CN102212280A - Antistatic coating composition - Google Patents

Antistatic coating composition Download PDF

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Publication number
CN102212280A
CN102212280A CN2011100502856A CN201110050285A CN102212280A CN 102212280 A CN102212280 A CN 102212280A CN 2011100502856 A CN2011100502856 A CN 2011100502856A CN 201110050285 A CN201110050285 A CN 201110050285A CN 102212280 A CN102212280 A CN 102212280A
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solvent
weight
methyl
compound
static electricity
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CN102212280B (en
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冈崎佳奈
菊辻刚辅
大宅徹
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Toyo Ink Mfg Co Ltd
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Toyo Ink Mfg Co Ltd
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Priority claimed from JP2010119958A external-priority patent/JP4600605B1/en
Priority claimed from JP2010249073A external-priority patent/JP4678451B1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties

Abstract

The invention provides an antistatic film with anti-static property and sufficient wear resistance and excellent durability as a hard coating layer. A light-hardening coating composition and an anti-static layer using the same are also provided. The antistatic coating composition contains the following components in a predetermined allocation ratio: an antistatic copolymer (A) with quaternary ammonium salt group-containing compound (a-1) and oxyalkylene chain compound (a-2) as the essential constituents thereof; compound (B) with three or more ethylenically unsaturated groups; photopolymerization initiator (C); solvent (D) containing acetate-based solvent (d-2) with the carbon number thereof 3-5, anyone selected from carbonate or cyclic ethers solvent (d-3) and alcohol (d-1).

Description

The constituent that anti-static coating is used
Technical field
The invention relates to static electricity resistance, wear resistant (antiabrasion), the transparency, excellent in te pins of durability photo-hardening coating with constituent and use this coating with the antistatic backing of constituent, form the antistatic film that this antistatic backing forms.
Background technology
Before at the goods that plastics film is used as base material, purpose was to implement hard coating processing for the surface protection of plastics film.
But, be used in the hardened coating film of the hard coating processing on plastics film surface, formed by the compound (hereinafter referred to as " photo-hardening compound ") that utilizes ultraviolet isoreactivity energy line to give hardened to have (methyl) acryl.Therefore, the intrinsic sheet resistance value of hardened coating film uprises, static is easy to take place, and produces and result from the absorption and the electrostatic difficulty of dust.
For example, at display surfaces such as LCD or PDP, though it is useful with atraumatic hard coating processing, or the TAC film or the PET film of various photoprocess are implemented in use, adhering to but because of dust, and significantly undermine the visibility of image, or in production stage, difficulty takes place to produce, and generation significantly undermines the problem of productivity etc. because of static.
In order to solve these problems, and for the film static electricity resistance is provided, the contriver begins to attempt various researchs.For example known have a static electricity resistance coating constituent that has contained the quarternary ammonium salt based polyalcohol with having used, and coats plastics film, the method that makes static electricity resistance and hard coating and deposit.
But, generally contain the quarternary ammonium salt based polyalcohol, water absorbability height, because of bad, so when formation is filmed with the photo-hardening compound mutual solubility of the high hard coating of water repellency, in constituent, contain utmost point juicy, have the situation of precipitate, irregular, the irregular generation of quality of sclerosis.
In order to solve this kind problem, a kind of static electricity resistance coating of motion constituent is arranged, it is as the containing level Four ammonium alkali monomer and contain oxyalkylene and construct monomeric co-polymer of antistatic agent, and uses the monofunctional monomer (with reference to Japanese kokai publication hei 6-73305 communique, Japanese kokai publication hei 8-311366 communique, TOHKEMY 2001-323029 communique, TOHKEMY 2007-332181 communique) that contains polar group.
But, at preceding method, though can improve precipitate due to the moisture absorption, sclerosis is irregular, quality is irregular, but because of being to use the monofunctional monomer that contains polar group, thus the cross-linking density of filming reduce, as the hardness of film deficiency of necessity of hard coating.
Again, in recent years, in field of display about the portability machine, though require the height water-repellancy, but the former method of stating films gained and impregnated in situation in the warm water, molten because of hydrolysis from 4 grades of ammonium salts, have the situation that undermines static electricity resistance.
Again, using in the technical field that the present invention belongs to of constituent about coating, purpose for improve with the adherence of base material, lower interfere irregular etc., then motion 1 is arranged, the utilization of 3-dioxin-pentane, methylcarbonate equal solvent at TOHKEMY 2010-59280 communique, TOHKEMY 2007-108449 communique, TOHKEMY 2007-160513 communique.
Summary of the invention
The present invention has static electricity resistance, apply as hard simultaneously, possess sufficient wear resistant, the transparency, moreover, the purpose of this invention is to provide a kind of antistatic film, it also can cater in recent years and to require the water-repellancy that increases day by day, and the coating of the photo-hardening of excellent in te pins of durability with constituent, and formation use the antistatic film that this coating forms with the antistatic backing of constituent.
The inventor etc. are in order to address this problem, and through the investigation of joining hands, the result reaches the present invention.
That is anti-electrostatic of the present invention coating constituent is the anti-electrostatic coating constituent that contains static electricity resistance multipolymer (A), has compound (B), Photoepolymerizationinitiater initiater (C) and the solvent (D) of 3 above ethene unsaturated groups,
This static electricity resistance multipolymer (A) is the multipolymer of the compound with oxyalkylene chain (a-2) shown in compound with quarternary ammonium salt base (a-1) shown in the following general formula (1) and the following general formula (2) as essential constituent, this solvent (D) contain following any:
(i) the acetic ester series solvent (d-2) of pure series solvent (d-1) and carbon number 3 to 5;
(ii) pure series solvent (d-1) and be selected from carbonates or the solvent of ring-type ethers (d-3),
With respect to this compound (B) 100 weight parts, contain this static electricity resistance multipolymer (A) 1 to 20 weight part, this Photoepolymerizationinitiater initiater (C) 0.1 to 20 weight part,
Under the situation of this (i), in the total 100 weight % of this (A) to (D), solvent (D) contains 30 to 80 weight %, in the 100 weight % of this solvent (D), the content of alcohol series solvent (d-1) is that the content of the acetic ester series solvent (d-2) of 5 to 25 weight %, carbon number 3 to 5 is 55 to 90 weight %
Under this situation (ii), in the total 100 weight % of this (A) to (D), contain solvent (D) 20 to 80 weight %, in the 100 weight % of this solvent (D), the content that the content of pure series solvent (d-1) is 5 to 30 weight %, be selected from the solvent (d-3) of carbonates or ring-type ethers is 20 to 95%.
General formula (1)
CH 2＝C(R 1)COZ(CH 2) kN +(R 2)(R 3)R 4·X -
(in the formula, R 1Expression H or CH 3R 2To R 4It is the alkyl of carbon number 1 to 9 independently of one another; Z represents Sauerstoffatom or NH base; K represents 1 to 10 integer; X -Represent 1 valency negatively charged ion);
General formula (2)
CH 2＝C(R 5)COO(AO) nR 6
(in the formula, R 5Expression H or CH 3R 6The alkyl of expression hydrogen or carbon number 1 to 22; N represents 2 to 200 integer; A represents the alkyl of stretching of carbon number 2 to 4).
Again, the invention relates to the anti-electrostatic coating constituent of aforementioned invention, it is characterized by the R in the general formula (1) 2To R 4Be separately independently, do not have the alkyl of the carbon number 1 to 9 that replaces, the R in the general formula (2) 6Expression hydrogen or do not have the alkyl of the carbon number 1 to 22 of replacement.
Again, the present invention is each described anti-electrostatic coating constituent of aforementioned invention, and it is characterized by pure series solvent (d-1) is to be selected from by methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, hexalin, 2-methyl cellosolve, cellosolvo, 2-propoxy-ethanol, butoxy ethanol; 1-methoxyl group-2-propyl alcohol, 3-methoxyl group-1-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, 2-oxyethyl group-1-propyl alcohol and the group that the 3-oxyethyl group-the 1-propyl alcohol is constituted.
Again, the invention relates to each described anti-electrostatic coating constituent in the aforementioned invention, it is characterized by the solvent (d-3) that is selected from carbonates or ring-type ethers, be to be selected from methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, 1,3-dioxin-pentane (dioxolane), 1, the group that 4-dioxy land surround (dioxane), tetrahydrofuran (THF) and tetrahydrochysene piperazine are muttered and constituted.
