CN101928436A - Process for producing silica dispersion, energy-ray curable resin compositions, and films - Google Patents
Process for producing silica dispersion, energy-ray curable resin compositions, and films Download PDFInfo
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- CN101928436A CN101928436A CN2010102117172A CN201010211717A CN101928436A CN 101928436 A CN101928436 A CN 101928436A CN 2010102117172 A CN2010102117172 A CN 2010102117172A CN 201010211717 A CN201010211717 A CN 201010211717A CN 101928436 A CN101928436 A CN 101928436A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
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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
- 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
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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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
- 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
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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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
- 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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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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Abstract
The invention provides a process for producing silica dispersion, energy-ray curable resin compositions, and films. The process comprises: supplying slurry from a slurry supply port to a stator of a wet ball mill consisting of a cylindrical stator, a slurry supply port, a rotating shaft, a rotor and an impeller type separator, wherein the slurry contains (methyl) acrylic polymer (B) with a molecular structure comprising (methyl) acrylamide of 200-600g/eq and hydroxy of 90-280mg KOH/g, and silica particles (F); rotating to drive the rotor in the stator to stir and mix the medium and slurry, leading silica particles (F) in the slurry to be crushed and dispersed in the (methyl) acrylic polymer (B), simultaneously separating the slurry and the medium through centrifugal function in the separator driven by rotation, and discharging the slurry attracted to the shaft center of the separator from a hollow discharge channel in the rotating shaft.
Description
Technical field
The manufacture method of the dispersion of the package stability excellence that the present invention relates to silicon dioxide microparticle is dispersed in the active energy ray-curable composition and form, contain the dispersion that obtains by this manufacture method energy ray curable resin composition, have the said composition of making and solidify the film of the cured layer that obtains, silicon dioxide microparticle with reactive media and the reactive dispersion agent of silicon dioxide microparticle of disperseing.
Background technology
In order to improve the hardness of the cured coating film that active energy ray-curable resin composition is solidified and obtain, have silicon dioxide microparticle is dispersed in method in the active energy ray-curable resin composition.The aerosil that silicon dioxide microparticle has the colloid silica made by wet method, makes by dry method.Silica particle surface has the silanol base, and silicon dioxide microparticle is hydrophilic.Therefore, poor with affinity as the organic phase of the principal constituent in the composition of active energy ray curable monomer, oligopolymer etc.In addition, the proportion of silicon dioxide microparticle is bigger than organic phase.Therefore; make silicon dioxide microparticle in active energy ray-curable resin composition, reach long-time stable dispersion normally the difficulty; if containing the active energy ray-curable resin composition of silicon dioxide microparticle places for a long time; aggegation and sedimentation etc. can take place in silicon dioxide microparticle, and package stability is poor.In addition, aggegation consumingly can take place because of acting on intermolecular forces between initiating particle and electrostatic force etc. in silicon dioxide microparticle usually, and this also produces detrimentally affect to package stability.
As making silicon dioxide microparticle stably be dispersed in method in the active energy ray-curable resin composition, for example recorded by silicon dioxide microparticle being carried out surface treatment with reactive silane coupling agent with hydrophobic group, with the method for silica particle surface hydrophobization (for example, referring to patent documentation 1), but, the dispersion stabilization of silicon dioxide microparticle in active energy ray-curable resin composition that obtains by the method for putting down in writing in the patent documentation 1 is still not enough, if at room temperature preserve a week, will produce the sediment of silicon dioxide microparticle.In addition, also need to heat up in a steamer the by product that uses after silane coupling agent carries out surface treatment, be used to give package stability and the solvent that carries out concentrates and miscellaneous manufacturing process such as solvent replacing, not good economically yet.
[prior art document]
Patent documentation 1: TOHKEMY 2006-348196 (the 12nd page)
Brief summary of the invention
Invent technical problem to be solved
Technical problem to be solved by this invention provide the dispersion of the package stability excellence that silicon dioxide microparticle is dispersed in the active energy ray-curable composition and forms manufacture method, contain the dispersion that obtains by this manufacture method and silicon dioxide microparticle and can keep the energy ray curable resin composition of stable dispersion state for a long time and have the film of the cured layer of this energy ray curable resin composition as hard coat.
The means of dealing with problems
In order to address the above problem; the inventor furthers investigate; found that; as silicon dioxide microparticle (F) is dispersed in the molecular structure having (methyl) acryl and hydroxyl and (methyl) acryl equivalent is 200～600g/eq; hydroxyl value is the dispersion manufacture method in 90～280mgKOH/g's (methyl) acrylic acid polymer (B); use has the wet-type ball mill of impeller type separator; medium and slurry are mixed in this wet-type ball mill inside; make the silicon dioxide microparticle (F) in the slurry pulverize and be dispersed in (methyl) acrylic acid polymer (B); simultaneously by centrifugal action slurry is separated with medium in the impeller type separator portion; thereby the dispersion of obtaining; in this way can be easily and make silica dispersion of package stability excellence etc. easily by making, thus the present invention finished.
Promptly; the present invention relates to the manufacture method of dispersion; this manufacture method is characterised in that; to contain in the molecular structure that to have (methyl) acryl and hydroxyl and (methyl) acryl equivalent be that 200～600g/eq, hydroxyl value are that the slurry of (methyl) acrylic acid polymer (B) of 90～280mgKOH/g and silicon dioxide microparticle (F) is provided in the stator from the described slurry supplying opening of the wet-type ball mill that comprises following structure
1) inside be filled with medium the round tube type stator,
2) be arranged at the said stator lower end the slurry supplying opening,
3) be positioned at the axle center of said stator, and its top be provided with the hollow form liquid discharge channel the turning axle that is rotated driving,
4) with above-mentioned turning axle carry out rotor that coaxial rotation drives and
5) be arranged at above-mentioned turning axle top with coaxial shape, and discharge the impeller type separator that is rotated driving that the parting liquid form constitutes to be communicated with above-mentioned hollow form liquid discharge channel,
Drive above-mentioned rotor at the stator internal rotation, medium and slurry are mixed, make the silicon dioxide microparticle (F) in the slurry pulverize and be dispersed in (methyl) acrylic acid polymer (B), simultaneously the separator portion that drives in rotation makes slurry separate with medium by centrifugal action, with the shape discharge-channel discharge of the slurry that attracted to position, the separator axle center hollow in the above-mentioned turning axle.
The invention still further relates to energy ray curable resin composition, it is characterized in that containing the dispersion that obtains by above-mentioned manufacture method.
The invention still further relates to a kind of film, it is characterized in that on membranaceous base material, having the cured layer that above-mentioned energy ray curable resin composition is solidified and obtain.
The invention still further relates to a kind of silicon dioxide microparticle and disperse media with reactivity; it is characterized in that, contain in the molecular structure that to have (methyl) acryl and hydroxyl and (methyl) acryl equivalent be that 200～600g/eq, hydroxyl value are (methyl) acrylic acid polymer (B) of 90～280mgKOH/g.
The invention still further relates to the reactive dispersion agent of a kind of silicon dioxide microparticle; it is characterized in that, contain in the molecular structure that to have (methyl) acryl and hydroxyl and (methyl) acryl equivalent be that 200～600g/eq, hydroxyl value are (methyl) acrylic acid polymer (B) of 90～280mgKOH/g.
The invention effect
According to the present invention, can be easily and make the silica dispersion of the package stability excellence that silicon dioxide microparticle is dispersed in the active energy ray-curable composition and forms easily.In addition, can also provide the energy ray curable resin composition that can make silicon dioxide microparticle keep stable dispersion state for a long time.In addition, the present invention can also provide the film with the high cured layer of hardness.In addition, the present invention can also provide the reactive dispersion agent that is applicable to the dispersed silicon dioxide particulate.
Brief Description Of Drawings
Fig. 1 is the sketch chart that possesses the feed slurry pulverization process loop of the above-mentioned wet-type ball mill that uses in the dispersion manufacture method of the present invention.
Fig. 2 is the longitudinal section of the above-mentioned wet-type ball mill that uses in the dispersion manufacture method of the present invention.
Fig. 3 is the longitudinal section of the above-mentioned wet-type ball mill that uses in the dispersion manufacture method of the present invention supplying opening when supplying with slurry.
The longitudinal section of supplying opening when Fig. 4 is the medium discharge.
Fig. 5 is the longitudinal section of another example of the above-mentioned wet-type ball mill that uses in the dispersion manufacture method of the present invention.
Fig. 6 has shown the cross-sectional view of the separator of the wet-type ball mill shown in Fig. 5.
The working of an invention mode
(methyl) acrylic acid polymer (B) that uses among the present invention is to be used as to be used for making silicon dioxide microparticle (F) dispersive reactive dispersion media or to be used to make silicon dioxide microparticle (F) to be dispersed in the material of (methyl) described later acrylic acid polymer (B) compound with (methyl) acryl in addition; it is characterized in that; have (methyl) acryl and hydroxyl in the molecular structure, and (methyl) acryl equivalent is that 200～600g/eq, hydroxyl value are 90～280mgKOH/g.Herein, (methyl) acryl equivalent is meant the solid substance weight (g/eq) of (methyl) acryloyl acid based polymer (B) of per 1 mole of (methyl) acryl (referring to acryl and/or methacryloyl).By (methyl) acryl equivalent is in 200～600g/eq scope, can realize high crosslink density, the result just can reach high rigidity.In addition, (methyl) of the present invention acrylic acid polymer (B) has hydroxyl, and the silanol base that exists on this hydroxyl and the silica particle surface forms hydrogen bond.By hydroxyl value is in the scope of 90～280mgKOH/g, can cover silica sphere thick and fast with (methyl) acrylic acid polymer (B), can realize polymolecularity.Can make thus the silicon dioxide microparticle that is scattered in (methyl) acrylic acid polymer (B) for a long time stable existence in active energy ray-curable resin composition.
