reaction when irradiated with heat or light in the presence of a polymerization initiator, and is a vinyl other than (meth) acrylate compounds, epoxy resins, and acrylate compounds. There are compounds. These may be used alone or in combination of two or more.
- (Meth) acrylate compounds include polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, polybutadiene (meth) acrylate, polystyryl (meth) acrylate, polycarbonate diacrylate, Propylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Pentyl (meth) acrylate, dipentaerythritol
- Epoxy resins include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A, etc. and phenolic compounds such as glycidyl ether type epoxy resins and orthocresol novolac type epoxy resins obtained by reaction of epichlorohydrin.
- Epoxidized novolak resin obtained by condensation or co-condensation with aldehyde compound
- glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, diaminodiphenylmethane, isocyanuric acid, etc.
- Glycidylamine type epoxy resin obtained by reaction of polyamine and epichlorohydrin, linear aliphatic epoxy obtained by oxidizing olefinic bonds with peracid such as peracetic acid Resin, alicyclic epoxy resin.
- vinyl compounds excluding acrylate compounds include aromatic vinyl compounds such as styrene, vinyltoluene, ⁇ -methylstyrene, and divinylbenzene.
- a radical polymerization initiator that is a polymerization initiator is a compound that releases a substance that initiates radical polymerization by light irradiation and / or heating, and specifically includes organic peroxide imidazole derivatives, bisimidazole derivatives, N-aryls. Examples thereof include glycine derivatives, organic azide compounds, titanocenes, aluminate complexes, N-alkoxypyridinium salts, and thioxanthone derivatives.
- the organic peroxide includes hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide; t-butyl peroxylaurate Peroxyesters such as t-butylperoxybenzoate and t-butylperoxydecanoate; peroxyketals such as 1,5-di-t-butylperoxy-3,3,5-trimethylcyclohexane; Ketone peroxides such as ethyl acetoacetate; and diacyl peroxides such as benzoyl peroxide.
- hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide
- t-butyl peroxylaurate Peroxyesters such as t-butylperoxybenzoate and t-
- benzoin benzoin isopropyl ether, benzoin isobutyl ether, 2,2-diethoxyacetophenone, 2,2-dimethoxyphenylacetophenone, 2-ethylanthraquinone, 1,3-di (tert-butyldioxycarbonyl) benzophenone, 4, 4′-tetrakis (tert-butyldioxycarbonyl) benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1, 2-diphenylethane-1-one (trade name Irgacure (registered trademark) 651, manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name Irgacure (registered trademark) 184, manufactured by BASF), 2-benzyl - -Dimethylamino-1- (4-morpholinopheny
- curable composition or cured product of the present invention other components can be added and blended depending on the purpose within a range that does not impair the characteristics.
- these blending components include fillers, flame retardants, plasticizers, antistatic agents, and the like.
- Example 1 Manufacture of polymer
- THF tetrahydrofuran
- Li chloride n-butyllithium (15.4 wt% hexane solution)
- diisopropyl Amine 0.81 g was charged and stirred for 15 minutes.
- 0.87 g of methyl isobutyrate was charged and stirred for 15 minutes.
- TMPMA 2,2,6,6-tetramethyl-4-piperidine methacrylate
- allyl methacrylate dissolved in 28.92 g of THF
- PMMA standard mobile phase THF, polymethylmethacrylate as a standard
- Example 2 90.30 g of THF and 0.16 g of lithium chloride were added to a 200 mL flask and cooled to ⁇ 60 ° C. n-Butyllithium (3.25 g, 15.4 wt% hexane solution) and diisopropylamine (0.83 g) were charged and stirred for 15 minutes. Next, 0.84 g of methyl isobutyrate was charged and stirred for 15 minutes. 15.21 g of TMPMA and 15.21 g of glycidyl methacrylate dissolved in 28.26 g of THF were added dropwise over 40 minutes and aged for 15 minutes.
- Example 3 A 200 mL flask was charged with 97.23 g of THF and 0.34 g of lithium chloride, cooled to ⁇ 60 ° C., and then charged with 4.8 mL of n-butyllithium (15.4 wt% hexane solution) and 0.80 g of diisopropylamine. Stir for minutes. Next, 0.82 g of methyl isobutyrate was charged and stirred for 15 minutes. 9.24 g of N-chloro-2,2,6,6-tetramethyl-4-piperidine methacrylate and 16.78 g of 1-ethoxyethyl methacrylate dissolved in 9.24 g of THF were added dropwise over 30 minutes and aged for 45 minutes. did.