Again, the invention relates to a kind of antistatic film, its one side at least that to be each the described anti-static coating that will use aforementioned invention be formed at the tri acetyl cellulose transparent support with the antistatic backing of constituent forms.
With the formed antistatic backing of coating constituent, have sufficient static electricity resistance by anti-electrostatic of the present invention, show excellent in resistance abradability, the transparency simultaneously, even moreover in the warm water immersion test, also have a height weather resistance.Therefore, anti-static coating constituent of the present invention can suitably be used in the used for surface applying of upper layer such as indicating meter, plastic molded article etc., is required except static electricity resistance, adds the various uses of hard coating and the transparency.
Embodiment
Now the form that describes enforcement of the present invention in detail is as follows, and the below explanation of Ji Zai constitutive requirements is examples (typical example) of embodiments of the present invention, as long as be no more than main idea of the present invention, does not then have specific with regard to these contents.In addition, the record of " counting A arbitrarily to counting B arbitrarily " is in number A and the bigger scope of several A in this manual, the meaning of the scope that number B and several B are littler.
[first embodiment]
The static electricity resistance multipolymer (A) of first embodiment of the invention, be with the compound with quarternary ammonium salt base (a-1) shown in the following general formula (1), with the compound with oxyalkylene chain (a-2) shown in the following general formula (2) as necessary constituent, moreover can according to needs will be with this (a-1), (a-2) but the compound (a-3) of copolymerization carries out free-radical polymerized gained in pure series solvent (d-1).
General formula (1)
CH 2＝C(R 1)COZ(CH 2) kN +(R 2)(R 3)R 4·X -
(in the formula, R 1Expression H or CH 3R 2To R 4Represent the alkyl of carbon number 1 to 9 independently of one another; Z represents Sauerstoffatom or NH base; K represents 1 to 10 integer; X -Represent 1 valency negatively charged ion).
General formula (2)
CH 2＝C(R 5)COO(AO) nR 6
(in the formula, R 5Expression H or CH 3R 6The alkyl of expression hydrogen or carbon number 1 to 22; N represents 2 to 200 integer; A represents the alkyl of stretching of carbon number 2 to 4).
＜have a compound (a-1) of quarternary ammonium salt base 〉
The compound with quarternary ammonium salt base (a-1) of first embodiment is to represent with this general formula (1).In the general formula (1), R 2To R 4The alkyl of carbon number 1 to 9 are independent separately optional bases of selecting generation or not having replacement, being preferably does not have the base that replaces, being more preferred from does not have the alkyl that replaces.Do not have the alkyl aspect that replaces, can use the ramose base, branchiess base also can use any one.Compound (a-1) also can be also with more than 2 kinds.
R 2To R 4Carbon number than 10 bigger situations, the water repellency of the static electricity resistance multipolymer (A) that is produced increases, the result, the water absorbability that contains the antistatic backing of this static electricity resistance multipolymer (A) reduces, and has the situation that can't obtain good antistatic performance.
The R of general formula (1) 2To R 4In, the alkyl aspect that do not have to replace is preferably the alkyl of carbon number 1 to 3, sees it by handy viewpoint, be preferably have methyl, the thing of alkyl that the nothing of ethyl, n-propyl, sec.-propyl etc. replaces.
Compound (a-1) with quarternary ammonium salt base for example gives level Fourization with the level Four agent and can obtain to have (methyl) esters of acrylic acid or (methyl) acrylic amide of amido.Also can use commercially available (methyl) esters of acrylic acid or (methyl) acrylic amide with quarternary ammonium salt base again.
In the general formula (1), example in order to (methyl) esters of acrylic acid with amido of forming compound (a-1) (it is that Z is the compound with quarternary ammonium salt base of Sauerstoffatom) can exemplify (methyl) DMAM, (methyl) vinylformic acid dimethyl amido propyl ester, (methyl) vinylformic acid dimethyl amido butyl ester, (methyl) vinylformic acid diethyl amido ethyl ester, (methyl) vinylformic acid diethyl amido propyl ester, (methyl) vinylformic acid dipropyl amido ethyl ester, (methyl) vinylformic acid dibutyl amido ethyl ester, (methyl) vinylformic acid dihydroxy ethyl amido ethyl ester etc.
In order to the example of (methyl) acrylic amide of forming compound (a-1) (it is that Z is the compound with quarternary ammonium salt base of NH base), can exemplify dimethyl amido ethyl (methyl) acrylamide in the general formula (1) with amido, dimethyl amido propyl group (methyl) acrylamide, dimethyl amido butyl (methyl) acrylamide, diethyl amido ethyl (methyl) acrylamide, diethyl amido propyl group (methyl) acrylamide, dipropyl amido ethyl (methyl) acrylamide, dibutyl amido ethyl (methyl) acrylamide, dihydroxy ethyl amido ethyl (methyl) acrylamide etc.
With so that (methyl) acrylic amide that has (methyl) esters of acrylic acid of this amido or have this amido gives level Four chlorating level Four agent aspect, can use various halogenide classes such as kelene benzyl, zephiran chloride, chlorination alkyl, bromination alkyl; The alkyl sulfide acids of dimethyl sulfate, diethyl sulfuric acid, dipropyl sulfuric acid etc.; Sulfonic acid esters such as methyl tosylate, methyl benzenesulfonate; Alkylphosphonic acid carboxylic acid classes such as trimethyl phosphite.
＜have a compound (a-2) of oxyalkylene chain 〉
Then, with regard to the formation of the employed static electricity resistance multipolymer of first embodiment (A) employed another must composition, the compound (a-2) with oxyalkylene chain is illustrated.
Compound (a-2) with oxyalkylene chain is with this general formula (2) expression, for example after ring-opening polymerization due to the alkanol of oxyethane, by with the transesterification reaction of (methyl) methyl acrylate, perhaps by getting with the acrylic acid reaction of chlorination (methyl).
In this general formula (2), oxyalkylene group (AO) is the oxyalkylene group of carbon number 2 to 4, can exemplify for example Oxyranyle, propylene oxide base, butylene oxide ring base.In same monomer, also can there be the different oxyalkylene group of carbon number again.
The number of oxyalkylene group (n) is 2 to 200 integer, is preferably 10 to 100 integer.In the situation below 2 or more than 101, as described later, have can't obtain with molecule in have the situation of abundant mutual solubility of the compound (B) of 3 above ethene unsaturated groups.
R 6The alkyl of expression hydrogen or carbon number 1 to 22.At carbon number more than 23, because of raw material is so that high price is can't practicability.
Aspect the alkyl of carbon number 1 to 22, the optional base of selecting generation or not having replacement, being preferably does not have the base that replaces, and being preferably does not have the alkyl that replaces.Aspect the alkyl that do not have to replace, can use have the ramose base, branchiess base, also can use any.Oxyalkylene group also can be also with more than 2 kinds.
Compound (a-2) aspect with oxyalkylene chain, concrete speech exemplify for example polyethyleneglycol (methyl) acrylate, polypropylene propylene glycol list (methyl) acrylate, poly-butyleneglycol list (methyl) acrylate of stretching, poly-(ethylene glycol and 1,2-propylene glycol) single (methyl) acrylate, poly-(ethylene glycol-stretch butyleneglycol) single (methyl) acrylate, poly-(propylene glycol-stretch butyleneglycol) single (methyl) acrylate, polyethyleneglycol (methyl) acrylate monomethyl ether, polyethyleneglycol (methyl) acrylate monobutyl ether, polyethyleneglycol (methyl) acrylate list octyl ether, polyethyleneglycol (methyl) acrylate list benzyl oxide, polyethyleneglycol (methyl) acrylate monophenyl ether, polyethyleneglycol (methyl) acrylate list ether in the last of the ten Heavenly stems, polyethyleneglycol (methyl) acrylate list ten diether, polyethyleneglycol (methyl) acrylate list ten tetraethers, polyethyleneglycol (methyl) acrylate list margaron, single (methyl) acrylate octyl ether of polyethyleneglycol (methyl) acrylate list 18 ethers poly-(ethylene glycol and 1,2-propylene glycol), poly-(ethylene glycol and 1,2-propylene glycol) single (methyl) acrylate 18 ethers, poly-(ethylene glycol and 1,2-propylene glycol) single (methyl) acrylate nonyl phenylate etc.Again, compound (B) also can be also with more than 2 kinds.