(methyl) acryl equivalent that (methyl) of the present invention acrylic acid polymer (B) has is preferably 200～400g/eq.In addition, hydroxyl value is preferably 140～280mgKOH/g.By (methyl) acryl and hydroxyl value are in these scopes, the dispersion stabilization excellence of the dispersion that obtains, and use the cured coating film of the active energy ray-curable resin composition that this dispersion obtains to become high rigidity and film.
As above-mentioned (methyl) acrylic acid polymer (B), for example can enumerate the resultant of reaction (b1) that makes the monomer (c) with (methyl) acryl and carboxyl and (methyl) acrylic acid polymer (a1) carry out addition reaction and form with epoxy group(ing); the resultant of reaction (b2) that makes monomer (d) with (methyl) acryl and epoxy group(ing) and monomer (methyl) acrylic acid polymer (a2) carry out addition reaction and form with carboxyl; and make the monomer (e) with an isocyanate group and (methyl) acryl and (methyl) acrylic monomer (a3) carry out addition reaction and the resultant of reaction (b3) that forms etc. with hydroxyl.
As (methyl) acrylic acid polymer (a1) of use in preparation above-mentioned resultant of reaction (b1) with epoxy group(ing), the homopolymerization of polymerizable monomer that for example can be by having (methyl) acryl and epoxy group(ing) or obtain with the copolyreaction of other polymerizable monomer.
As above-mentioned polymerizable monomer with (methyl) acryl and epoxy group(ing); for example can enumerate (methyl) glycidyl acrylate; α-ethyl (methyl) glycidyl acrylate; α-n-propyl (methyl) glycidyl acrylate; α-normal-butyl (methyl) glycidyl acrylate; (methyl) vinylformic acid-3; 4-epoxy group(ing) butyl ester; (methyl) vinylformic acid-4; 5-epoxy group(ing) pentyl ester; (methyl) vinylformic acid-6; 7-epoxy group(ing) pentyl ester; α-ethyl (methyl) vinylformic acid-6; 7-epoxy group(ing) pentyl ester; Beta-methyl glycidyl (methyl) acrylate; (methyl) vinylformic acid-3; 4-epoxy group(ing) cyclohexyl; interior ester modified (methyl) vinylformic acid-3,4-epoxy group(ing) cyclohexyl; vinyl epoxy hexane etc.These monomers can use separately, also can use simultaneously more than 2 kinds.
(methyl) acrylic acid polymer (a1) can be the homopolymer with polymerizable monomer of (methyl) acryl and epoxy group(ing), also can be the multipolymer with other polymerizable monomer.When forming the multipolymer with other polymerizability unsaturated monomer; preferably by (polymerizable monomer with (methyl) acryl and epoxy group(ing)): (other polymerizable monomer) is 25～100 mass parts: the scope of 75～0 mass parts is used, and more preferably by 40～100 mass parts: the scope of 60～0 mass parts is used.
As (methyl) acrylic acid polymer (a2) of use in preparation above-mentioned resultant of reaction (b2) with carboxyl, the homopolymerization of polymerizable monomer that for example can be by having (methyl) acryl and carboxyl or obtain with the copolyreaction of other polymerizable monomer.
As polymerizable monomer, for example can enumerate (methyl) vinylformic acid with (methyl) acryl and carboxyl; β-carboxy ethyl (methyl) acrylate, 2-acryloxy ethyl succinate, 2-acryloxy ethyl phthalic ester, 2-acryloxy ethyl hexahydrophthalic acid ester and their lactone modifier etc. have the unsaturated monocarboxylic of ester bond; Toxilic acid etc.These monomers can use separately, also can use simultaneously more than 2 kinds.
(methyl) acrylic acid polymer (a2) can be the homopolymer with polymerizable monomer of (methyl) acryl and carboxyl, also can be the multipolymer with other polymerizable monomer.When forming the multipolymer with other polymerizability unsaturated monomer; preferably by (polymerizable monomer with (methyl) acryl and carboxyl): (other polymerizable monomer) is 25～100 mass parts: the scope of 75～0 mass parts is used, and more preferably by 40～100 mass parts: the scope of 60～0 mass parts is used.
As (methyl) acrylic acid polymer (a3) of use in preparation above-mentioned resultant of reaction (b3) with hydroxyl, the homopolymerization of polymerizable monomer that for example can be by having (methyl) acryl and hydroxyl or obtain with the copolyreaction of other polymerizable monomer.
As polymerizable monomer with (methyl) acryl and hydroxyl; for example can enumerate vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, vinylformic acid 4-hydroxyl butyl ester, vinylformic acid 2; 3-dihydroxyl propyl ester, 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, methacrylic acid 4-hydroxyl butyl ester, methacrylic acid 2,3-dihydroxyl propyl ester etc.These monomers can use separately, also can use simultaneously more than 2 kinds.
(methyl) acrylic acid polymer (a3) can be the homopolymer with polymerizable monomer of (methyl) acryl and hydroxyl, also can be the multipolymer with other polymerizable monomer.When forming the multipolymer with other polymerizability unsaturated monomer; preferably by (polymerizable monomer with (methyl) acryl and hydroxyl): (other polymerizable monomer) is 25～100 mass parts: the scope of 75～0 mass parts is used, and more preferably by 40～100 mass parts: the scope of 60～0 mass parts is used.
Above-mentioned other polymerizable monomer that carries out copolymerization when reaching (a3) as preparation (methyl) acrylic acid polymer (a1), (a2) for example can be enumerated following polymerizable monomer.
(1) (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid cetyl ester, (methyl) stearyl acrylate ester, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid docosyl ester etc. has (methyl) esters of acrylic acid that carbonatoms is 1～22 alkyl;
(2) (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid dicyclo pentyl ester, (methyl) vinylformic acid double cyclopentenyl 2-ethoxyethyl acetate etc. have (methyl) esters of acrylic acid of ester ring type alkyl;
(3) (methyl) vinylformic acid benzoyl 2-ethoxyethyl acetate, (methyl) benzyl acrylate, (methyl) phenylethyl, (methyl) phenoxyethyl acrylate, (methyl) vinylformic acid phenoxy group binaryglycol ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester etc. have (methyl) esters of acrylic acid of aromatic nucleus;
(4) (methyl) Hydroxyethyl acrylate; (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, (methyl) vinylformic acid glyceryl ester; (methyl) acrylate etc. that interior ester modified (methyl) Hydroxyethyl acrylate, (methyl) polyalkylene glycol acrylate ester, (methyl) vinylformic acid polypropylene glycol ester etc. have the polyalkylene glycol base has the esters of acrylic acid of hydroxyalkyl;
(5) unsaturated dicarboxylic acid ester classes such as dimethyl fumarate, DEF, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, fumaric acid methyl ethyl ester, fumaric acid first butyl ester, methylene-succinic acid methyl ethyl ester;
(6) styrene derivatives classes such as vinylbenzene, alpha-methyl styrene, chloro-styrene;
(7) diene compounds such as divinyl, isoprene, piperylene, dimethylbutadiene;
(8) halogen ethene and vinylidene halide class such as vinylchlorid, bromine ethene;
(9) unsaturated ketone such as methyl vinyl ketone, butyl vinyl ketone;
(10) vinyl ester such as vinyl acetate, vinyl butyrate;
(11) vinyl ethers such as methylvinylether, butyl vinyl ether;
(12) vinyl cyanide classes such as vinyl cyanide, methacrylonitrile, vinylidene dicyanide;
(13) acrylamide and alkyd substituted amide class thereof;
(14) N-substituted maleimide such as N-phenylmaleimide, N-cyclohexyl maleimide;
(15) the fluorine-containing alpha-olefines of vinyl fluoride, vinylidene, trifluoro-ethylene, chlorotrifluoroethylene, bromotrifluoethylene, five fluorine propylene or R 1216 and so on; Or the carbonatoms of (entirely) fluoroalkyl of trifluoromethyl trifluoro vinyl ether, pentafluoroethyl group trifluoro vinyl ether or seven fluoropropyl trifluoro vinyl ethers and so on is (entirely) fluoroalkyl perfluorovinyl sulfide ethers of 1 to 18; 2,2,2-trifluoroethyl (methyl) acrylate, 2,2,3,3-tetrafluoro propyl group (methyl) acrylate, 1H, 1H, 5H-octafluoro amyl group (methyl) acrylate, 1H, 1H, 2H, the carbonatoms of (entirely) fluoroalkyl of 2H-17 fluorine decyl (methyl) acrylate or perfluor ethyl oxygen ethyl (methyl) acrylate and so on are 1 to 18 fluorine-containing ethylene unsaturated monomer classes such as (entirely) fluoroalkyl (methyl) esters of acrylic acid;
(16) gamma-methyl allyl acyloxypropyl trimethoxysilane etc. contains (methyl) esters of acrylic acid of silyl;
(17) N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate or N, N such as N-diethylamino propyl group (methyl) acrylate, N-dialkyl aminoalkyl (methyl) acrylate etc.
Other polymerizability unsaturated monomer that these preparations (methyl) acrylic acid polymer (a1), (a2) carry out copolymerization when reaching (a3) can use separately, also can be with using more than 2 kinds.
Above-mentioned (methyl) acrylic acid polymer (a1), (a2) and (a3) use known customary way to carry out polymerization (copolymerization) can to obtain, its copolymerization mode is restriction especially.Can make by addition polymerization in the presence of catalyzer (polymerization starter), can be in random copolymers, segmented copolymer, the graft copolymer etc. any.In addition, polymerization process also can use mass polymerization, solution polymerization, suspension polymerization, the medium known polymerization process of letex polymerization.