- Example 4 75.30 g of THF and 0.11 g of lithium chloride were added to a 200 mL flask and cooled to ⁇ 60 ° C. n-Butyllithium (2.03 g, 15.4 wt% hexane solution) and then diisopropylamine (0.63 g) were added and the mixture was stirred for 10 minutes. 12.24 g of TMPMA dissolved in THF (50% THF solution) was added dropwise over 15 minutes and stirred for 20 minutes. A part was sampled and monomer disappearance was confirmed by GC measurement.
- the obtained polymer was analyzed by GPC (mobile phase DMF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 2,340 and the molecular weight distribution (Mw / Mn) was 1.17.
- GMA glycidyl methacrylate
- the obtained copolymer was analyzed by GPC (mobile phase DMF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 5,520 and the molecular weight distribution (Mw / Mn) was 1.20. From the ICP-AES analysis, the chlorine concentration in the copolymer was 9.0% (theoretical value: 8.8%).
- Example 5 A 200 mL flask was charged with 89.37 g of THF and 0.14 g of lithium chloride, cooled to ⁇ 60 ° C., and then charged with 2.05 g of n-butyllithium (15.4 wt% hexane solution) and 0.60 g of diisopropylamine. Stir for minutes. Next, 0.55 g of methyl isobutyrate was charged and stirred for 15 minutes. 9.53 g of N-chloro-2,2,6,6-tetramethyl-4-piperidine methacrylate and 9.53 g of allyl methacrylate dissolved in 5.82 g of THF were added dropwise over 15 minutes and aged for 30 minutes.
- Example 6 (Preparation of photocurable thin film) [Example 6] In a 100 mL flask, 40 g of THF, 2.8 g of the copolymer obtained in Example 1, 17.2 g of dipentaerythritol hexaacrylate (DPHA), photopolymerization initiator (2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one and 0.8 g of Irgacure (registered trademark) 907 (manufactured by BASF) were mixed to obtain a photocurable composition. The photocurable composition was formed into a film on a glass substrate with a # 12 bar coater, and dried at 80 ° C.
- DPHA dipentaerythritol hexaacrylate
- Irgacure registered trademark
- a condensing type high-pressure mercury lamp (UV light mainly composed of light of 365 nm, 313 nm, and 254 nm, manufactured by Eye Graphics, one lamp type, 120 W / cm, lamp height 9.8 cm, conveyor speed 5. 7 m / min) was irradiated with ultraviolet light having an integrated dose of 400 mJ / cm 2 (254 nm) to obtain a photocurable thin film having a thickness of 2 ⁇ m.
- the total light transmittance (TT) is the ratio (%) of the total amount of light that has passed through the sample when the intensity of the incident light is 100%, and is the ratio (%) of the amount of light diffused by the sample. It is the sum of the diffused light transmittance (DF) and the parallel light transmittance that is the ratio (%) of the amount of light that goes straight in the incident direction.
- TT (DF) + (parallel light transmittance)
- the haze rate (Hz) (%) is the ratio (%) of the amount of light that is diffused and transmitted away from the incident light beam while the incident light passes through the sample.
- (Hz) (DF) / (TT) ⁇ 100
- Antimicrobial test 1. Test Method The antibacterial test was based on JIS-Z-2801, using Staphylococcus aureus NBRC12732 (Staphylococcus aureus) as a test bacterium, and using the glass substrate with a photocurable thin film obtained in Example 6 as a test sample. The surface was inoculated with the test bacteria, and the number of viable bacteria immediately after the inoculation was confirmed.
- Inoculation method The test bacteria pre-cultured in the Nutrient Agar medium are diluted with a 500-fold diluted Nutrient broth medium to give a bacterial solution for inoculation, and 0.4 ml is inoculated on the sample (50 ⁇ 50 mm) and coated film (sterilized) (40x40mm).
- Culture conditions 35 ⁇ 1 ° C, relative humidity 95% (in a constant temperature and humidity chamber), 24-hour viable count: Wash sample surface and coated film with 10 ml of SCDLP medium. The number of bacteria per 1 ml of the washed out solution is calculated by counting the number of colonies using NA medium. Contrast: Place an underlay film on the petri dish, and inoculate the fungus solution, and then cover the film.