＜with (a-1), (a-2) but the compound (a-3) of copolymerization
The employed static electricity resistance multipolymer of first embodiment (A), be the compound (a-1) that will have the quarternary ammonium salt base with the compound (a-2) with oxyalkylene chain as necessary constituent, moreover can according to needs at random will be with this (a-1), (a-2) but the compound (a-3) of copolymerization in pure series solvent (d-1), carry out free-radical polymerized and get.
In first embodiment with (a-1), (a-2) but the compound (a-3) of copolymerization, so long as it is then good to have a compound of 1 ethene unsaturated group, though be not particularly limited, but can exemplify for example (methyl) alkyl acrylate of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) dodecyl acrylate, (methyl) octadecyl acrylate etc.; (methyl) vinylformic acid hydroxyl alkane ester of (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester etc.; Various (methyl) acrylate or vinylbenzene, the vinyl toluene etc. of (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid two cyclopentenes esters, (methyl) vinylformic acid dicyclopentenyl 2-ethoxyethyl acetate, (methyl) vinylformic acid ethoxy ethyl ester, (methyl) vinylformic acid ethyl carbitol ester, (methyl) vinylformic acid butoxy ethyl ester, (methyl) vinylformic acid cyano group ethyl ester, (methyl) acrylic acid epoxy propyl ester etc.
The employed static electricity resistance multipolymer of first embodiment (A), can reaching compound (a-1), (a-2) at random, (a-3) carries out free-radical polymerized in pure series solvent (d-1) and obtains.Compound (a-1), (a-2) and usage quantity (a-3) are that compound (a-1) is seen it by the viewpoint of antistatic performance, is preferably 30 to 60 weight % in the total 100 weight % of free-radical polymerised compound; Compound (a-2) is seen it by described later with the mutual solubility viewpoint with compound (B) of 3 above ethene unsaturated groups, is preferably 10 to 50 weight %.Compound (a-3), under by the static electricity resistance of adjusting the static electricity resistance multipolymer (A) that is produced, solvability, inflexible purpose, can be according to using in the scope of 0 to 50 weight %.
Static electricity resistance multipolymer (A), solution polymerization process that can be by using polymerization starters such as the two systems of peroxidation system or azo etc., and can obtain to reach at random (a-3) with aforementioned weight ratio institute's blended compound (a-1), (a-2).
Aspect the solvent that when polymerization, uses, be not particularly limited, be preferably and use pure series solvent (d-1), it is to be selected from by methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, hexalin, 2-methyl cellosolve, cellosolvo, 2-propoxy-ethanol, butoxy ethanol, 1-methoxyl group-2-propyl alcohol, 3-methoxyl group-1-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, 2-oxyethyl group-1-propyl alcohol and group that the 3-oxyethyl group-the 1-propyl alcohol is constituted.These can use a kind separately, perhaps make up more than 2 kinds and use.
The usage quantity of static electricity resistance multipolymer (A), with respect to compound (B) 100 weight parts with 3 above ethene unsaturated groups described later, be preferably 1 to 20 weight part, be more preferred from 3 to 15 weight parts, special good be 3 to 10 weight parts.Being lower than 1 weight part, then can't obtain sufficient antistatic performance, if when surpassing 20 weight parts, then the wear resistant of formed antistatic backing or obdurability reduce.
Then, the anti-electrostatic with regard to first embodiment is illustrated with the employed compound (B) with 3 above ethene unsaturated groups of coating constituent.
Having the compound (B) of 3 above ethene unsaturated groups, is the crosslinking reaction compound that has (methyl) acryl more than at least 3 in molecule, can contain ehter bond, thioether bond, ester bond, amido linkage, urethane linkages etc. at this intramolecularly.
Compound (B) aspect with 3 above ethene unsaturated groups, can exemplify for example new Doutrate of three (methyl) vinylformic acid in specific words, the new Doutrate of four (methyl) vinylformic acid, three (methyl) vinylformic acid trishydroxymethyl propyl ester, EO modification three (methyl) vinylformic acid trishydroxymethyl propyl ester, PO modification three (methyl) vinylformic acid trishydroxymethyl propyl ester, ginseng (acryloxy ethyl) isocyanuric acid ester, caprolactone modification ginseng (acryloxy ethyl) isocyanuric acid ester, three (methyl) vinylformic acid trishydroxymethyl ethyl ester, four (methyl) vinylformic acid, two new Doutrates, five (methyl) vinylformic acid, two new Doutrates, six (methyl) vinylformic acid, two new Doutrates, alkyl-modified three (methyl) vinylformic acid two new Doutrates, alkyl-modified four (methyl) vinylformic acid two new Doutrates, alkyl-modified five (methyl) vinylformic acid two new Doutrates, caprolactone modification six (methyl) vinylformic acid two new Doutrates, four (methyl) vinylformic acid 1,2, the polyvalent alcohol of 3-cyclohexyl etc. and (methyl) acrylic acid ester cpds;
Polyurethane gathers (methyl) acrylate, polyester gathers (methyl) acrylate, polyethers gathers (methyl) acrylate, polyacrylic acid gathers (methyl) acrylate, poly-(methyl) acrylate of polyalcohols acid, poly-(methyl) acrylate of poly-epoxy group(ing), poly-(methyl) acrylate of poly-spiral acetal, polyhutadiene gathers (methyl) acrylate, the polythiol polyenoid gathers (methyl) acrylate, poly-(methyl) acrylic compound of polyfunctional compounds such as poly-(methyl) acrylate of poly-silicon;
By multivalence alcohol and polyprotonic acid and (methyl) vinylformic acid institute synthetic ester cpds, for example can exemplify by trimethylolethane/succsinic acid/vinylformic acid=2/1/4 (mol ratio) institute synthetic ester cpds etc.
In addition, in the present invention, (methyl) acrylate is meant record person when omitting acrylate, methacrylic ester.Also identical in explanation about compound (a-1), (a-2).
The compound (B) that these have 3 above ethene unsaturated groups can use separately or use as the mixture more than 2 kinds.
In addition, have the compound of 2 following ethene unsaturated groups, also can be at wear resistant that requires formed antistatic backing or obdurability, and use in the scope that can satisfy this wear resistant or obdurability.
Photoepolymerizationinitiater initiater in first embodiment (C), so long as have the thing that can begin the function of radical polymerization because of optical excitation, then be not particularly limited, can exemplify for example aceotphenone compound, st-yrax compound, benzophenone compound, phosphine oxide compound, ketal (ketal) compound, anthraquinone compounds, 9-Yang Liu mound compound etc.In specific words, can exemplify benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diethoxy phenyl methyl ketone, benzyl dimethyl ketal, 1-hydroxy-cyclohexyl benzophenone, benzophenone, oxidation 2,4,6-trimethylammonium st-yrax diphenyl phosphine, N, N-dimethyl amido isoamyl benzoate, 2-chlorine 9-Yang Liu mound, 2,4-diethyl 9-Yang Liu mound etc.Also can add known organic amine as sensitizing agent (sensitizer) again.
The usage quantity of Photoepolymerizationinitiater initiater (C) with respect to aforesaid compound (B) 100 weight parts with 3 above ethene unsaturated groups, is preferably 0.1 to 20 weight part, is more preferred from 1 to 10 weight part.Be lower than 0.1 weight %, then can't obtaining polymerization and cause effect, when surpassing 20 weight %, then hard coating has the anxiety of reduction.
Then, the solvent (D) with regard to first embodiment is illustrated.
Before, be used in the solvent of anti-electrostatic, because of being dissolves each other the high photo-hardening constituent of the high static electricity resistance multipolymer of wetting ability and water repellency, so generally be the low polar solvent of the high polar solvent of alcohol mixture etc. and ether, ketone, ester, hydrocarbon etc. with the coating constituent.
In the first embodiment, by static electricity resistance multipolymer (A), see it with the viewpoint of mutual solubility of compound (B) with 3 above ethene unsaturated groups, by and be used as high polar solvent pure series solvent (d-1), with acetic ester series solvent (d-2) as the carbon number 3 to 5 of low polar solvent, then just can simultaneously keep sufficient antistatic performance, one side significantly improves hard coating property.