Herein, as using solvent in solution polymerization etc., if enumerate representative solvents, for example can enumerate ketone series solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, methyl n hexyl ketone, diethyl ketone, ethyl normal-butyl ketone, di ketone, diisobutyl ketone, pimelinketone, sym.-diisopropylideneacetone;
Ether series solvents such as ether, isopropyl ether, n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, Diethylene Glycol, dioxane, tetrahydrofuran (THF);
Ethyl formate, propyl formate, n-buty formate, vinyl acetic monomer, n-propyl acetate, Iso Butyl Acetate, n-butyl acetate, n-Amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetic ester, diethylene glycol ether acetate alone, propylene glycol monomethyl ether acetate, ethyl-ester series solvents such as 3-ethoxy-c acid esters;
Methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, diacetone alcohol, 3-methoxyl group-1-propyl alcohol, 3-methoxyl group-1-butanols, 3-methyl-pure series solvents such as 3-methoxybutanol;
Hydrocarbon system solvents such as toluene, dimethylbenzene, SOLVESSO 100, SOLVESSO 150, SWAZOL 1800, SWAZOL310, Isopar E, Isopar G, Exxon Naphtha 5, Exxon Naphtha 6.These solvents can use separately, also can use simultaneously more than 2 kinds.
As (methyl) acrylic acid polymer (a1) or the solvent that (a2) uses during polymerization, because when carrying out under 100～150 ℃ the high temperature as being reflected at of the reaction of (methyl) acrylic acid polymer (a1) of the follow-up subordinate phase of these polymeric reaction and monomer (c), (methyl) acrylic acid polymer (a2) and monomer (d) is preferred on reaction efficiency, therefore preferred use boiling point is more than 100 ℃, preferably 100～150 ℃ solvent.The solvent that uses during as (methyl) acrylic acid polymer (a3) polymerization, because during as being reflected at 50～120 ℃ scope and carrying out of (methyl) acrylic acid polymer (a3) of the follow-up subordinate phase of this polymeric reaction and monomer (e) is preferred on reaction efficiency, therefore preferred use boiling point is more than 60 ℃, preferably 60～150 ℃ solvent.
In addition, as above-mentioned catalyzer, can use the known material that is used as radical polymerization initiator usually, for example can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two azo-compounds such as (4-methoxyl group-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide pivalate, t-butyl peroxy ethylhexoate, 1, organo-peroxide such as 1 '-two (tert-butyl peroxide) hexanaphthene, peroxidation tert-pentyl-2-ethylhexanoate, peroxidation uncle hexyl-2-ethylhexanoate and hydrogen peroxide etc.
When using superoxide, also superoxide can be used with reductive agent, form the oxidation-reduction type initiator as catalyzer.
Above-mentioned resultant of reaction (b1) makes aforesaid (methyl) acrylic acid polymer (a1) with epoxy group(ing) react with the monomer (c) with (methyl) acryl and carboxyl and obtains.As the monomer with (methyl) acryl and carboxyl (c), for example can enumerate (methyl) vinylformic acid; β-carboxy ethyl (methyl) acrylate, 2-acryloxy ethyl succinate, 2-acryloxy ethyl phthalic ester, 2-acryloxy ethyl hexahydrophthalic acid ester and their lactone modifier etc. have the unsaturated monocarboxylic of ester bond; Toxilic acid etc.
In addition, as monomer (c), after also can using acid anhydrides such as succinyl oxide and maleic anhydride and pentaerythritol triacrylate etc. to contain multifunctional (methyl) acrylate monomer reaction of hydroxyl, multifunctional (methyl) acrylate monomer that contains carboxyl of formation.Monomer (c) with (methyl) acryl and carboxyl can be distinguished use separately, also can use simultaneously more than 2 kinds.
The reaction of (methyl) acrylic acid polymer (a1) and above-mentioned monomer (c) is normally undertaken by two kinds of compositions being mixed, being heated to about 80～120 ℃.Usage quantity for (methyl) acrylic acid polymer (a1) and monomer (c); as long as (methyl) acryl equivalent of the resultant of reaction (b1) that obtains is in the scope of 200～600g/eq; have no particular limits; usually 1 mole of the epoxy group(ing) in preferred (methyl) acrylic acid polymer (a1) relatively is in 0.4～1.1 mole the scope mole number of the carboxyl in the monomer (c).
Above-mentioned resultant of reaction (b2) makes aforesaid (methyl) acrylic acid polymer (a2) with carboxyl react with the monomer (d) with (methyl) acryl and epoxy group(ing) and obtains.As the monomer with (methyl) acryl and epoxy group(ing) (d); for example can enumerate (methyl) glycidyl acrylate; α-ethyl (methyl) glycidyl acrylate; α-n-propyl (methyl) glycidyl acrylate; α-normal-butyl (methyl) glycidyl acrylate; (methyl) vinylformic acid-3; 4-epoxy group(ing) butyl ester; (methyl) vinylformic acid-4; 5-epoxy group(ing) pentyl ester; (methyl) vinylformic acid-6; 7-epoxy group(ing) pentyl ester; α-ethyl (methyl) vinylformic acid-6; 7-epoxy group(ing) pentyl ester; Beta-methyl glycidyl (methyl) acrylate; (methyl) vinylformic acid-3; 4-epoxy group(ing) cyclohexyl; interior ester modified (methyl) vinylformic acid-3,4-epoxy group(ing) cyclohexyl; vinyl epoxy hexane etc.These monomers can use separately, also can use simultaneously more than 2 kinds.
The reaction of (methyl) acrylic acid polymer (a2) and above-mentioned monomer (d) is normally undertaken by two kinds of compositions being mixed, being heated to about 80～120 ℃.Usage quantity for (methyl) acrylic acid polymer (a2) and monomer (d); as long as (methyl) acryl equivalent of the resultant of reaction (b2) that obtains is in the scope of 200～600g/eq; have no particular limits; usually 1 mole of the carboxyl in preferred (methyl) acrylic acid polymer (a2) relatively is in 0.4～1.1 mole the scope mole number of the epoxy group(ing) in the monomer (d).
Above-mentioned resultant of reaction (b3) makes aforesaid (methyl) acrylic acid polymer (a3) with hydroxyl react with the monomer (e) with an isocyanate group and (methyl) acryl and obtains.As monomer (e), for example can enumerate monomer, monomer, monomer, monomer, have the monomer an of isocyanate group and five (methyl) acryls etc. with an isocyanate group and four (methyl) acryls with an isocyanate group and three (methyl) acryls with an isocyanate group and two (methyl) acryls with an isocyanate group and (methyl) acryl with an isocyanate group and (methyl) acryl.As this monomer, the preferred compound of the following general formula of illustration 1 expression for example.
In the general formula (1), R
1Be hydrogen atom or methyl.R
2It for carbonatoms 2 to 4 alkylidene group.N represents 1～5 integer.These compounds can be enumerated, 2-(methyl) acryloxy ethyl isocyanate, 1 for example, 1-two (acryloyl-oxy ylmethyl) ethyl isocyanates etc. have Karenz AOI, Karenz MOI, Karenz BEI commodity such as (trade(brand)name, clear and electrician's (strain) systems) specifically.As other example, the reaction adducts of diisocyanate cpd and hydroxy acrylate etc. is arranged.,, can use known material herein with being not particularly limited, for example can enumerate tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. as diisocyanate cpd.As hydroxy acrylate; get final product so long as have the compound of hydroxyl and (methyl) acryl; not restriction especially; known material be can use, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, vinylformic acid 4-hydroxyl butyl ester, glycerine diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, Dipentaerythritol five acrylate etc. for example can be enumerated.Wherein, consider preferably have the material of (methyl) acryl more than two in the molecule as KarenzBEI from improving cross-linking density.These compounds can use separately, also can be with using more than 2 kinds.
(methyl) acrylic acid polymer (a3) and the method for monomer (e) reaction are not limited especially, can adopt known method.Specifically, for example can drip monomer (e) in (methyl) acrylic acid polymer (a3), be heated to 50～120 ℃, more preferably 60～90 ℃ are reacted and get final product.Also have; usage quantity for (methyl) acrylic acid polymer (a3) and monomer (e); as long as (methyl) acryl equivalent of the resultant of reaction (b3) that obtains is in the scope of 200～600g/eq; have no particular limits; usually 1 mole of the hydroxyl in preferred (methyl) acrylic acid polymer (a3) relatively is in 0.8～1.2 mole the scope mole number of the isocyanate group in the monomer (e).
The above-mentioned reaction that has (methyl) acrylic acid polymer (a1) of epoxy group(ing) and have the monomer (c) of (methyl) acryl and carboxyl, have (methyl) acrylic acid polymer (a2) of carboxyl and have the reaction of monomer (d) of (methyl) acryl and epoxy group(ing) and the reaction that has (methyl) acrylic acid polymer (a3) of hydroxyl and have a monomer (e) an of isocyanate group and (methyl) acryl also can be undertaken by for example following method.
Method 1:, in reaction system, add monomer (c) and react with (methyl) acryl and carboxyl by solution polymerization process polymerization (methyl) acrylic acid polymer (a1).
Method 2:, in reaction system, add monomer (d) and react with (methyl) acryl and epoxy group(ing) by solution polymerization process polymerization (methyl) acrylic acid polymer (a2).
Method 3:, in reaction system, add monomer (e) and react with an isocyanic ester and (methyl) acryl by solution polymerization process polymerization (methyl) acrylic acid polymer (a3).