- Test results Table 2 shows the antibacterial test results of the copolymer of the present invention, and Table 3 shows the results of the blank test.
- the composition of the present invention is excellent in antibacterial properties and also in transparency.
- the copolymer of the present invention is excellent in the transparency of the coating film in addition to the reproducible antibacterial property, so that these properties are required, for example, optical articles, clear paints, transparent adhesives, military articles Suitable for applications such as medical and hygiene products and food packaging materials.
Abstract
Description
本願は、2013年12月3日に出願された日本国特許出願第2013-250326号に対し優先権を主張し、その内容をここに援用する。
さらに特許文献1には、上記式(III)に示す化合物からなるポリマーが、乳化重合することにより得られること、及び当該ポリマーの水分散体を水性エマルジョン塗料に添加して使用できることも記載されている。
本発明は、上記の事情に鑑みてなされたものであり、環状ハラミン構造を有する新規の共重合体であり、さらに、塗膜を作成した際に高い透明性の塗膜を得ることができる共重合体、を提供することを目的とする。また、該共重合体を含有する硬化性組成物を提供することを目的とする。
(3)架橋性官能基を有する繰り返し単位が、下記式(II)
(4)架橋性官能基が、エポキシ基、オキセタニル基、ジオキサニル基、カルボキシル基、炭素-炭素二重結合性不飽和基、水酸基、活性水素を有するアミノ基、イソシアネート基、イソチオシアネート基、シアノ基、メルカプト基、アジド基、プロパギル基、ベンゾシクロブテニル基及び、架橋性シリル基から群から選ばれる基である上記(1)~(3)のいずれかに記載の共重合体、及び
(5)重量平均分子量が1,000~50,000である上記(1)~(4)のいずれかに記載の共重合体に関する。
(6)上記(1)~(5)のいずれかに記載の共重合体、硬化性化合物、及び重合開始剤を含む硬化性組成物、
(7)上記(6)に記載の硬化性組成物を含むコーティング剤、塗料又は接着剤、
(8)上記(6)に記載の硬化性組成物を硬化させて得られる硬化物、及び
(9)上記(1)~(5)のいずれかに記載の共重合体を樹脂と混合する、樹脂への抗菌活性付与方法に関する。
(式(I)で表される繰り返し単位について)
R2は、水素原子、又は炭素数1~18の飽和又は不飽和アルキル基を表し、炭素数1~18の飽和又は不飽和アルキル基としては、炭素数1~18アルキル基、炭素数2~18アルケニル基、又は炭素数2~18のアルキニル基を表す。
炭素数1~18の飽和又は不飽和アルキル基としては、具体的には、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、t-ブチル基、n-ペンチル基、イソペンチル基、s-ペンチル基、t-ペンチル基、ネオペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、n-ノニル基、n-デシル基、n-ウンデシル基、n-ドデシル基、n-トリデシル基、n-テトラデシル基、n-ペンタデシル基、n-ヘキサデシル基、n-ヘプタデシル基、またはn-オクタデシル基等の炭素数1~18アルキル基;ビニル基、アリル基、2-ブテニル基、オレイル基、またはリノレイル基等の炭素数2~18アルケニル基;アセチレン基、プロパルギル基、1-プロピニル基、または2-ブチニル基等の炭素数2~18アルキニル基を例示することができる。
R11~R14はそれぞれ独立に、水素原子、又はアルキル基を表し、具体的には、R2の炭素数1~18アルキル基と同様の具体例を例示することができる。但し、R11~R14のうち少なくとも2つがアルキル基を表す。具体的には、R11~R14がアルキル基の場合、R11~R13がアルキル基でR14が水素原子の場合、R11とR12がアルキル基でR13とR14が水素原子の場合、またはR11とR13がアルキル基でR12とR14が水素原子の場合等を例示することができる。これらのうち、炭素数1~3のアルキル基であるのが好ましく、メチル基又はエチル基であるのがより好ましく、R11~R14がすべてメチル基であるのがさらに好ましい。