That is, as low polar solvent, solvent beyond the acetic ester series solvent, carbonates or the ring-type ethers that use carbon number 3 to 5, for example when ester (except the carbonates), ether (except the ring-type ethers), ketone, hydrocarbon system solvent etc., have wear resistant and reduce, or make the situation of static electricity resistance reduction with the warm water immersion test.This phenomenon is with as transparent support, and is remarkable especially in the situation that uses tri acetyl cellulose.Though reason is indeterminate, but the contriver infers when the aforementioned low polar solvent beyond acetic ester series solvent, carbonates or the ring-type ethers of volume use carbon number 3 to 5, in the exsiccant step, static electricity resistance multipolymer (A) localizes significantly in film coated surface, thereby the cross-linking density of film coated surface is reduced.In addition, in second embodiment, detailed description is arranged with regard to carbonates or ring-type ethers.
Again, in the acetic ester series solvent, in the acetic ester series solvent of carbon number more than 6, compared to pure series solvent (d-1), the evaporation rate of ester is slack-off, and the surface localization of static electricity resistance multipolymer (A) can't produce smoothly, can produce detrimentally affects such as static electricity resistance reduction or film albefaction.
Pure in the first embodiment series solvent (d-1) aspect, but illustration and the illustrated identical person of thing of use gained solvent when obtaining static electricity resistance multipolymer (A) can be used singly or in combination of two or more thereof.
Aspect the acetic ester series solvent (d-2) of carbon number 3 to 5, can exemplify methyl acetate, ethyl acetate, propyl acetate.These can use a kind separately, perhaps make up more than 2 kinds and use.
The anti-electrostatic of first embodiment coating constituent, be in the solution of static electricity resistance multipolymer (A), also can add pure series solvent (d-1) identical and acetic ester series solvent (d-2) and obtain, also can add different pure series solvent (d-1) of thing when being used in multipolymer (A) generation and acetic ester series solvent (d-2) and obtain with being used in the thing of static electricity resistance multipolymer (A) when producing.Perhaps,, add acetic ester series solvent (d-2), then can obtain to be the anti-electrostatic of suitable viscosity coating constituent filming by pure series solvent (d-1) solution at static electricity resistance multipolymer (A).
The anti-electrostatic of first embodiment coating constituent, as solvent (D), be with the acetic ester series solvent (d-2) of this alcohol series solvent (d-1) and carbon number 3 to 5, can use the solvent of ether, ketone, ester, hydrocarbon etc. arbitrarily in the scope that does not undermine purpose of the present invention.In specific words, in solvent 100 weight %, other preferred solvents is below the 20 weight %.
For example, dissolve the tri acetyl cellulose support, and the solvent of adherence is provided, known have 1,3-dioxin-pentane (dioxolane), 1, the ethers of 4-dioxy land surround (dioxane), tetrahydrofuran (THF) etc.; The ketone of acetone, methylethylketone, pimelinketone, diacetone alcohol etc.; The carbonates of methylcarbonate, diethyl carbonate etc. etc.These can use a kind separately, perhaps make up more than 2 kinds and use.
Anti-electrostatic is with the content of solvent (D) in the coating constituent, by the viscosity of constituent, all the viewpoint of levelling, drying property is seen it, in the total 100 weight % of (A) to (D), is preferably and contains 30 to 80 weight %, is more preferred from and contains 30 to 60 weight %.
Then, in the 100 weight % of this solvent (D), the content of alcohol series solvent (d-1) is that the content of the acetic ester series solvent (d-2) of 5 to 25 weight %, carbon number 3 to 5 is 55 to 90 weight %, is more preferred from pure series solvent (d-1) 10 to 20 weight %, acetic ester series solvent (d-2) 65 to 85 weight %.
The content of alcohol series solvent (d-1) has the solubleness deficiency of static electricity resistance multipolymer (A) when being lower than 5 weight %, produces throw out in the coating constituent, or produces in filming and separate out dysgenic situations such as orange peel shape (orange peel) or albefaction.On the one hand, when surpassing 25 weight %, have the solubleness deficiency of compound (B) with 3 above ethene unsaturated groups, and the suitable property reduction that uprises, films of the viscosity of coating constituent, or the surface localization of static electricity resistance multipolymer (A) is difficult to produce the anxiety of antistatic performance reduction.
Again, the acetic ester series solvent (d-2) of carbon number 3 to 5 is lower than the situation of 55 weight %, reaches (d-2) with (d-1), and the amount of other solvent arbitrarily of Shi Yonging becomes many relatively simultaneously, the wear resistant that the result has hardened coating film reduces, or static electricity resistance has the situation of reduction in the warm water immersion test.When acetic ester series solvent (d-2) surpasses 90 weight %, have the solubleness deficiency of static electricity resistance multipolymer (A), in the coating constituent, produce throw out, or in filming, separate out, become the dysgenic situation of orange peel shape or albefaction etc.
Anti-static coating constituent at first embodiment, can add light sensitizer, photostabilizer, UV light absorber, catalyst, tinting material, lubricant, all flat agent, defoamer, polymerization retarder, polymerization promotor, antioxidant, incombustible agent, infrared absorbent, interfacial agent, surface modifier, thixotropy (thixotropy) agent, spherical filling agent etc. according to needs.
The anti-static coating constituent of first embodiment can be filmed to various supports, obtains attached antistatic backing member.The anti-static coating constituent of first embodiment is preferably and films in plastics film, uses as antistatic film.Can make known functional layers such as high refractive index layer, low-index layer, near infrared absorption layer, electromagnetic shielding layer be formed at the upper strata or the lower floor of antistatic backing according to needs again.
Form the method aspect of antistatic backing on base material in the first embodiment, can exemplify with excellent coating method, the cutter coating method, method of spin coating, contrary roller coating method, mould coating method (die coating), the spray coating method, the roller coating method, the intaglio plate coating method, nick version coating method, die lip coating method (lip coating), the airblade coating method, the coating method of dip-coating (dipping) method etc., anti-static coating is filmed behind the substrate resin surface with constituent, make solvent seasoning according to necessity, the active energy ray of further irradiation ultraviolet radiation etc. carries out crosslinked hardened method with the anti-static coating constituent through filming.
This active energy ray aspect, can use from light source sent the ultraviolet ray of xenon lamp, low pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halid lamp, carbon arc lamp, tungsten lamp etc. or, uses Ke Kelaofu-Wo Er of common 20 to 2000KeV gulp down (Cockroft-Walton) type, Fan Degeruifu (vandegraaf) type, the transformation (resonancetransformer) that resonates type, insulating core transformer type, linear pattern, the electron beam that electron-beam accelerator took out, α line, β line, γ line etc. of nanometer (dynamitron) type, high-frequency type etc.
Thickness with the antistatic backing of this method gained is not particularly limited, and is generally 1 to 20 μ m, is preferably 3 to 10 μ m.When the thickness of antistatic backing is lower than 3 μ m, have the anxiety of pencil hardness or wear resistant reduction, surpass the situation of 10 μ m, have the anxiety of be full of cracks generation.
In first embodiment, support (also being called base material) aspect is not particularly limited, and can exemplify glass, resin formed substance, film support etc.
Aspect resin formed substance, can exemplify polymethylmethacrylate or methyl methacrylate as the forming composition beyond the film of the multipolymer system of main constituent, polystyrene system, styrene-methylmethacrylate copolymer system, styrene-acrylonitrile copolymer system, polycarbonate system, cellulose acetate butyrate resin system, polyene propyl group Diethylene Glycol carbonate resin system, polyvinyl chloride (PVC) RESINS system, vibrin system etc.
Again; film support aspect can exemplify for example polyester film; polyethylene film; polypropylene film; the cellulose film film; the diacetyl cellulose film; the tri acetyl cellulose film; ethanoyl cellulose butylate film; polyvinyl chloride film; poly-protochloride vinyl film; PVA (PVOH) FILM; ethylene vinyl alcohol film; polyolefin film; polystyrene film; polycarbonate film; polymethylpentene (pentene) film; polysulphone film; poly (ether ether ketone) film; the polyethersulfone film; the polyetherimide film; Kapton; fluorine resin film; the nylon film; acrylate film etc.
In addition, in the situation of using film as support, also can use acrylic resin further is set in film, copolyester is that resin, polyurethane are the so-called easily film of bonding type of resin layers such as resin, phenylethylene-maleic diacid grafted polyester resin, acrylic acid-grafted vibrin.
The anti-electrostatic coating agent of first embodiment, the transparency, static electricity resistance, wear resistant excellence, moreover the weather resistance after the immersion is also extremely excellent.