In addition, (methyl) acrylic acid polymer (B) that uses among the present invention preferably the monomer that has a polymerizability unsaturated double-bond in each molecule is carried out polymerization and the structure that obtains as the polymkeric substance of main framing, but can when polymerization, not take place to use monomer simultaneously in the scope of gelation with two above polymerizability unsaturated double-bonds yet.
As (methyl) acrylic acid polymer (B) that uses among the present invention; be preferably the resultant of reaction (b1) that makes monomer (c) with (methyl) acryl and carboxyl and (methyl) acrylic acid polymer (a1) carry out addition reaction and form, wherein more preferably make (methyl) vinylformic acid and (methyl) acrylic acid polymer that obtains by the polymerizable monomer polymerization that contains (methyl) glycidyl acrylate carry out addition reaction and the resultant of reaction that forms with epoxy group(ing) with epoxy group(ing).
As above-mentioned epoxy equivalent (weight), be preferably 140～500g/eq, more preferably 140～300g/eq with (methyl) acrylic acid polymer (a1) of epoxy group(ing).In addition, the second-order transition temperature as (methyl) acrylic acid polymer (a1) with epoxy group(ing) is preferably more than 30 ℃, more preferably 30～100 ℃.
Need to prove that the epoxy equivalent (weight) among the present invention is the value by the JIS-K-7236 definition.
The mensuration of weight-average molecular weight and number-average molecular weight is to use gel permeation chromatography (GPC) among the present invention, measures by following condition.
Determinator: the system HLC-8220 of TOSOH Co., Ltd
Post: the system Guide Column H of TOSOH Co., Ltd
XL-H
The system TSKgel G5000HXL of+TOSOH Co., Ltd
The system TSKgel G4000HXL of+TOSOH Co., Ltd
The system TSKgel G3000HXL of+TOSOH Co., Ltd
The system TSKgel G2000HXL of+TOSOH Co., Ltd
Detector: RI (differential refractometer)
Data processing: the system SC-8010 of TOSOH Co., Ltd
Condition determination: 40 ℃ of column temperatures
Solvents tetrahydrofurane
Flow velocity 1.0ml/ minute
Standard specimen: polystyrene
Sample: the tetrahydrofuran solution that will be converted into the resin solid substance and be 0.4 weight % filters the sample (100 μ l) that obtains with micro-filter
Consider that from cure shrinkage effect and levelling property aspect the weight-average molecular weight of (methyl) acrylic acid polymer (B) that uses among the present invention is preferably 5,000～100,000, more preferably 5,000～50,000.
(methyl) acrylic acid polymer (B) that uses among the present invention has hydroxyl.The hydroxyl that (methyl) acrylic acid polymer (B) has also can react in the scope of not damaging effect of the present invention with the monomeric isocyanate group with an isocyanate group and (methyl) acryl.Thus, can suitably regulate (methyl) acryl equivalent and hydroxyl equivalent.
As above-mentioned monomer, for example can enumerate monomer, monomer, monomer, the monomer with an isocyanate group and (methyl) acryl, monomer with an isocyanate group and five (methyl) acryls with an isocyanate group and four (methyl) acryls with an isocyanate group and three (methyl) acryls with an isocyanate group and two (methyl) acryls with an isocyanate group and (methyl) acryl.As this monomer, the preferred compound of the following general formula of illustration 1 expression for example.
In the general formula (1), R
1Be hydrogen atom or methyl.R
2It for carbonatoms 2 to 4 alkylidene group.N represents 1～5 integer.These compounds can be enumerated, 2-(methyl) acryloxy ethyl isocyanate, 1 for example, 1-two (acryloyl-oxy ylmethyl) ethyl isocyanates etc. have Karenz AOI, Karenz MOI, Karenz BEI commodity such as (trade(brand)name, clear and electrician's (strain) systems) specifically.As other example, the reaction adducts of diisocyanate cpd and hydroxy acrylate etc. is arranged.,, can use known material herein with being not particularly limited, for example can enumerate tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. as diisocyanate cpd.As hydroxy acrylate; get final product so long as have the compound of hydroxyl and (methyl) acryl; not restriction especially; known material be can use, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, vinylformic acid 4-hydroxyl butyl ester, glycerine diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, Dipentaerythritol five acrylate etc. for example can be enumerated.Wherein, consider preferably have the material of (methyl) acryl more than two in the molecule as KarenzBEI from improving cross-linking density.
(methyl) acrylic acid polymer (B) that uses among the present invention and have the restriction especially of method of the monomer reaction an of isocyanate group and (methyl) acryl can adopt known method.Specifically, for example can drip the monomer with an isocyanate group and (methyl) acryl in (methyl) of the present invention acrylic acid polymer (B), be heated to 50～120 ℃, more preferably 60～90 ℃ are reacted and get final product.Also have; for (methyl) acrylic acid polymer (B) with have the monomeric usage quantity an of isocyanate group and (methyl) acryl; usually the hydroxyl (mole) of (methyl) acrylic acid polymer (B): the monomeric isocyanate group (mole) with an isocyanate group and (methyl) acryl is 1: 0.1～1: 0.9, is preferably 1: 0.1～1: 0.7.
In dispersion manufacture method of the present invention, the various silicon dioxide microparticles of suitable use.As silicon dioxide microparticle, can enumerate dry-process fine silica particle, wet silicon dioxide particulate etc.Dry type silicon-dioxide for example is the silicon dioxide microparticle by making silicon tetrachloride burn and obtain in oxygen or hydrogen flame.In addition, wet silicon dioxide is for example for in the mineral acid and the silicon dioxide microparticle that obtains of water glass.Manufacturing method according to the invention, under the situation of using any silicon dioxide microparticle, resulting dispersion all can keep good dispersion stabilization for a long time.In addition, this dispersion is added to when preparing active energy ray-curable resin composition in carbamate (methyl) acrylate, epoxy (methyl) acrylate isoreactivity energy ray-curable oligopolymer or the active energy ray curable monomer, and silicon dioxide microparticle also can keep stable dispersion for a long time in this active energy ray-curable resin composition.
As the silicon dioxide microparticle that uses among the present invention (F), preferred average initial particle is the particulate of 10nm～300nm, and more preferably average initial particle is the particulate of 10nm～200nm.
In the present invention, silicon dioxide microparticle (F) is dispersed in above-mentioned (methyl) acrylic acid polymer (B), thus the preparation dispersion.Not restriction especially of the content of each composition in the dispersion that obtains, but preferably according to making ((methyl) acrylate copolymer (B)): (silicon dioxide microparticle (F)) is 10～90 mass parts: 90～10 mass parts, more preferably 30～90 mass parts: 70～10 mass parts contain (methyl) acrylate copolymer (B) and silicon dioxide microparticle (F).In addition, it is 1～50 quality % that the total containing ratio that obtains (methyl) acrylate copolymer (B) in the dispersion and silicon dioxide microparticle (F) by the present invention preferably is scaled solid substance, more preferably 1～30 quality %.
The slurry that uses among the present invention contains (methyl) acrylate copolymer (B) and silicon dioxide microparticle (F), except that these compositions, can also contain (methyl) acrylate copolymer (B) compound with (methyl) acryl in addition.As (methyl) acrylate copolymer (B) compound in addition, for example can enumerate active energy ray curable monomer (M) and/or active energy ray curable oligopolymer (O) etc. with (methyl) acryl.The content of each composition has no particular limits, preferably according to making ((methyl) acrylate copolymer (B)): (active energy ray curable monomer (M) and/or active energy ray curable oligopolymer (O)) is 10～90 mass parts: 90～10 mass parts, more preferably 30～90 mass parts: 70～10 mass parts contain (methyl) acrylate copolymer (B) and active energy ray curable monomer (M) and/or active energy ray curable oligopolymer (O).
Here; use (methyl) acrylate copolymer (B) in addition have the compound of (methyl) acryl the time, (methyl) acrylate copolymer (B) can be used as and make silicon dioxide microparticle (F) be scattered in dispersion agent in this (methyl) acrylate copolymer (B) compound with (methyl) acryl in addition.
As above-mentioned active energy ray curable monomer (M), for example the polymerizable monomer that uses except raw material etc. as (methyl) acrylate copolymer (B), can enumerate ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, four propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, 1,3-butyleneglycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexamethylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, addition caprolactone on the hydroxy new pentane acid neopentyl glycol and two (methyl) acrylate of the compound that forms, NPGA neopentyl glycol adipate two (methyl) acrylate, TriMethylolPropane(TMP), two TriMethylolPropane(TMP)s, tetramethylolmethane, Dipentaerythritol, tetramethylol methane and hydroxy-containing compounds that the epoxy alkane of 1～20 mole of these compound addition is formed etc. have the compound of 3 above hydroxyls with the resulting compound of (methyl) acrylic molecules formation ester bond more than 3 etc.
As above-mentioned active energy ray curable oligopolymer (O), for example can enumerate more than one (methyl) acrylic compound that are selected from addition acryl (methyl) acrylate of acrylic acid polymer (B), carbamate (methyl) acrylate, polyester (methyl) acrylate, epoxy (methyl) acrylate etc.
As above-mentioned carbamate (methyl) acrylate, for example can enumerate (methyl) acrylic compound reaction that makes isocyanate compound and contain hydroxyl and polyfunctional carbamate (methyl) acrylate that forms.As the isocyanate compound that uses, for example can enumerate aliphatics or ester ring type diisocyanate cpds such as hexamethylene diisocyanate, isophorone diisocyanate, Xylene Diisocyanate, hydrogenated xylene diisocyanate, dicyclohexyl methane diisocyanate, norbornene alkyl diisocyanate herein; Tolylene diisocyanate, 4, aromatic diisocyanates such as 4 '-diphenylmethanediisocyanate; As the trimeric isocyanuric acid ester type of diisocyanate cpd isocyanate prepolymer etc.In addition, when making this carbamate (methyl) acrylate, also can replace and carry out polymerization with 2 yuan～4 yuan alcohol and/or polyol compound pair and the part of the compound of (methyl) acrylate of the hydroxyl of isocyanate compound reaction.