また、R11とR12、もしくはR13とR14は、結合して環を形成してもよく、具体的には、-(CH2)m-(mは、2以上の整数を表す、)、-CH2CH2C(CH3)2CH2CH2-、-CH(CH3)-CH2CH2CH(CH3)-等の炭素数2~10の炭化水素鎖;-CH2CH2OCH2CH2-、-CH2CH2SCH2CH2-、又は-CH2CH2C(=O)CH2CH2-等の酸素原子、硫黄原子、カルボニル基等を有する炭素数2~10の炭化水素鎖等を例示することができる。
Xは、-O-、-NR20-、を表し、式中、R20は、水素原子又はアルキル基を表す。ここで、アルキル基としては、具体的には、R2の炭素数1~18アルキル基と同様の具体例を例示することができ、中でも-O-が好ましい。
Yは、ハロゲン原子を表し、具体的には、塩素原子、臭素原子、フッ素原子、ヨウ素原子を表す。
nは、0又は1を表す。
式(I)で表される繰り返し単位として、具体的には、以下の式で表される繰り返し単位を例示することができる。
本発明の架橋性官能基を有する繰り返し単位は、式(I)で表される繰り返し単位と相俟って共重合体を形成することができる繰り返し単位であって、当該繰り返し単位中に、架橋性官能性部位を有するものであれば特に制限されない。
架橋性官能基は、架橋剤に含まれる複数の官能基と反応して結合し、又は、架橋性官能基同士で自己縮合して、鎖状の高分子鎖同士を結合して、2次元また3次元構造を形成することができる官能基であれば、特に制限されない。
具体的には、エポキシ基、オキセタニル基、ジオキサニル基、カルボキシル基、炭素-炭素二重結合性不飽和基、水酸基、活性水素を有するアミノ基、イソシアネート基、イソチオシアネート基、シアノ基、メルカプト基、アジド基、プロパギル基、ベンゾシクロブテニル基、架橋性シリル基等を例示することができる。
式(I)で表される繰り返し単位と相俟って共重合体を形成できる架橋性官能基を有する繰り返し単位として、式(I)で表される繰り返し単位に誘導される単量体である(メタ)アクリル酸誘導体と重合反応が可能な二重結合を有する単量体から誘導される繰り返し単位であれば、特に制限されず、具体的には、以下の式で表される繰り返し単位を例示することができる。
架橋性官能基を有する繰り返し単位として、さらに具体的には、以下の式で表される繰り返し単位を例示することができる。
本発明の重合体の分子量は特に制限されないが、ゲルパーミエーションクロマトグラフィー(標準物質スチレンで換算)(以下GPCと略す)を用いて測定した重量平均分子量(Mw)は、1,000~50,000の範囲であるのが好ましく、1,000~30,000、さらに2,000~10,000の範囲であるのが好ましい。また、GPCを用いて測定した重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)は、1.01~10.0の範囲が好ましく、1.01~5.00、1.01~3.00、1.01~2.00、さらに1.01~1.50の範囲が好ましい。
また、本発明の重合体の構造は、ランダム型、ブロック型、スター型、ハイパーブランチ型、グラフト型等のあらゆる構造をとることができる。具体的には、主鎖に式(I)で表される繰り返し単位と架橋性官能基を有する繰り返し単位が任意に結合しているランダム構造、主鎖に式(I)で表される繰り返し単位を有するブロックと架橋性官能基を有する繰り返し単位を有するブロックが結合しているブロック構造、主鎖に式(I)で表される繰り返し単位を含み、側鎖に架橋性官能基を有する繰り返し単位を含むようなグラフト型構造、コアに式(I)で表される繰り返し単位を含み、アームに架橋性官能基有する繰り返し単位を含むスター型構造等を例示することができる。
本発明の共重合体には、式(I)で表される繰り返し単位及び架橋性官能基を有する繰り返し単位のほか、他の繰り返し単位を含んでいてもよい。そのような繰り返し単位として、式(I)で表される繰り返し単位及び架橋性官能基を有する繰り返し単位と共重合体を形成できる繰り返し単位であれば特に制限されず、具体的には、スチレン、α-メチルスチレン、4-クロロスチレン、(メタ)アクリル酸メチル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸ベンジル等に由来する繰り返し単位を例示することができる。
式(III)で表されるモノマーとして具体的には、以下に示す化合物を例示することができる。