The transparency can mist degree (HAZE) be estimated, and is preferably 10% below, is more preferred from below 5%, the spy is good is below 1%.
Static electricity resistance can the sheet resistance value evaluation, is preferably 5 * 10 12Ω/ is (below the Ω/sq).
Again, the radical evaluation that wear resistant can damage, below 5 for good, be more preferred from 0.
According to first embodiment, behind warm water immersion, can keep these all rerum naturas again.These effects; in the situation of using tri acetyl cellulose (TAC) film as support; remarkable especially with the viewpoint sight of wear resistant; the anti-static coating constituent of first embodiment can suitably be used in the optical display purposes of LCD or PDP etc., the surface coated purposes of plastic molded article etc.; requiring except static electricity resistance, and hard coating and transparent various uses.
[second embodiment]
The anti-electrostatic of second embodiment of the invention coating constituent, the kind of solvent (D) is also inequality with the coating constituent with the anti-electrostatic of aforementioned first embodiment with the allotment ratio.That is, in aforementioned first embodiment, solvent (D) is the thing that contains the acetic ester series solvent (d-2) of pure series solvent (d-1) and carbon number 3 to 5, with respect to this, in second embodiment, by solvent is to contain pure series solvent (d-1), and is selected from the point of the solvent (d-3) of carbonates or ring-type ethers, with and allotment than then different.
The anti-electrostatic of second embodiment coating constituent is the thing that contains static electricity resistance multipolymer (A), has compound (B), Photoepolymerizationinitiater initiater (C) and the solvent (D) of 3 above ethene unsaturated groups.Wherein, with regard to static electricity resistance multipolymer (A), compound (B), light trigger (C), then be as elaborating in first embodiment, repeat no more, and, then be described in detail as follows with regard to solvent (D) and allotment ratio thereof in this explanation.
The solvent of second embodiment (D) is to contain pure series solvent (d-1) and be selected from carbonates or the thing of the solvent of ring-type ethers (d-3).The solvent of second embodiment (D) contains following allotment ratio.That is in the total 100 weight % of aforementioned (A) to (D), solvent (D) contains 20 to 80 weight %.Among the 100 weight % of solvent (D), the content of pure series solvent (d-1) becomes 5 to 30 weight %, and makes the content of the solvent (d-3) that is selected from carbonates or ring-type ethers become 20 to 95%.In addition, with respect to compound (B) 100 weight parts, the content of the content of static electricity resistance multipolymer (A), light trigger (C) is that first embodiment is put down in writing as described above.
Before, be used in the solvent of anti-electrostatic, because of being dissolves each other the high photo-hardening constituent of the high static electricity resistance multipolymer of wetting ability and water repellency, so generally be the low polar solvent of the contour polar solvent of alcohol mixture and ether, ketone, ester, hydrocarbon etc. with the coating constituent.
In second embodiment, see it by the static electricity resistance multipolymer (A) and the viewpoint of the mutual solubility of compound (B) with 3 above ethene unsaturated groups, by and be used as high polar solvent pure series solvent (d-1), with as the solvent (d-3) that is selected from carbonates or ring-type ethers of low polar solvent, just can one side can keep sufficient antistatic performance, one side significantly improves hard coating property.
That is, low polar solvent, solvent beyond the acetic ester series solvent, carbonates or the ring-type ethers that use carbon number 3 to 5, for example when ester (except the carbonates), ether (except the ring-type ethers), ketone, hydrocarbon system solvent etc., it is insufficient to have manifesting of antistatic performance, or wear resistant is reduced, or make the situation of static electricity resistance reduction in the warm water immersion test.Though reason is non-clear and definite, but the contriver infers when the aforementioned low polar solvent beyond acetic ester series solvent, carbonates or the ring-type ethers of volume use carbon number 3 to 5, then with drying step, make static electricity resistance multipolymer (A) near film coated surface, not have orientation fully, and antistatic performance manifests insufficient, or make significantly localization of static electricity resistance multipolymer (A) near surface on the contrary, thereby the cross-linking density of film coated surface is reduced.In addition, with regard to the acetic ester series solvent of carbon number 3 to 5, then be that first embodiment is described as described above.
In second embodiment, aspect pure series solvent (d-1), but illustration is used the illustrated identical person of thing of gained solvent when obtaining static electricity resistance multipolymer (A), and can be used singly or in combination of two or more thereof.
Be selected from aspect the solvent (d-3) of carbonates or ring-type ethers, can exemplify two methylcarbonates, Ue-5908, Methyl ethyl carbonate, 1,3-dioxin-pentane (dioxolane), 1,4-dioxy land surround (dioxane), tetrahydrofuran (THF), tetrahydrochysene piperazine are muttered.These can be used singly or in combination of two or more thereof.
The anti-electrostatic of second embodiment coating constituent, be in the solution of static electricity resistance multipolymer (A), add to produce identical pure series solvent (d-1) and the carbonates of the time user of institute with static electricity resistance multipolymer (A) or add the solvent (d-3) of ring-type ethers and get, also can add the solvent (d-3) of the different pure series solvent (d-1) of thing used when producing and carbonates or interpolation ring-type ethers and get with multipolymer (A).Perhaps,, add the solvent (d-3) of carbonates or ring-type ethers, then can obtain to be the anti-electrostatic of proper viscosity coating constituent filming by in pure series solvent (d-1) solution of static electricity resistance multipolymer (A).
The anti-electrostatic of second embodiment coating constituent, as solvent (D), then,, use the solvent of ether, ketone, ester, hydrocarbon etc. arbitrarily in the scope that does not undermine purpose of the present invention with the solvent (d-3) of this alcohol series solvent (d-1) and carbonates or ring-type ethers.In specific words, in solvent 100 weight %, other preferred solvents is for being lower than 60 weight %, being more preferred from and being lower than 40 weight %.
For example, dissolving the tri acetyl cellulose support, and the solvent aspect of adherence, the known ketone that acetone, methylethylketone, pimelinketone, diacetone alcohol etc. are arranged are being provided; The acetate esters of methyl acetate, ethyl acetate, propyl acetate, butylacetate etc. etc.These can be used singly or in combination of two or more thereof.
At the content of anti-electrostatic, by constituent viscosity, all the viewpoint of levelling, drying property is seen it, in the total 100 weight % of (A) to (D), be preferably and contain 20 to 80 weight %, be more preferred from and contain 20 to 60 weight % with solvent (D) in the coating constituent.
Then, in the 100 weight % of this solvent (D), the content of alcohol series solvent (d-1) is that the content of the solvent (d-3) of 5 to 30 weight %, carbonates or ring-type ethers is preferably 20 to 95 weight %, and the solvent (d-3) that is more preferred from pure series solvent (d-1) and is 10 to 20 weight %, carbonates or ring-type ethers is 30 to 85 weight %.
When the content of alcohol series solvent (d-1) is lower than 5 weight %, then have the solubleness deficiency of static electricity resistance multipolymer (A), in the coating constituent, produce throw out, or in filming, separate out, and produce dysgenic situations such as orange peel shape or albefaction.On the one hand, when surpassing 30 weight %, solubleness deficiency with compound (B) of 3 above ethene unsaturated groups, the viscosity that has the coating constituent uprise, film, and the surface localization of reduction of suitable property or static electricity resistance multipolymer (A) is difficult to produce, the anxiety of antistatic performance reduction.
Again, the solvent of carbonates or ring-type ethers (d-2) is lower than the situation of 20 weight %, then reach (d-2) the employed together relative result who increases of amount of other solvent arbitrarily with (d-1), the wear resistant that has hardened coating film reduces or reduces in the warm water immersion test situation of static electricity resistance.When the solvent of carbonates or ring-type ethers (d-2) surpasses 95 weight %, then have the solubleness deficiency of static electricity resistance multipolymer (A), in the coating constituent, produce throw out, in filming, separate out, become the dysgenic situation of orange peel shape or albefaction etc.
At the anti-static coating constituent of second embodiment, can be according to needs, can add with the interpolation material of first embodiment explanation etc.
Anti-static coating constituent of the present invention, identical with aforementioned first embodiment, can various supports be filmed, and obtain the member of attached antistatic backing.The anti-static coating constituent of second embodiment is preferably and films in plastics film, and uses as antistatic film.Again, also can have various films and lamination constructor, then identical with first embodiment.With regard to antistatic backing, because of can similarly forming, so explanation is omitted with first embodiment.