As above-mentioned polyester (methyl) acrylate, can enumerate to make and be selected from ethylene glycol, propylene glycol, Diethylene Glycol, neopentyl glycol, dihydroxyphenyl propane, Hydrogenated Bisphenol A, the ethoxylation dihydroxyphenyl propane, the ethoxylation Hydrogenated Bisphenol A, propoxylated bisphenol, more than one materials in the above polyvalent alcohol of propoxylation Hydrogenated Bisphenol A and binary and being selected from Tetra hydro Phthalic anhydride, isophthalic anhydride, terephthalic anhydride, hexanodioic acid, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, trimellitic acid 1,2-anhydride, pyromellitic acid acid anhydrides etc. are for more than one materials in the polyprotonic acid of representative carry out the ester polyol that esterification obtains containing hydroxyl, again this ester polyol are carried out (methyl) acroleic acid esterification and multifunctional ester (methyl) acrylate of forming etc.
As above-mentioned epoxy acrylate, for example can enumerate divalence epoxy (methyl) acrylic compound that makes (methyl) vinylformic acid carry out addition and obtain to the bicyclic oxygen compounds such as triglycidyl group etherate of dibasic alcohol such as propylene glycol, butyleneglycol, pentanediol, hexylene glycol, Diethylene Glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, TEG, polyoxyethylene glycol, polypropylene glycol, neopentyl glycol, hydroxy new pentane acid neopentyl glycol, dihydroxyphenyl propane, ethoxylation dihydroxyphenyl propane; Trivalent alcohols such as TriMethylolPropane(TMP), ethoxylated trimethylolpropane, propoxylation TriMethylolPropane(TMP), glycerine are carried out epoxidation and obtain epoxy compounds, make (methyl) acrylate and this epoxy compounds carry out addition again and average epoxy three (methyl) acrylic compound of free-radical polymerised unsaturated double-bond more than 3 of having of obtaining; Make glycidyl ether and have the polyphenol of at least one aromatic nucleus or its alkylene oxide adduct and react and form epoxy compounds, make (methyl) acrylate and this epoxy compounds carry out addition reaction again and multifunctional aromatic epoxies acrylate such as the phenol linear phenolic resin that obtains, cresols linear phenolic resin; Multifunctional ester ring type epoxy acrylate as the hydrogenated version of these multifunctional aromatic epoxies acrylate; After an isocyanic ester of secondary hydroxyl that exists in by molecule and diisocyanate cpd carried out urethane, (methyl) acrylate that makes the isocyanate group of residual single end and hydroxyl reacted and urethane-modified epoxy acrylate of obtaining etc.
In these compounds, have the average excelling in abrasion resistance of the cured coating film of polyester (methyl) acrylate of free-radical polymerised unsaturated double-bond and carbamate (methyl) acrylate more than 3, be particularly preferred therefore.
In the slurry of Shi Yonging, also can add organic solvent as required in the present invention.Contain organic solvent (S) in the preferred slurries.
As the organic solvent that uses among the present invention (S), for example can enumerate acetone, methyl ethyl ketone (MEK), ketones such as methyl iso-butyl ketone (MIBK), tetrahydrofuran (THF) (THF), ring-type ethers such as dioxolane, ritalin, vinyl acetic monomer, ester classes such as N-BUTYL ACETATE, toluene, the fragrant same clan such as dimethylbenzene, Trivalin SF, cellosolve, methyl alcohol, Virahol, butanols, alcohols such as propylene glycol monomethyl ether, these solvents can use individually or simultaneously, wherein, consider from the volatility and the solvent recuperation aspect in when coating, preferably as the methyl ethyl ketone of the synthetic of reactive dispersion agent.
Usage quantity as above-mentioned organic solvent, preferably total 100 mass parts with respect to (methyl) acrylic acid polymer (B) and silicon dioxide microparticle (F) are 150～500 mass parts, slurry separated with medium well when ball mill was operated when wherein being 200～300 mass parts, and the operation short period of time of slurry when concentrating can finish, be preferred therefore.
Preparation is during slurry, preferably adds organic solvent in above-mentioned (methyl) acrylic acid polymer (B) and after obtaining organic solvent solution, interpolation silicon dioxide microparticle (F).
Add various additives as required in the slurry that also can use in the present invention.
As the various additives that use among the present invention, for example can enumerate coupling agent.As coupling agent, for example can enumerate ethene base system silane coupling agent, epoxy and be silane coupling agent, polystyrene silane coupling agent, methacryloxy and be silane coupling agent, acryloyl-oxy base system silane coupling agent, amino and be silane coupling agent, uride and be silane coupling agent, chloropropyl and be silane coupling agent, sulfydryl and be silane coupling agent, sulfide-based silane coupling agent, isocyanate-based silane coupling agent, aluminium is silane coupling agent etc.
As ethene base system silane coupling agent, for example can enumerate vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy triethoxyl silane, to the styryl Trimethoxy silane, 3-methacryloxypropyl methyl dimethoxysilane, the 3-methyl allyl acyloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxyl silane, 3-acryloyl-oxy propyl trimethoxy silicane, N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-3-aminopropyltriethoxywerene werene, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-triethoxysilyl-N-(1,3-dimethyl butylidene) propyl group amine, N-phenyl-3-TSL 8330, the hydrochloride of N-(vinyl benzyl)-2-amino-ethyl-3-TSL 8330, special aminosilane, 3-uride propyl-triethoxysilicane, the 3-r-chloropropyl trimethoxyl silane, 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl trimethoxy silicane, two (triethoxysilylpropyltetrasulfide) tetrasulfide, 3-isocyanate group propyl-triethoxysilicane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilanis, diethoxymethylvinylschane, the trieline base silane, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane.
As epoxy is silane coupling agent, for example can enumerate diethoxy (glycidoxy propyl group) methyl-monosilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-triethoxysilicane etc.
As the polystyrene silane coupling agent, for example can enumerate styryl Trimethoxy silane etc.
As methacryloxy is silane coupling agent, for example can illustration 3-methacryloxypropyl methyl dimethoxysilane, 3-methyl allyl acyloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxyl silane.
As acryloyl-oxy base system silane coupling agent, for example can enumerate 3-acryloyl-oxy propyl trimethoxy silicane etc.
As amino is silane coupling agent, for example can enumerate N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-3-aminopropyltriethoxywerene werene, 3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propyl group amine, N-phenyl-3-TSL 8330 etc.
As uride is silane coupling agent, for example can enumerate 3-uride propyl-triethoxysilicane etc.
As chloropropyl is silane coupling agent, for example can illustration 3-r-chloropropyl trimethoxyl silane.
As sulfydryl is silane coupling agent, for example can enumerate 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl trimethoxy silicane etc.
As sulfide-based silane coupling agent, for example can enumerate two (triethoxysilylpropyltetrasulfide) tetrasulfide etc.
As the isocyanate-based silane coupling agent, for example can enumerate 3-isocyanate group propyl-triethoxysilicane etc.
As aluminium is coupling agent, for example can enumerate acetyl aluminum alkoxide diisopropyl alcoholization thing etc.
Dispersion manufacture method of the present invention is characterised in that, above-mentioned slurry is provided to from the slurry supplying opening comprise
1) inside be filled with medium the round tube type stator,
2) be arranged at the said stator lower end the slurry supplying opening,
3) be positioned at the axle center of said stator, and its top be provided with the hollow form liquid discharge channel the turning axle that is rotated driving,
4) with above-mentioned turning axle carry out rotor that coaxial rotation drives and
5) be arranged at above-mentioned turning axle top with coaxial shape, and discharge the impeller type separator that is rotated driving that the parting liquid form constitutes to be communicated with above-mentioned hollow form liquid discharge channel
The stator of wet-type ball mill in, drive above-mentioned rotor at the stator internal rotation, medium and slurry are mixed, make the silicon dioxide microparticle (F) in the slurry pulverize and be dispersed in (methyl) acrylic acid polymer (B), the separator portion that drives in rotation makes slurry separate with medium by centrifugal action simultaneously, and the slurry that attracted to position, separator axle center is discharged from the hollow bleed passage in the above-mentioned turning axle.
Below, utilize accompanying drawing that the manufacture method of the present invention of using aforesaid wet-type ball mill is elaborated.
Among Fig. 1, will be provided to the wet-type ball mill 3 from supplying opening 16 with the slurry of feedstock pump 2 extraction from the head tank 1 of storing slurry.About this wet-type ball mill, can enumerate the round tube type stator 7 among Fig. 2 particularly.Be filled with medium in this stator 7, the rotor 11 that drives by rotation mixes slurry and medium, make the silicon dioxide microparticle (F) in the slurry pulverize and be dispersed in (methyl) acrylic acid polymer (B), the impeller type separator 4 that utilizes rotation to drive makes slurry separate with medium by centrifugal action simultaneously.At this moment, heavy medium radially flies out outwardly, and is relative therewith, the slurry that proportion is little is absorbed into the axial portions of separator 4, by being arranged at the hollow form liquid discharge channel 9 on turning axle 5 tops, turn back in the jar 1 via pump 64, thereby the circulation of carrying out silicon dioxide microparticle is pulverized.In the process that circulation is pulverized, suitably measure the granularity of slurry, stop when reaching desired value.