また、上記した架橋性官能基は、必要に応じて保護基で保護をしておき、必要に応じて保護基を脱離させて用いることもできる。
環状アミン部位をN-ハロゲン化環状アミンへ変換する方法としては、特に制限されないが、具体的には、環状アミン部位を有する共重合体を、ハロゲン化剤で処理する方法等を例示することができる。ハロゲン化剤として、具体的には、塩素、臭素、ヨウ素、フッ素等のハロゲン、ジハロイソシアヌル酸ナトリウム、次亜ハロゲン酸ナトリウム、N-ハロスクシンイミド、1,3-ジハロヒダントイン及び次亜ハロゲン酸カルシウム等を例示することができる。ここでハロは塩素、臭素、フッ素又はヨウ素を表す。
また、ハラミン構造は還元されてN-H構造になる場合があるが、上記のハロゲン化剤で処理することによりハラミン構造を再生することができる。
架橋性官能基の導入方法として、重合後に官能基変換により架橋性官能基を導入する方法を例示することができる。具体的には、二重結合部位を酸化することにより、エポキシ基、または水酸基を導入する方法、二重結合にヒドロキシシランを付加させることにより、架橋性シリル基を導入する方法等を例示することができる。
本発明の硬化性組成物には、上記共重合体の他、硬化性化合物や重合開始剤が含まれる。硬化反応は、加熱又は光照射によって行うことができる。
光照射に用いる光として、具体的には、紫外線、可視光、X線、電子線等を例示することができるが、紫外線を好ましく例示することができる。紫外線はエネルギーが高いため、紫外線を硬化性組成物に照射することにより硬化反応を促進することができ、硬化性組成物の硬化速度を速めることが出来ると共に、硬化物における未反応の硬化性組成物の量を低減することが出来る。
硬化状態は、フーリエ変換赤外分光分析装置や光化学反応熱量計等を用いて測定することが出来るので、硬化物が完全に硬化するための硬化条件(光の照射時間、光強度等、加熱温度、加熱時間等)を適宜選定することが出来る。
[実施例1]
200mLフラスコに、テトラヒドロフラン(以下、THFと略す)104.33g、塩化リチウム0.17gを仕込み、-60℃に冷却後、n-ブチルリチウム3.37g(15.4重量%濃度ヘキサン溶液)、ジイソプロピルアミン0.81gを仕込み、15分間撹拌した。次いでイソ酪酸メチル0.87gを仕込み、15分間撹拌した。THF28.92gに溶解したメタクリル酸2,2,6,6-テトラメチル-4-ピペリジン(以下TMPMAと略す)15.38g、メタクリル酸アリル15.38gを40分間かけて滴下し、15分間熟成した。一部をサンプリングし、GC測定によりモノマー消失を確認した後、メタノール1.2gを加えて反応を停止した。
得られた共重合体をGPC(移動相THF、ポリメチルメタクリレートを標準(以下PMMAスタンダードと略す))により分析し、分子量(Mn)が3,860、分子量分布(Mw/Mn)が1.11であることを確認した。
得られた重合体をGPC(移動相THF、PMMAスタンダード)により分析し、分子量(Mn)が4,850、分子量分布(Mw/Mn)が1.11であることを確認した。
ICP-AES分析より、共重合体中の塩素濃度は6.8%(理論値7.3%)であった。
200mLフラスコにTHF90.30g、塩化リチウム0.16gを加え、-60℃まで冷却した。n-ブチルリチウム3.25g(15.4重量%濃度ヘキサン溶液)、ジイソプロピルアミン0.83gを仕込み、15分間撹拌した。次いでイソ酪酸メチル0.84gを仕込み、15分間撹拌した。THF28.26gに溶解したTMPMA15.21g、メタクリル酸グリシジル15.21gを40分間かけて滴下し、15分間熟成した。一部をサンプリングし、GC測定によりモノマー消失を確認した後、メタノール1.2gを加えて反応を停止した。
得られた共重合体をGPC(移動相THF、PMMAスタンダード)により分析し、分子量(Mn)が3,410、分子量分布(Mw/Mn)が1.24であることを確認した。
得られた共重合体をGPC(移動相THF、PMMAスタンダード)により分析し、分子量(Mn)が5,180、分子量分布(Mw/Mn)が1.33であることを確認した。
ICP-AES分析より、共重合体中の塩素濃度は7.7%(理論値7.3%)であった。
200mLフラスコに、THF97.23g、塩化リチウム0.34gを仕込み、-60℃に冷却後、n-ブチルリチウム4.8mL(15.4重量%濃度ヘキサン溶液)、ジイソプロピルアミン0.80gを仕込み、15分間撹拌した。次いでイソ酪酸メチル0.82gを仕込み、15分間撹拌した。THF9.24gに溶解したメタクリル酸N-クロロ-2,2,6,6-テトラメチル-4-ピペリジン9.24g、メタクリル酸1-エトキシエチル16.78gを30分間かけて滴下し、45分間熟成した。一部をサンプリングし、GC測定によりモノマー消失を確認した後、メタノール1.21gおよび酢酸0.37gを加えて反応を停止した。