The anti-electrostatic coating agent of second embodiment, the transparency, static electricity resistance, wear resistant excellence, moreover the weather resistance after the immersion is also excellent.
The transparency can the mist degree evaluation, be preferably below 10%, be more preferred from below 5%, special good be below 1.0%.
Static electricity resistance can the sheet resistance value evaluation, is preferably 5 * 10 12Below Ω/.
Again, the radical evaluation that wear resistant can damage is preferably below 5, is more preferred from 0.
According to second embodiment, can behind warm water immersion, keep these all rerum naturas again.These effects; in the situation of using tri acetyl cellulose (TAC) film as support; remarkable especially with the viewpoint sight of wear resistant; the anti-static coating constituent of second embodiment; can suitably be used in the optical display purposes of LCD or PDP etc., the surface coated purposes of plastic molded article etc.; requiring except static electricity resistance, and requiring hard coating and transparent various uses.
Embodiment
Now it is as follows further to specify the present invention with embodiment, but following examples and unmatchful interest field of the present invention are done any restriction." part " is expression " weight part " in addition, in an embodiment.
Synthesis example 1
＜have a manufacturing of the compound (a-2-1) of oxyalkylene chain 〉
In the autoclave that possesses whipping appts, thermometer, oxyalkylene ingress pipe and nitrogen ingress pipe, 352.5 parts of the lauryl alcohols of packing into, 713 parts of toluene, and 2 parts in potassium hydroxide are after replacing with nitrogen in being, in reaction vessel, in pressure 8kgf/cm 2Below, temperature is below 90 ℃, 2500 parts in oxyethane (is 30 times of moles with respect to lauryl alcohol) was pressed into through 4 hours, moreover makes it to react 5 hours in 90 ℃.Then by air and after removing unreacted oxyethane, add the sorbent material of consonance chemical industry limited-liability company system Kyowaad600[alkali (great soil group) metal hydroxides] 42.0 parts, under dry air 5kPa, 30 ℃ condition, after handling in 2 hours, leached, filtrate from gained is removed toluene with the heating decompression, obtain polyethylene oxide addition alcohol.
The polyethylene oxide addition alcohol of gained is moved to the flask that whipping appts, thermometer, air leading-in conduit, liquid interpolation pipeline and rectifying tower are installed for 300.9 parts, pack into 0.04 part of methyl methacrylate 200 parts (is 10 times of moles with respect to polyethylene oxide addition alcohol), hydroquinone monomethyl ether, one side is blown into dry air, after one side is heated to 80 ℃, per hour add 0.2 part of titanic hydroxide four different third salt, and carry out transesterification reaction.In reaction, can be according to need be with the methyl alcohol of by-product and methyl methacrylate as azeotropic mixture, and heat up in a steamer except that in reaction system.After 4 hours, after becoming 95%, pure transformation ratio (conversion ratio) just finishes reaction.
With the solution cooling of gained, wash, dewater, concentrate, filtered, obtain to have the compound (a-2-1) of oxyethane radix 30 and dodecyl.
In addition, the oxyalkylene radix is to represent with the mol ratio (theoretical value) of alcohol with the oxyalkylene that uses in the oxyalkylene addition step.
The manufacturing (polymerization process) of＜static electricity resistance multipolymer (A-1) 〉
Agitating vane, reflux cooler are being provided, are reaching in the flask of gas introduction port; pack into 30 parts of aforementioned synthetic (a-2-1), 50 parts of methyl chloride acryl oxygen ethyl TMA (TriMethylAmine), 20 parts of methyl methacrylates, 1.5 parts of azobis isobutyronitriles, 233 parts of ethanol; under nitrogen gas stream, in 70 ℃ of reactions 8 hours.After reaction is finished, cooled off, obtain the ethanolic soln (solids component 30 weight %) of static electricity resistance multipolymer (A-1).
Synthesis example 2
In the oxyalkylene addition step of synthesis example 1, use 246.4 parts of octanols substituting lauryl alcohol, and the amount of change toluene is 393.0 parts.With 2500 parts of 666.7 parts in oxyethane (is 8 times of moles with respect to octanol) displaced loop oxidative ethanes, and after being pressed in 2 hours, then, 659.2 parts of propylene oxide (is 6 times of moles with respect to octanol) were pressed into through 2 hours again.Again, in esterif iotacation step, except the polyethylene polypropylene propylene oxide addition alcohol with this oxyalkylene addition step gained used 165.8 parts, other then carried out same operation with synthesis example 1, obtains to have the compound (a-2-2) of oxyethane radix 8, propylene oxide radix 6 and octyl group.Moreover, in polymerization process, changing to this compound (a-2-2) except making compound (a-2-1), other then carries out same operation with synthesis example 1, obtains the ethanolic soln (solids component 30 weight %) of static electricity resistance multipolymer (A-2).
Synthesis example 3
In the polymerization process of synthesis example 1, except the change methyl methacrylate was lauryl methacrylate(LMA), other then carried out identical operations with synthesis example 1, obtained the ethanolic soln (solids component 30 weight %) of static electricity resistance multipolymer (A-3).
Synthesis example 4
In the oxyalkylene addition step of synthesis example 1, except using 246.4 parts of octanols to substitute lauryl alcohol, and the amount of change oxyethane 833.3 parts (is 10 times of moles with respect to octanol), toluene is 269.9 parts, again, in esterif iotacation step, the amount of polyethylene oxide addition alcohol is made as beyond 113.9 parts, and other then carries out same operation with synthesis example 1, obtains to have the compound (a-2-3) of oxyethane radix 10 and octyl group.Moreover, in copolymerization process, except modification compound (a-2-1) is this compound (a-2-3), and the change methyl methacrylate is beyond the lauryl methacrylate(LMA), other then carries out same operation with synthesis example 1, obtains the ethanolic soln (solids component 30 weight %) of static electricity resistance multipolymer (A-4).
Synthesis example 5
In the copolymerization process of synthesis example 1, become the compound (a-2-3) of synthesis example 4 gained except modification compound (a-2-1), and the change methyl methacrylate is beyond the cyclohexyl methacrylate, other then carries out same operation with synthesis example 1, obtains the ethanolic soln (solids component 30 weight %) of static electricity resistance multipolymer (A-5).
Synthesis example 6
In the oxyalkylene addition step of synthesis example 1, except using 511.7 parts of stearyl alcohol (with respect to stearyl alcohol, use the oxyethane of 30 times of moles) to substitute lauryl alcohol and to make more 752.9 parts of the quantitative changes of toluene, again, in esterif iotacation step, except the amount that makes polyethylene oxide addition alcohol becomes 317.7 parts, other then carries out same operation with synthesis example 1, obtains to have the compound (a-2-4) of oxyethane radix 30 and octadecyl.Moreover, in polymerization process, except compound (a-2-1) is changed to this compound (a-2-4), and methyl methacrylate changed to beyond the cyclohexyl methacrylate, other then carries out and synthesis example 1 identical operations, obtains the ethanolic soln (solids component 30 weight %) of static electricity resistance multipolymer (A-6).
Synthesis example 7
In the polymerization process of synthesis example 1, change to the benzyl methacrylate except making methyl methacrylate, other then carries out same operation with synthesis example 1, obtains the ethanolic soln (solids component 30 weight %) of static electricity resistance multipolymer (A-7).
Synthesis example 8
In the polymerization process of synthesis example 1, except modification compound (a-2-1) is a compound (a-2-2) with synthesis example 2 gained, and the change methyl methacrylate is beyond the benzyl methacrylate, other then carries out same operation with synthesis example 1, obtains the ethanolic soln (solids component 30 weight %) of static electricity resistance multipolymer (A-8).
Embodiment 1
In new penta tetrol triacrylate hexamethylene diisocyanate amido formate prepolymer (chemistry limited-liability company of common prosperity company system: UA-306H) 50 weight parts, six vinylformic acid, two new Doutrates (the synthetic limited-liability company in East Asia system: AronicsM405) 40 weight parts, the new Doutrate of tetrapropylene acid (Japanese chemical drug limited-liability company system: KAYARADPET30) in 10 weight parts, add the ethanolic soln of 1 synthetic static electricity resistance of synthesis example multipolymer, so that the static electricity resistance multipolymer becomes 5 weight parts with solids component, moreover, the constituent that Irgacure184 (Ciba spy uses chemical system) 5 weight parts form as Photoepolymerizationinitiater initiater will be added, with methyl acetate, ethanol and 1-methoxyl group-2-propyl alcohol dilution, and modulation anti-electrostatic constituent, it contains the solvent 50 weight % that solvent composition is methyl acetate/ethanol/1-methoxyl group-2-propyl alcohol=80/15/5 (weight ratio).(an alcoholic acid part is to sneak into from the static electricity resistance copolymer solution in the solvent composition).