In manufacture method of the present invention, by feedstock pump slurry is supplied with the circular flow of wet-type ball mill 3, the per 1 liter of inner capacities with respect to wet-type ball mill 3 is generally 30～100L/ hour, is preferably 50～80L/ hour.By circular flow is in this scope, the residence time of slurry in wet-type ball mill 3 reaches optimum condition, and dispersion efficiency increases.At this moment, the time of disperseing to be spent is preferably 5～60 minutes, more preferably 10～40 minutes usually.
Medium as filling in the stator 7 for example can use various small beads.As the raw material of small bead, for example can enumerate zirconium white, glass, titanium oxide, copper, zirconium silicate etc.
Particle diameter for medium, from separator 4 slurry and medium separate good, and in the rotor 11 pulverizing of silicon dioxide microparticle also good, disperse required time also be difficult for elongated, to the impact of silicon dioxide microparticle can be not strong excessively, be not easy to produce the consideration of dispersion phenomenon aspect because of silicon dioxide microparticle is damaged, preferably the median size in median particle diameter is 15～300 μ m, more preferably 15～50 μ m.
The above-mentioned dispersion phenomenon of crossing is meant that the silicon dioxide microparticle breakage causes new active surface to generate, and agglutinative phenomenon again occurs.If cross dispersion, then dispersion liquid becomes gelatin.
The filling ratio of medium is preferably 80～90 volume % of stator internal volume usually in the stator.By making filling ratio is 80～90 volume % of stator internal volume, and the needed power of goods slurry that obtains unit weight is minimum.That is, can pulverize most effectively.
Order when slurry is supplied with stator 7 is as follows.In the stator 7 of wet-type ball mill 3 after the filled media,, then drive feedstock pump 2 in valve- off 58,59 and 60 and open under the state of valve 61,62 and 64 at first drivingmotor 12.Rotate driving rotor 11 and separator 4 by the driving of the former electric motor 12, driving by latter's feedstock pump 2 is by the introducing port 27 of the feed slurry in the head tank 1 being sent into supplying opening 16 at every turn a certain amount ofly on the other hand, and the slit that forms between edge by valve seat 24 and the valve body 25 supplies in the wet-type ball mill thus.
Also have, the wet-type ball mill 3 shown in Fig. 1 possesses the conveying end 19 that is used for making the slurry discharge after dispersion is finished, but in the present invention, as this ball mill 3, also can use the ball mill that does not possess conveying end 19.
By disperseing as upper type, the slurry granularity reaches desired value, and the order when stopping disperseing is as follows.
At first, do not have the situation of conveying end 9, can enumerate following method: temporarily stop feedstock pump 2, then stop electric motor 12, thereby wet-type ball mill 3 is shut down, stop pulverizing for wet-type ball mill 3.Afterwards, behind the valve-off 61, open valve 59.Start once more by feedstock pump 2 then, the goods slurry in the head tank 1 is delivered to the goods jar 67 from relief outlet 66.On the other hand, in order to extract goods slurry residual in the stator out, valve-off 59 when stopping feedstock pump 2.Then, will be connected on the goods jar 67 via the pipeline conversion that valve 64 turns back to head tank 1.Fill the solvent as raw material in the head tank 1 that becomes sky, according to operating with the above-mentioned identical order of slurry of supplying with in stator 7, drivingmotor 12 once more, drive feedstock pump once more simultaneously, and goods slurry residual in the stator 7 is recovered in the goods jar.
Have the situation of conveying end 9 for wet-type ball mill 3, the order when stopping disperseing is as follows.
Temporarily stop feedstock pump 2, then stop electric motor 12, thereby wet-type ball mill 3 is shut down, stop pulverizing.Open valve 58 and 59 then, while valve- off 61,62 and 64, and start feedstock pump 2 and electric motor 12 once more, open valve 60 then.Thus, the goods slurry in the head tank 1 is extracted out by feedstock pump 2 and is transported to the goods jar 67 from relief outlet 66.On the other hand, the goods slurry in the wet-type ball mill 3 also relies on pressurized air or the N that supplies in the wet-type ball mill 3 by valve 60 and hollow form liquid discharge channel 9 simultaneously owing to the rotation of rotor 7 is stirred
2Gas and being extruded by screen cloth 18 is transported to the goods jar 67 from relief outlet 65 through conveying end 19.Press with upper type, the goods slurry that reaches in the wet-type ball mill 3 in the head tank 1 is recycled in the goods jar 67.
Also have, use when having the wet-type ball mill of conveying end 19, make rotor 7 rotations be when reclaiming goods because, can not occur being present in unevenly the lower floor position of wet-type ball mill 3 during mixing, thereby prevent the clogging of screen of screen cloth 18 because of the medium sedimentation.And, also can open valve 63 and import suitable pressurized air or N from conveying end 19 in order to eliminate clogging of screen
2Gas, thus screen cloth 18 is carried out counterflush.
Based on Fig. 1～Fig. 4 the device that uses in the manufacture method of the present invention is illustrated in greater detail.
As above-mentioned wet-type ball mill 3, shown in detailed among Fig. 2, be round shape longitudinally, have: the stator 7 that has been equipped with the chuck 6 of circulation water coolant, be arranged at the slurry supplying opening 16 of stator lower end, be positioned at the axle center of stator and the turning axle that is rotated driving 5 that its top is provided with the hollow form liquid discharge channel 9 that is communicated with head tank 1, carry out needle-like or the discous rotor 11 that coaxial rotation drives what above-mentioned turning axle end portion was provided with towards radially giving prominence to turning axle, be fixed in the belt pulley 13 of the electric motor 12 shown in the Fig. 1 on turning axle top and hang the belt pulley 14 of belt, be installed in the swivel joint 15 of the opening end of turning axle upper end, and be positioned near the separator that is used for separating medium 4 that is fixed in the stator internal upper part on the turning axle 5.In addition, when stator bottom had above-mentioned conveying end 19, this conveying end 19 was disposed at the eccentric position of stator bottom, specifically, was made of reticulation screen cloth support 17 and the screen cloth that is used for separating medium 18 that is installed on this screen cloth support 17.
Separator 4 is formed with the blade 22 that is connected two disks 21 with fixed pair of discs 21 by existing at regular intervals on turning axle 5, constitute impeller, carry out coaxial rotation with above-mentioned turning axle 5, make medium and the slurry that enters between the disk applied centrifugal force, utilize its proportion official post medium radially outwards to fly out, on the other hand, the above-mentioned hollow form liquid discharge channel 9 in the axle center of slurry by being arranged at turning axle 5 is discharged from.
Supplying opening 16 as feed slurry, as among Fig. 3 in detail shown in, by the valve seat 24 that is formed at the stator bottom, liftably be embedded in the reverse frustoconic valve body 25 of valve seat 24, from the stator bottom outstanding downwards and be formed with feed slurry introducing port 27 round-ended cylinder body 26 is arranged and outstanding downwards and possess pressurized air or N from this cylinder
2Conductance inlet 29 round-ended cylinder 28 arranged, liftably be entrenched in the piston 31 on the cylinder 28, the bar 32 that connects piston 31 and valve body 25, be installed on the piston in the cylinder 28 and when depressing piston 31 to valve body 25 spring 33 of downward reactive force usually, with protrude in cylinder 28 and be screwed into the end of bar and the composition of the nut 34 that install adjustably the position, if valve body 25 is pressed to owing to the supply of feed slurry, then and between the valve seat 24 form annular slot, feed slurry just is fed in the ball mill thus, but the width in above-mentioned slit can tightening by nut 34, loosen and adjust, even nut 34 comes to a dead end on cylinder 28 and forms maximum width when base feed thereby this width can be set at, medium still can not pass.Valve body 25 during base feed is pressed and resist the interior pressure of wet-type ball mill 3 and the effect of spring 33 is risen owing to the supply of sending into the feed slurry in the cylinder 26, and form the slit between the valve seat 24, but the wavelength width of a slit that forms because of base feed is pressed in the supply of feed slurry, be slightly less than the maximum wavelength width of a slit of nut 34 defineds, so rich amount is also arranged between the cylinder 28 of nut 34 slightly.
In the feed slurry that is fed into through the slit that forms between valve seat 24 and the valve body 25 in the ball mill, contain coarse particle, can expect it can sandwich between valve seat and the valve body and produce and stop up, in when, because of sandwiching obstruction having taken place, make valve body 25 rise to the limit by improving to supply with to press, it is maximum that wavelength width of a slit reaches.Therefore the coarse particle that sandwiches flows out, and stops up and eliminates.Eliminate if stop up, then supply with drops, valve body 25 falls.
In order to eliminate the obstruction at place, slit, in illustrated embodiment, utilize elliptical pressurized air or N in the diagram again
2Source of the gas feeds pressurized air or N in setter 23
2Gas, and supply to the cylinder 28 from introducing port 29 through electromagnetic switching valve 30, switch by in than short period, carrying out ON-OFF repeatedly, thereby supply with pressurized air or N discontinuously
2Gas, valve body 25 rises to the knee-action of upper limit position repeatedly in than short period thus, can eliminate the problem of sandwiching.
The vibration of this valve body 25 can be carried out always, or carries out when containing a large amount of coarse particle in feed slurry, in addition, presses when rising owing to stopping up the supply that makes feed slurry, also can link with it.
After pulverize stopping, the medium after stirring is taken out with the goods slurry, or when after extracting the goods slurry out, taking out, the installation site that reduces nut 34 as shown in the figure.Electromagnetic switching valve is switched to ON.Thus, pressurized air or the N that imports from introducing port 29
2Gas rises to more than the edge of valve seat 24 valve body 25.