得られた重合体をGPC(移動相THF、PMMAスタンダード)により分析し、分子量(Mn)が3,720、分子量分布(Mw/Mn)が1.14であることを確認した。
ICP-AES分析より、共重合体中の塩素濃度は4.8%(理論値5.6%)であった。
200mLフラスコにTHF75.30g、塩化リチウム0.11gを加え、-60℃まで冷却した。n-ブチルリチウム2.03g(15.4重量%濃度ヘキサン溶液)、次いで、ジイソプロピルアミン0.63gを加えて10分間撹拌した。THFに溶解したTMPMA12.24g(50%THF溶液)を15分間かけて滴下し、20分間撹拌した。一部をサンプリングし、GC測定によりモノマー消失を確認した。また、得られた重合体をGPC(移動相DMF、PMMAスタンダード)により分析し、分子量(Mn)が2,340、分子量分布(Mw/Mn)が1.17であることを確認した。
次いで、メタクリル酸グリシジル(以下、GMAと略す)7.75gを10分間かけて滴下し、15分間撹拌した。一部をサンプリングし、GC測定によりモノマー消失を確認した後、メタノール0.8gを加えて反応を停止した。得られた共重合体をGPC(移動相DMF、PMMAスタンダード)により分析し、分子量(Mn)が4,340、分子量分布(Mw/Mn)が1.19であることを確認した。
得られた共重合体をGPC(移動相DMF、PMMAスタンダード)により分析し、分子量(Mn)が5,520、分子量分布(Mw/Mn)が1.20であることを確認した。
ICP-AES分析より、共重合体中の塩素濃度は9.0%(理論値8.8%)であった。
200mLフラスコに、THF89.37g、塩化リチウム0.14gを仕込み、-60℃に冷却後、n-ブチルリチウム2.05g(15.4重量%濃度ヘキサン溶液)、ジイソプロピルアミン0.60gを仕込み、15分間撹拌した。次いでイソ酪酸メチル0.55gを仕込み、15分間撹拌した。THF5.82gに溶解したメタクリル酸N-クロロ-2,2,6,6-テトラメチル-4-ピペリジン9.53g、メタクリル酸アリル9.53gを15分間かけて滴下し、30分間熟成した。一部をサンプリングし、GC測定によりモノマー消失を確認した後、メタノール0.8gを加えて反応を停止した。
得られた重合体をGPC(移動相THF、PMMAスタンダード)により分析し、分子量(Mn)が4,760、分子量分布(Mw/Mn)が1.22であることを確認した。
ICP-AES分析より、共重合体中の塩素濃度は6.6%(理論値6.8%)であった。
1000mLフラスコにTHF376.57g、塩化リチウム0.60gを加え、-60℃まで冷却した。n-ブチルリチウム10.75g(15.4重量%濃度ヘキサン溶液)、ジイソプロピルアミン2.65gを仕込み、15分間撹拌した。THF101.40gに溶解したTMPMA101.17gを60分間かけて滴下し、15分間熟成した。一部をサンプリングし、GC測定によりモノマー消失を確認した後、メタノール4.0gを加えて反応を停止した。
得られたホモ重合体をGPC(移動相DMF、PMMAスタンダード)により分析し、分子量(Mn)が3,850、分子量分布(Mw/Mn)が1.11であることを確認した。
得られたホモ重合体をGPC(移動相DMF、PMMAスタンダード)により分析し、分子量(Mn)が5,180、分子量分布(Mw/Mn)が1.10であることを確認した。
ICP-AES分析より、ホモ重合体中の塩素濃度は13.9%(理論値13.6%)であった。
1000mLフラスコにChimassorb(登録商標)2020FDL(BASF社製)93.60g、クロロホルム300mLを仕込み、溶解した。ジクロロイソシアヌル酸ナトリウム水溶液(32%、292.33g)を加え、不均一状態のまま、室温で3時間熟成した。不溶物をろ過後、分液し、二回水洗した。有機層を濃縮後、30%THF溶液に調整し、大量のメタノールで再沈した。得られた重合体を真空乾燥することにより、白色粉末98.33gを得た。
ICP-AES分析より、重合体中の塩素濃度は15.7%であった。
[実施例6]
100mLフラスコにTHF40g、実施例1で得られた共重合体2.8g、ジペンタエリスリトールヘキサアクリレート(DPHA)17.2g、光重合開始剤(2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン、Irgacure(登録商標)907(BASF社製)0.8gを混合し、光硬化性組成物を得た。
その光硬化性組成物を、ガラス基板上に#12のバーコーターにて成膜し、温風循環型乾燥機で80℃、3分間乾燥した。続いて、集光型高圧水銀灯(365nm、313nm、254nmの波長の光を主成分とするUV光、アイグラフィックス社製、1灯型、120W/cm、ランプ高9.8cm、コンベア速度5.7m/分)により積算照射量400mJ/cm2(254nm)の紫外光を照射し、膜厚2μmの光硬化性薄膜を得た。