At the tri acetyl cellulose film (photo film limited-liability company of Fuji system) of the about 80 μ m of thickness or the polyethylene terephthalate film is easily then handled on the surface, and (limited-liability company's system is spun by Japan: CosmoshineA4100); use excellent coating machine to be coated with this constituent; with hot-air roaster remove desolvate after; high voltage mercury lamp radiation ultraviolet ray with output 80w/cm; make the coating layer sclerosis, obtain the hard coated film of anti-electrostatic of thickness 6 μ m.
With regard to the film with the hard coat of anti-electrostatic of gained, estimate with the evaluation method of next, the result is as shown in table 1.
(1) appearance of film: with the outward appearance of visual valuation antistatic backing.Metewand carries out in the following manner.
Zero: the generation of no condensation product, orange peel shape or albefaction.
*: can see generation, orange peel shape or the albefaction of condensation product.
(2) surface resistivity: under 25 ℃, relative humidity 40% atmosphere, place after 24 hours, use TOA corporate system surface resistivity meter (SM-8000 series SME-8310), under the condition of 25 ℃ of temperature, relative humidity 40%, apply impressed voltage 100V, measure 1 minute rear surface resistivity (Ω/).Metewand is to carry out as following mode.
◎: below 1.0E+10 Ω/
Zero: 1.0E+10 Ω/ is to being lower than 1.0E+11 Ω/
△: 1.0E+11 Ω/ is to being lower than 1.0E+12 Ω/
*: more than 1.0E+12 Ω/
(3) the full transmittance of mist value: measure mist value (Hz) and full transmittance (TT) with Japan electric look corporate system haze meter NDH2000.
(4) wear resistant (antiabrasion): 1 square centimeter the dihedral pad that the steel wool (steelwool) of #0000 will be installed is positioned on the test portion surface, load carry out under the 500g 10 times back and forth after, with the visual valuation outward appearance, measure the radical of damage.
(5) pencil hardness: estimate according to JIS K5400.
(6) adherence test: peel off method according to JIS K5400 chessboard eye, make cut channel 100 lattice of the chessboard eye shape at 1 millimeter interval with cutting knife at antistatic backing, sticking glass paper self-adhesive tape (Nichiban corporate system), after giving disposable peeling, counting does not have to be peeled off and the grid number of residual antistatic backing, and represents with n/100.Example) 100/100: do not have and peel off.0/100: all peel off.
(7) surface resistivity after the hot and humid degree long duration test: with the inner face of the hard coated film of adhesive tape joining anti-electrostatic (with antistatic backing be opposition side; that is tri acetyl cellulose pellicular front or polyethylene terephthalate pellicular front) in the test portion of sheet glass; after under 85 ℃, the environment of 85%RH, placing 100 hours, measure surface resistivity and give evaluation with these (2) same method.
(8) surface resistivity after the test of heatproof water-based: test portion that will be identical with aforementioned (7) flooded in 85 ℃ water after 20 minutes, to be same as the method for these (2), measured surface resistivity and evaluation.
Embodiment 2 to 12, comparative example 1 to 3
Except the static electricity resistance multipolymer that uses, shown in table 1 and table 2, make static electricity resistance multipolymer (A-1 to 8) ethanolic soln with synthesis example 1 to 8 gained, and setting solvent becomes shown in table 1 and the table 2 beyond the ratio, and other then obtains the anti-electrostatic constituent similarly to Example 1.Moreover carrying out same evaluation, its result is shown in table 1 and table 2.
Embodiment 13
The ethanolic soln of the static electricity resistance multipolymer (A-2) of synthesis example 2 gained is dropped in the hexane, leach precipitate after, by drying, obtain the solid of static electricity resistance multipolymer (A-2).In solid 5 weight parts of the static electricity resistance multipolymer (A-2) of gained, add ethanol 10 weight parts, ethyl acetate 85 weight parts, methylethylketone 5 weight parts, further add new penta tetrol triacrylate hexamethylene diisocyanate amido formate prepolymer (chemistry limited-liability company of common prosperity company system: UA-306H) 50 weight parts, six vinylformic acid, two new Doutrates (the synthetic limited-liability company in East Asia system: AronicsM405) 40 weight parts, the new Doutrate of tetrapropylene acid (Japanese chemical drug limited-liability company system: 10 weight parts KAYARAD PET30), as Irgacure 184 (Ciba spy uses chemical system) 5 weight parts of Photoepolymerizationinitiater initiater, and the modulation solvent composition is the anti-electrostatic constituent of the solids component 52 weight % of methyl acetate/ethanol/methylethylketone=85/10/5 (weight ratio).Moreover, carrying out evaluation similarly to Example 1, it the results are shown in table 1.
Table 1
Figure BDA0000048581830000181
Continuous table 1
Figure BDA0000048581830000191
Table 2
Figure BDA0000048581830000201
Table 1,2 common
EtOH: ethanol
PGM:1-methoxyl group-2-propyl alcohol
MeAc: methyl acetate
EtAc: ethyl acetate
N-PrAc: n-propyl acetate
BuAc: butylacetate
MEK: methylethylketone
1,3-DOX:1,3-dioxin-pentane
Writing a Chinese character in simplified form in the table 1,2 is as described below:
Solvent (D)
EtOH: ethanol
PGM:1-methoxyl group-2-propyl alcohol
MEK: methylethylketone
MeAc: methyl acetate
EtAc: ethyl acetate
N-PrAc: n-propyl acetate
1,3-DOX:1,3-dioxin-pentane
As shown in Table 1, at comparative example 1, because of solvent (D) only is a pure series solvent (d-1); so detrimentally affect of the reduction of the static electricity resistance after generation orange peel shape, the test of heatproof water-based etc.; moreover at the tri acetyl cellulose supporting carrier film, adherence also manifests low result.
At comparative example 2, because of solvent (D) is pure series solvent (d-1) and ketone series solvent, so in the tri acetyl cellulose supporting carrier film, wear resistant is low, the static electricity resistance behind the heatproof water test manifests the result of reduction.
Again, at comparative example 3, because of solvent (D) is the acetic ester series solvent of pure series solvent (d-1) and carbon number 6, so static electricity resistance manifests low result.
With respect to this, all are the acetic ester series solvents (d-2) that in solvent (D), use pure series solvent (d-1) and carbon number 3 to 5 at embodiment 1 to 12, can obtain the harmonious good film of transparent static electricity resistance hardness.By embodiment 4 to 6 as can be known, in solvent (D), with the acetic ester series solvent (d-2) of pure series solvent (d-1) and carbon number 3 to 5, can use ether, ketone, etc. solvent.Again, by embodiment 4 and 6 and embodiment 5 more as can be known, the acetic ester series solvent (d-2) of carbon number 3 to 5 is preferable more than 55 weight % in solvent (D).
Embodiment 14
In new penta tetrol triacrylate hexamethylene diisocyanate amido formate prepolymer (chemistry limited-liability company of common prosperity company system: UA-306H) 50 weight parts, six vinylformic acid, two new Doutrates (the synthetic limited-liability company in East Asia system: AronicsM405) 40 weight parts, new penta tetrol triacrylate (Japanese chemical drug limited-liability company system: KAYARADPET30) in 10 weight parts, add the ethanolic soln of 1 synthetic static electricity resistance of synthesis example multipolymer, so that the solids component of static electricity resistance multipolymer becomes 5 weight parts, further the constituent that Irgacure184 (Ciba is special with chemical limited-liability company system) 5 weight parts form as Photoepolymerizationinitiater initiater will be added, with two methylcarbonates, ethanol and 1-methoxyl group-2-propyl alcohol dilution, modulating solvent composition is that the two methylcarbonates/ethanol/1-methoxyl group-solvent of 2-propyl alcohol=80/15/5 (weight ratio) contains the anti-electrostatic constituent of 50 weight %.(an alcoholic acid part in the solvent composition is to sneak into from the static electricity resistance copolymer solution).