In the above-described embodiment, rotor 11 and separator 4 all are fixed in the axle rotation 5, but are fixed in other embodiments on the different rotary axle of arranged coaxial, are rotated driving respectively.In rotor and separator are installed on above-mentioned embodiment on the same turning axle, drive unit has a cover to get final product, therefore simple in structure, relative therewith, be installed on the disalignment for rotor and separator, be rotated with different drive units in the embodiment of driving, can make rotor and separator be rotated driving by optimum revolution respectively.Fig. 5 is the longitudinal section of the wet type agitating ball mill in this embodiment, and Fig. 6 is the cross-sectional view of the separator of expression wet type agitating ball mill shown in Figure 5.
The turning axle 43 of ball mill shown in Figure 5 is made step shaft, embed separator 44 from the turning axle lower end, then alternately embed dividing plate 45 and discoid or needle-like rotor 46, use fixedly stopper 47 of screw 48 then in the turning axle lower end, step 43a and stopper 47 by axle 43 are clamped separator 44, dividing plate 45 and rotor 46, it is connected and fixed, separator 44 as shown in Figure 6, by the pair of discs 52 that has formed blade embedded groove 51 on the apparent surface of inboard respectively, the annular baffle 56 that makes two disks keep certain intervals and be formed with the hole 55 that is communicated with discharge-channel 54 is formed, and has constituted impeller.
Use wet-type ball mill in the dispersion manufacture method of the present invention.As wet-type ball mill, for example can enumerate the ball mill ス タ one ミ Le (trade(brand)name) that Ashizawa Finetech (strain) makes; MSC-MILL, SC-MILL, the Attritor MA01SC that make in Mitsui mine (strain); Shallow field ironworker's (strain) NANO GRAIN MILL, Pico Grain Mill, Pure Grain Mill, Mechagaper Grain Mill, Cerapower Grain Mill, Dual Grain Mill, AD Mill, Twin AD Mill, Basket Mill, Twin basket mill; Apex Mill, commodity such as Ultra Apex Mill, Super ApexMill that longevity industry (strain) is made.Wherein preferred Ultra Apex Mill.
In addition, the ball mill ト タ one ミ Le that also preferably uses Ashizawa Finetech (strain) to make in the manufacture method of the present invention.This ball mill ス タ one ミ Le is following medium stirring-type shredding unit, it possesses an end and has the slurry inlet cylindrical container, the stir shaft that rotates freely that in said vesse, disposes in vertical extension mode, with be in the outside drive unit that is connected with above-mentioned stir shaft of said vesse, above-mentioned stir shaft has mixing component, space between above-mentioned stir shaft and the said vesse internal surface has added crushing medium, importing slurry from above-mentioned slurry inlet on one side utilizes above-mentioned drive unit rotation to drive above-mentioned stir shaft on one side, thereby the silicon dioxide microparticle in this slurry is pulverized, above-mentioned stir shaft has formed the hollow space with medium import near the said vesse the other end, formed the slit that this hollow space is communicated with above-mentioned space between above-mentioned stir shaft and the said vesse internal surface on the above-mentioned stir shaft, along with near the medium the above-mentioned the other end of the mobile arrival said vesse of slurry enters into the above-mentioned hollow space of above-mentioned stir shaft from above-mentioned slurry inlet, carry out returning the above-mentioned spatial cyclic motion between above-mentioned stir shaft and the said vesse internal surface from above-mentioned slit.This medium stirring-type shredding unit is characterised in that the above-mentioned hollow space internal configuration of above-mentioned stir shaft has slurry outlet, is provided with screen cloth in above-mentioned hollow space inside according to the mode of surrounding above-mentioned slurry outlet, and rotation drives above-mentioned screen cloth.
In above-mentioned medium stirring-type shredding unit, be rotated owing to be used for being driven from the screen cloth that slurry is isolated medium, arrive also to have brought out near slurry of screen cloth and the medium and rotatablely move, this rotatablely moves, and what cause also is that medium side is higher than slurry side from power, so has just produced the isolating power of departing from from slurry in the medium.Therefore, medium is just kept off screen cloth ground and is circulated.Thereby can from slurry, remove medium effectively.
The dispersion that is obtained by manufacture method of the present invention can be by adding appropriate solvent, solvent evaporates being adjusted to be suitable for the concentration of coating process.As the solvent that adds, can enumerate above-mentioned organic solvent (S).
The dispersion itself that is obtained by manufacture method of the present invention can be used as the active energy ray-curable resin composition use, also can use with other compound as required.As these compounds, can enumerate above-mentioned active energy ray curable monomer (M), active energy ray curable oligopolymer (O), UV light absorber, silicon-type additive, organic bead, fluorine is additive, rheological control agent, defoamer, releasing agent, silane coupling agent, static inhibitor, antifogging agent, tinting material etc.
As above-mentioned UV light absorber, for example can enumerate 2-[4-{ (2-hydroxyl-3-dodecyl oxygen propyl group) oxygen }-the 2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-[4-{ (2-hydroxyl-3-tridecyl oxygen propyl group) oxygen }-the 2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, pyrrolotriazine derivatives such as 5-triazine, 2-(2 '-xanthene carboxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-adjacent nitro benzyloxy-5 '-aminomethyl phenyl) benzotriazole, 2-xanthene carboxyl-4-dodecyloxy benzophenone, the adjacent nitro benzyloxy of 2--4-dodecyloxy benzophenone etc.
As above-mentioned antioxidant, for example can enumerate hindered phenol is that antioxidant, hindered amine are that antioxidant, organosulfur are that antioxidant, phosphoric acid ester are antioxidant etc.
As aforementioned silicon-type additive, for example can enumerate the poly organo siloxane with alkyl and phenyl of dimethyl polysiloxane, methyl phenyl silicone, cyclic dimethyl polysiloxane, methylhydrogenpolysi,oxane, polyether-modified dimethyl polysiloxane copolymer, polyester modification dimethyl polysiloxane copolymer, fluorine modification dimethyl polysiloxane copolymer, amino modified dimethyl polysiloxane copolymer etc. and so on.
As above-mentioned organic bead, for example can enumerate polymethylmethacrylate bead, polycarbonate bead, polystyrene bead, polyacrylic acid styrene beads, silicone resin bead, glass beads, acrylic bead, benzoguanamine and be resin beads, trimeric cyanamide and be resin beads, polyolefin-based resins bead, polyester based resin bead, polyamide resin bead, polyimide is resin beads, polyfluoroethylene resin bead, polyvinyl resin bead etc.The median size of these organic beads is 1～10 micron, can use any separately, also can use simultaneously more than 2 kinds.
Usage quantity as aforesaid various additives, consider and give full play to its effect, and to be in the scope that does not hinder ultraviolet curing, preferably, be in respectively in the scope of 0.01～40 mass parts with respect to this injection molding polymerization active energy ray-curable resin composition 100 mass parts.
As the Photoepolymerizationinitiater initiater that can add in the dispersion of the present invention, for example can enumerate benzophenone, 3,3 '-dimethyl-4-methoxy benzophenone, 4,4 '-two dimethylamino benzophenone, 4,4 '-two diethylamino benzophenone, 4,4 '-dichloro benzophenone, michaelis ketone, 3,3 ', benzophenones such as 4,4 '-four (t-butyl peroxy carbonyl) benzophenone; Xanthone, thioxanthone, 2-methyl thioxanthone, 2-clopenthixal ketone, 2, xanthone, thioxanthene ketones such as 4-diethyl thioxanthone; Acyloin ethers such as bitter almond oil camphor, benzoin methyl ether, ethoxybenzoin, bitter almond oil camphor isopropyl ether; α such as benzil, di-acetyl-two ketone; Tetramethyl-thiuram disulfide, to thioether classes such as toluene disulfides; Benzoic acids such as 4-dimethylamino M-nitro benzoic acid, 4-dimethylamino ethyl benzoate; 3; 3 '-carbonyl-two (7-diethylamino) tonka bean camphor; the 1-hydroxycyclohexylphenylketone; 2; 2 '-dimethoxy-1; 2-diphenylethane-1-ketone; 2-methyl isophthalic acid-(4-(methylthio group) phenyl)-2-morpholinyl propane-1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; two (2; 4; the 6-trimethylbenzoyl) phenyl phosphine oxide; 1-(4-(2-hydroxyl-oxethyl) phenyl)-2-hydroxy-2-methyl-1-propane-1-ketone; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone; 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone; 4-benzoyl-4 '-methyl dimethoxy base thioether; 2; 2 '-diethoxy acetophenone; the benzil dimethyl ketal; benzil-'beta '-methoxy ethyl acetals; o-benzoyl base M-nitro benzoic acid methyl; two (4-dimethylaminophenyl) ketone; to the dimethylamino benzoylformaldoxime; α; α-Er Lv-4-Ben Yangjibenyitong; amyl group-4-dimethylaminobenzoic acid ester; 2-(Chloro-O-Phenyl)-4; 5-diphenyl-imidazole quinoline dipolymer; 2; two (ethoxy carbonyl methyl) amino of the two trichloromethyl-6-[of 4-] phenyl-S-triazine; 2; two trichloromethyl-6-(4-oxyethyl group) phenyl of 4--S-triazine; 2, two trichloromethyl-6-(the 3-bromo-4-oxyethyl group) phenyl-S-triazine anthraquinone of 4-; 2-tertiary butyl anthraquinone; the 2-amyl anthraquinone; β-chloroanthraquinone etc.
Above-mentioned Photoepolymerizationinitiater initiater can use separately or be used in combination more than 2 kinds.Its consumption is restriction especially not, but in order to keep good light sensitivity, prevent that crystallization from separating out, coating characteristic variation etc., be 0.05～20 mass parts preferably, wherein especially preferably use by the scope of 0.1～10 mass parts with respect to active energy ray-curable resin composition 100 mass parts.