実施例1で得られた共重合体の代わりに比較例1で得られたホモ重合体を用いた以外は、実施例6と同様の方法で光硬化性薄膜を得た。
実施例1で得られた共重合体の代わりに比較例2で得られた重合体を用いた以外は、実施例6と同様の方法で光硬化性薄膜を得た。
<ヘイズ、全光線透過率の測定方法>
JIS K 7105に従い測定を行った。測定には日本電色工業株式会社製ヘーズメーターNDH-300Aを使用した。全光線透過率(TT)は、入射光の強さを100%とした場合、試料を通過してきた全ての光量の割合(%)であり、試料によって拡散された光量の割合(%)である拡散光線透過率(DF)と入射方向に直進する光量の割合(%)である平行光線透過率の和である。
(TT)=(DF)+(平行光線透過率)
また、ヘイズ率(Hz)(%)は、入射光が試料を通る間に、入射光束からはずれて拡散透過した光量の割合(%)である。
(Hz)=(DF)/(TT)×100
実施例1、比較例1及び比較例2で作製した光硬化性薄膜それぞれについて、ヘイズ測定と全光線透過率測定を行った。その結果を表1に示す。
1.試験方法
抗菌性試験は、JIS-Z-2801に準拠し、供試菌としてStaphylococcus aureus NBRC12732(黄色ぶどう球菌)を使用し、実施例6で得られた光硬化性薄膜つきガラス基板を供試体として、その表面に供試菌を接種して接種直後の生菌数を確認した。
接種方法:
ニュートリエントアガー培地で前培養した試験菌を、それぞれニュートリエントブロス培地500倍希釈液で希釈して接種用菌液とし、試料上(50×50mm)に0.4mlずつ接種し、被覆フィルム(滅菌済・40×40mm)を被せる。
培養条件:
35±1℃、相対湿度95%(恒温恒湿器中)、24時間
生菌数確認:
SCDLP培地10mlを用いてサンプル表面および被覆フィルムを洗い出す。洗い出した液1ml当たりの菌数をNA培地を用いてコロニー数計測により算出する。
対照:
シャーレに下敷き用のフィルムを設置し、菌液接種後、被覆フィルムを被せる。接種直後(Lmin)と24時間培養後(Lmax)の菌数を確認する。
成立要件:
〔1〕無加工試験片の接種直後の生菌数の対数値について、次の式が成立する。
(Lmax-Lmin)/Lmean ≦ 0.2
Lmax:生菌数対数値の最大値
Lmin:生菌数対数値の最小値
Lmean:3個の試験片の生菌数対数値の平均値
〔2〕無加工試験片の接種直後の生菌数平均値は、6.2×103~2.5×104個/cm2の範囲内である。
〔3〕無加工試験片の24時間後の生菌数は62個/cm2以上である。
本発明の共重合体の抗菌性試験結果を表2に、ブランク試験の結果を表3にそれぞれ示す。
Claims (11)
- 式(I)で表される繰り返し単位と架橋性官能基を有する繰り返し単位が99:1~1:99のモル比で含まれる、請求項1に記載の共重合体。
- 架橋性官能基が、エポキシ基、オキセタニル基、ジオキサニル基、カルボキシル基、炭素-炭素二重結合性不飽和基、水酸基、活性水素を有するアミノ基、イソシアネート基、イソチオシアネート基、シアノ基、メルカプト基、アジド基、プロパギル基、ベンゾシクロブテニル基及び、架橋性シリル基から群から選ばれる基である請求項1~3のいずれかに記載の共重合体。
- 重量平均分子量が1,000~50,000である請求項1~4のいずれかに記載の共重合体。
- 請求項1~5のいずれかに記載の共重合体、硬化性化合物、及び重合開始剤を含む硬化性組成物。
- 請求項6に記載の硬化性組成物を含むコーティング剤。
- 請求項6に記載の硬化性組成物を含む塗料。
- 請求項6に記載の硬化性組成物を含む接着剤。
- 請求項6に記載の硬化性組成物を硬化させて得られる硬化物。
- 請求項1~5のいずれかに記載の共重合体を樹脂と混合する、樹脂への抗菌活性付与方法。
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CN201480065203.7A CN105793304A (zh) | 2013-12-03 | 2014-12-01 | 具有环状卤胺结构的新型共聚物 |
JP2015551386A JP6063060B2 (ja) | 2013-12-03 | 2014-12-01 | 環状ハラミン構造を有する新規共重合体 |
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WO2016117323A1 (ja) * | 2015-01-20 | 2016-07-28 | 日本曹達株式会社 | 重合体の製造方法 |