Easily then handle polyethylene terephthalate film (Toray limited-liability company system: LumirrorU48) at the tri acetyl cellulose film (film limited-liability company of Fuji system) of the about 80 μ m of thickness or the surface of the about 100 μ m of thickness; use excellent coating machine to be coated with this constituent; with hot-air roaster remove desolvate after; high voltage mercury lamp radiation ultraviolet ray with output 80w/cm; make the coating layer sclerosis, obtain the hard coated film of anti-electrostatic of thickness 6 μ m.
With regard to the film with the hard coat of anti-electrostatic of gained, estimate with the evaluation method of next, the result is as shown in table 3.Evaluation method is the explanation as embodiment 1.
Embodiment 15 to 25, comparative example 4 to 7
Except the static electricity resistance multipolymer that will use, shown in table 3 and table 4, make static electricity resistance multipolymer (A-1 to the 8) ethanolic soln with synthesis example 1 to 8 gained, and setting solvent consists of shown in table 3 and the table 4 beyond the ratio, other then obtains the anti-electrostatic constituent similarly to Example 1.Moreover carrying out same evaluation, its result is shown in table 3 and table 4.
Embodiment 26
The ethanolic soln of the static electricity resistance multipolymer (A-2) of synthesis example 2 gained is dropped in the hexane, leach precipitate after, by drying, obtain the solid of static electricity resistance multipolymer (A-2).In solid 5 weight parts of the static electricity resistance multipolymer (A-2) of gained, add ethanol 10 weight parts, ethyl acetate 85 weight parts, methylethylketone 5 weight parts, further add new penta tetrol triacrylate hexamethylene diisocyanate amido formate prepolymer (chemistry limited-liability company of common prosperity society system: UA-306H) 50 weight parts, six vinylformic acid, two new Doutrates (the synthetic limited-liability company in East Asia system: AronicsM405) 40 weight parts, new penta tetrol triacrylate (Japanese chemical drug limited-liability company system: 10 weight parts KAYARAD PET30), as Irgacure184 (Ciba spy uses chemical system) 5 weight parts of Photoepolymerizationinitiater initiater, modulating solvent composition is the anti-electrostatic constituent of the solids component 52 weight % of two methylcarbonates/ethanol/methylethylketone=85/10/5 (weight ratio).Moreover carrying out the evaluation identical with embodiment 1, its result is as shown in table 3.
Table 3
Figure BDA0000048581830000231
Continuous table 3
Figure BDA0000048581830000241
Table 4
Table 3,4 common
EtOH: ethanol
PGM:1-methoxyl group-2-propyl alcohol
DMC: methylcarbonate
DEC; Diethyl carbonate
MEC: Methyl ethyl carbonate
1,3-DOX:1,3-dioxin-pentane
1,4-DOX:1,4-dioxy land surround
THF: tetrahydrofuran (THF)
N-PrAc: n-propyl acetate
MEK: methylethylketone
Write a Chinese character in simplified form as described below in the table 3,4
Solvent (D)
EtOH: ethanol
PGM:1-methoxyl group-2-propyl alcohol
DMC: two methylcarbonates
MEC: Ue-5908
1,3-DOX:1,3-dioxin-pentane
1,4-DOX:1,4-dioxy land surround
THF: tetrahydrofuran (THF)
N-PrAc: n-propyl acetate
MEK: methylethylketone
By the result of table 3, table 4 as can be known, in comparative example 4, because of solvent (D) only is pure series solvent (d-1); so can produce the detrimentally affect of orange peel shape, the electrostatic reduction of heatproof water-based test rear defence etc.; moreover at the tri acetyl cellulose supporting carrier film, adherence also manifests low result.
In comparative example 5, because of solvent (D) is pure series solvent (d-1) and ketone series solvent, so in the tri acetyl cellulose supporting carrier film, wear resistant is low, the static electricity resistance behind the heatproof water test manifests the result of reduction.
Again, at comparative example 6,7, because of solvent (D) is the allotment amount of carbonates or ring-type ethers (d-3) and insufficient, so the static electricity resistance behind the heatproof water test manifests low result.
With respect to this, all be in solvent (D), to use pure series solvent (d-1) and carbonates or ring-type ethers (d-3) at embodiment 14 to 26 with suitable allotment ratio, can obtain the harmonious good film of transparent static electricity resistance hardness.
As embodiment 17 to 20 as can be known, at solvent (D), be with pure series solvent (d-1) and carbonates or ring-type ethers (d-3), can use the solvent of ketone or ester class etc.Again, by embodiment 18 and comparative example 6,7 more as can be known, the amount of carbonates or ring-type ethers (d-3) is preferably more than the 20 weight % in solvent (D).
The application is willing to that with the Japanese publication spy that the Japanese publication patent 2010-085013 that was applied on April 1st, 2010, the special 2010-119958 of hope of Japanese publication that on May 26th, 2010 was applied for, on November 5th, 2010 are applied for 2010-249073 is as the basis, and the opinion right of priority, its disclosure is all quoted at this.

Claims (5)

1. anti-electrostatic coating constituent, it contains: the anti-electrostatic coating constituent of static electricity resistance multipolymer (A), compound (B), Photoepolymerizationinitiater initiater (C) and solvent (D) with 3 above ethene unsaturated groups,
Described static electricity resistance multipolymer (A) be the compound (a-1) that will have the quarternary ammonium salt base shown in the following general formula (1), and following general formula (2) shown in have an oxyalkylene chain compound (a-2) as multipolymer that must constituent,
Described solvent (D) contain following any:
(i) the acetic ester series solvent (d-2) of pure series solvent (d-1) and carbon number 3 to 5;
(ii) pure series solvent (d-1) and be selected from carbonates or the solvent of ring-type ethers (d-3),
With respect to described compound (B) 100 weight parts, described static electricity resistance multipolymer (A) contains 1 to 20 weight part, described Photoepolymerizationinitiater initiater (C) contains 0.1 to 20 weight part,
Under the situation of described (i), in the total 100 weight % of described (A) to (D), contain solvent (D) 30 to 80 weight %, in 100 weight % of described solvent (D), the content of alcohol series solvent (d-1) is that the content of the acetic ester series solvent (d-2) of 5 to 25 weight %, carbon number 3 to 5 is 55 to 90 weight %
Under described situation (ii), in the total 100 weight % of described (A) to (D), contain solvent (D) 20 to 80 weight %, in 100 weight % of described solvent (D), the content of alcohol series solvent (d-1) is 5 to 30 weight %, and the content that is selected from the solvent (d-3) of carbonates or ring-type ethers is 20 to 95%:
General formula (1)
CH 2＝C(R 1)COZ(CH 2) kN +(R 2)(R 3)R 4·X -
In the formula, R 1Expression H or CH 3R 2To R 4Represent the alkyl of carbon number 1 to 9 independently of one another; Z represents Sauerstoffatom or NH base; K represents 1 to 10 integer; X -Represent 1 valency negatively charged ion;
General formula (2)
CH 2＝C(R 5)COO(AO) nR 6
In the formula, R 5Expression H or CH 3R 6The alkyl of expression hydrogen or carbon number 1 to 22; N represents that 2 to 200 integer, A represent the alkyl of stretching of carbon number 2 to 4.
2. anti-electrostatic coating constituent as claimed in claim 1, wherein, R in the described general formula (1) 2To R 4Be independent separately, the carbon number that does not have replacement is 1 to 9 alkyl, R in the general formula (2) 6It is the alkyl of hydrogen or the carbon number that does not have replacement 1 to 22.
3. anti-electrostatic coating constituent as claimed in claim 1 or 2, wherein, described pure series solvent (d-1) is selected from methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, hexalin, 2-methyl cellosolve, cellosolvo, 2-propoxy-ethanol, butoxy ethanol; In 1-methoxyl group-2-propyl alcohol, 3-methoxyl group-1-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, 2-oxyethyl group-1-propyl alcohol and the 3-oxyethyl group-1-propyl alcohol one or more.
4. anti-electrostatic coating constituent as claimed in claim 1 or 2, wherein, be selected from the solvent (d-3) of carbonates or ring-type ethers, be to be selected from methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, 1,3-dioxin-pentane, 1, one or more during 4-dioxy land surround, tetrahydrofuran (THF) and tetrahydrochysene piperazine are muttered.
5. an antistatic film is characterized by and will use as the antistatic backing of each described anti-static coating of claim 1 to 4 with constituent, and the one side at least that is formed at the tri acetyl cellulose transparent support forms.
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