JP2021528537A (ja) * | 2018-06-18 | 2021-10-21 | コーネル・ユニバーシティーCornell University | 高性能、低コストかつ適用が容易な抗菌コーティングのためのn−ハラミン−ドーパミン共重合体のシステムおよび方法 |
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KR102146324B1 (ko) * | 2016-06-02 | 2020-08-21 | 에보니크 오퍼레이션즈 게엠베하 | 전극 물질을 제조하는 방법 |
CN108863909A (zh) * | 2018-08-03 | 2018-11-23 | 四川大学 | 一类新型卤胺结构化合物及其制备方法和抗菌领域应用 |
JP7417609B2 (ja) * | 2019-07-12 | 2024-01-18 | 株式会社ジーシー | 抗菌ポリマー粒子を含む組成物 |
CN111944097B (zh) * | 2020-07-22 | 2022-08-30 | 武汉纺织大学 | 抗菌聚丙烯熔喷材料及其制备方法和应用 |
CN114351460B (zh) * | 2020-10-13 | 2024-04-16 | 广州弘海材料科技有限公司 | 一种具抗菌功能的纤维材料、其制备方法及其纤维制品 |
EP4289907A1 (en) * | 2022-06-10 | 2023-12-13 | Arkema France | Hals as anti-microbial additives in free-radical systems |
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See also references of EP3078683A4 * |
YI DENG ET AL.: "Synthesis, characterization and antibacterial properties of multifunctional hindered amine light stabilizers", CHINESE CHEMICAL LETTERS, vol. 19, 2008, pages 1071 - 1074, XP022854382 * |
ZHENGBING CAO ET AL.: "Polymeric N-Halamine Latex Emulsions for Use in Antimicrobial Paints", APPLIED MATERIALS & INTERFACES, vol. 1, no. 2, 2009, pages 494 - 504, XP055346991 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2016117323A1 (ja) * | 2015-01-20 | 2016-07-28 | 日本曹達株式会社 | 重合体の製造方法 |
JP2021528537A (ja) * | 2018-06-18 | 2021-10-21 | コーネル・ユニバーシティーCornell University | 高性能、低コストかつ適用が容易な抗菌コーティングのためのn−ハラミン−ドーパミン共重合体のシステムおよび方法 |
EP3807252A4 (en) * | 2018-06-18 | 2022-03-02 | Cornell University | SYSTEMS AND PROCESSES FOR N-HALAMINE-DOPAMINE COPOLYMERS FOR HIGH-PERFORMANCE, AFFORDABLE AND EASY-TO-APPLY ANTI-MICROBIAL COATINGS |
Also Published As
Publication number | Publication date |
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JPWO2015083360A1 (ja) | 2017-03-16 |
JP6063060B2 (ja) | 2017-01-18 |
TW201529615A (zh) | 2015-08-01 |
EP3078683A1 (en) | 2016-10-12 |
CN105793304A (zh) | 2016-07-20 |
EP3078683A4 (en) | 2017-05-17 |
US20160297911A1 (en) | 2016-10-13 |
TWI527833B (zh) | 2016-04-01 |
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