As above-mentioned Photoepolymerizationinitiater initiater; be selected from the 1-hydroxycyclohexylphenylketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; 1-(4-(2-hydroxyl-oxethyl) phenyl)-2-hydroxy-2-methyl-1-propane-1-ketone; thioxanthone and thioxanthone derivates; 2; 2 '-dimethoxy-1; 2-diphenylethane-1-ketone; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; two (2; 4; the 6-trimethylbenzoyl) phenyl phosphine oxide; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone; a kind of in 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone or more than 2 kinds mixed system can obtain the high coating active energy ray-curable resin composition of solidified nature, be particularly preferred therefore.
As the commercially available product of above-mentioned Photoepolymerizationinitiater initiater, for example can enumerate Irgacure-184, Irgacure-149, Irgacure-261, Irgacure-369, Irgacure-500, Irgacure-651, Irgacure-754, Irgacure-784, Irgacure-819, Irgacure-907, Irgacure-1116, Irgacure-1664, Irgacure-1700, Irgacure-1800, Irgacure-1850, Irgacure-2959, Irgacure-4043, Darocur-1173 (Ciba Specialty Chemicals corporate system), Lucirin TPO (BASFF corporate system), KAYACURE-DETX, KAYACURE-MBP, KAYACURE-DMBI, KAYACURE-EPA, KAYACURE-OA (Japanese chemical drug (strain) system), VICURE-10, VICURE-55 (STAUFFER Co.LTD system), TRIGONALP1 (AKZOCo.LTD system), SANDORY 1000 (SANDOZ Co.LTD system), DEAP (APJOHN Co.LTD system), QUANTACURE-PDO, QUANTACURE-ITX, QUANTACURE-EPD (WARD BLEKINSOP Co.LTD system) etc.
In addition, for active energy ray-curable resin composition, can also in above-mentioned Photoepolymerizationinitiater initiater, use photosensitizers simultaneously.As photosensitizers, for example can enumerate amine, ureas, sulfocompound, P contained compound, chlorine-containing compound or nitrile or other nitrogenous compound etc.
In addition, in order to improve cementability,, can use other resin simultaneously for active energy ray-curable resin composition to film base material.
As above-mentioned other resin, for example can enumerate acrylic resins such as methyl-methacrylate resin, methyl methacrylate based copolymer; Polystyrene, methyl methacrylate-styrene based copolymer; Vibrin; Urethane resin; Polybutadiene such as polyhutadiene and butadiene-acrylonitrile based copolymer; Resins, epoxy such as bisphenol-type epoxy resin, phenoxy resin and novolac epoxy etc.
Use has following feature by the active energy ray-curable resin composition of the dispersion that manufacture method of the present invention obtains: also can obtain hardness when particularly being applied on the film like plastic basis material of film base material etc., and have low the contraction when solidifying, the warpage (curling) of film can not take place.In addition, therefore go for the coating of film base material.
As the glue spread in when coating on above-mentioned film base material, preferably on various film base materials, be 0.1～30g/m for example by weight after the drying
2Scope, be preferably 1～20g/m
2Scope be coated with.In addition, about the thickness of cured layer, be the hardness that film more than 3% reaches hard coat easily with respect to the thickness of membranaceous base material, be preferred therefore.Wherein, thickness about cured layer, more preferably be in film in 3～100% scopes with respect to the thickness of membranaceous base material, further the thickness of preferred consolidation layer is in 5～100% scopes with respect to the thickness of membranaceous base material, and the thickness of special preferred consolidation layer is in 5～50% scopes with respect to the thickness of membranaceous base material.
Membranaceous base material as the coating active energy ray-curable resin composition can use various known base materials.Specifically, can enumerate for example membranaceous base material of plastics etc.As the membranaceous base material of plastics, for example can enumerate film base materials such as polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefine, Resins, epoxy, melamine resin, cellulosetri-acetate resin, ABS resin, AS resin, norbornene resin, cyclic olefin, polyimide resin etc.
Coating process as active energy ray-curable resin composition, can use known method with being not particularly limited, for example can enumerate line rod coating method, the excellent coating method of silk with, airblade coating method with, intaglio plate coating method, counter-rotating intaglio plate coating method, adherography, flexographic printing method, silk screen print method etc.
As the active energy beam of irradiation, for example can enumerate ultraviolet ray or electron beam.When being cured with ultraviolet ray, use has xenon lamp, high pressure mercury vapour lamp, the metal halide lamp UV irradiation equipment as light source, regulate light quantity, light source configuration etc. as required, under the situation of using high pressure mercury vapour lamp, usually preferably with respect to a lamp of light quantity, be cured by 5～50m/ minute transfer rate with 80～160W/cm.On the other hand, preferred usually when being cured with electron beam booster machinery with 10～300kV acceleration voltage with electron beam, be cured by 5～50m/ minute transfer rate.
As mentioned above, shrinkability was little when above-mentioned active energy ray-curable resin composition solidified, and the hardness height.Therefore, by using said composition, can be provided in the cured layer that said composition is set on the film base material and the film that forms.It is the backing coat etc. of various protective membranes, antireflection film, scattering film and the plasma panel of representative that this film for example is suitable for optical article hard coating films such as polarization board protective film, touch pads.
In addition, above-mentioned active energy ray-curable resin composition not only is suitable for the protective membrane of plane article such as above-mentioned protection Polarizer, touch pad, also is applicable to the surface that for example is used for protecting moulding product such as tame electrical articles such as portable phone and bumper.
For using active energy ray-curable resin composition to form the method for the protective layer on protection moulding product surface, can enumerate finishing, transfer printing, sheet material bonding method etc.
Finishing is that the coating agent that will be made up of active energy ray-curable resin composition sprays, or with printing press such as curtain formula curtain coater, roller coating machine, intaglio plate coating machines after painting external coating (EC) on the moulding product, the irradiation active energy beam make the crosslinked method of external coating (EC).
Transfer printing is to be bonded in the molding surface having on the matrix sheet material of release property the formed transfer materials of coating active energy ray-curable resin composition, by peeling off the matrix sheet material external coating (EC) is transferred on the moulding product surface then, then shine active energy beam and make crosslinked filming, perhaps this transfer materials is bonded on the moulding product surface, shine active energy beam then and make crosslinked filming, then external coating (EC) is transferred to the lip-deep method of moulding product by peeling off the matrix sheet material.
The sheet material bonding method be will on the matrix sheet material, have the screening glass of protective layer and the decorative layer that uses in case of necessity be bonded on the plastic molded article, thereby in the method for moulding product surface formation protective layer.Wherein, coating of the present invention can be preferred for the purposes of transfer printing and sheet material bonding method with active energy ray-curable resin composition.Below the method for utilizing transfer printing, sheet material bonding method to form protective layer is elaborated.
For active energy ray-curable resin composition being formed protective layer, at first make transfer materials with transfer printing.Transfer materials can pass through, and is coated on the substrate sheets after for example active energy ray-curable resin composition being cooperated, mixes separately or with the polyfunctional isocyanate, makes curable resin composition carry out semicure (B-rankization) by heating and makes.
As the polyfunctional isocyanate who uses simultaneously with active energy ray-curable resin composition, restriction especially can not used known various polyfunctional isocyanate.For example can use isophorone diisocyanate, Xylene Diisocyanate, hydrogenated xylene diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, 1, the trimer of 6-hexane diisocyanate, above-mentioned substance, polyvalent alcohol and the formed prepolymer of above-mentioned di-isocyanate reaction etc.That is, hydroxyl contained in the polymkeric substance and polyfunctional isocyanate's isocyanate group is reacted and carry out the B-rankization.
Usage ratio for active energy ray-curable resin composition and polyfunctional isocyanate, the ratio of the hydroxyl of usually preferred active energy ray-curable resin composition and polyfunctional isocyanate's isocyanate group is 1/0.01～1/1, is preferably 1/0.05～1/0.8.
As substrate sheets, preferably has the sheet material of demoulding.As this substrate sheets, for example can enumerate the mixture of plastic sheet, tinsel, cellulose tablet, these sheet materials etc.
As above-mentioned plastic sheet, for example can enumerate above-mentioned plastic-like film etc.
As tinsel, for example can enumerate aluminium foil, Copper Foil etc.In addition, as above-mentioned cellulose tablet, for example can enumerate glassine paper, White Board, cellulose film etc.
As substrate sheets, preferred plastic sheet, wherein more preferably polyester chips.
In order to make transfer materials, at first on substrate sheets, be coated with active energy ray-curable resin composition.This resin combination forms the outermost layer on moulding product surface in protective layer formation method described later, be that the patterned layer on protection moulding product and the moulding product is avoided reagent and the layer of the infringement that rubs.As the method for coating transfer materials, for example can enumerate coating methods such as intaglio plate coating method, rolling method, spraying method, dip coating (lip coating), curtain formula curtain coating, print processes such as woodburytype, silk screen print method etc. with curable resin composition.During coating, considering from forming advantages of good abrasion and reagent resistance, is that the mode of 0.5～30 μ m is coated with according to making protective layer thickness preferably, is that the mode of 1～6 μ m is coated with according to making protective layer thickness more preferably wherein.
Above-mentioned protective layer is to the separability of matrix sheet material when good; protective layer directly is set on the matrix sheet material and is coated with transfer printing and get final product with curable resin composition; but in order to improve the separability of protective layer to the matrix sheet material; also can before on the matrix sheet material protective layer being set, form release layer comprehensively.As release layer, in the protective layer formation method of moulding product described later,, the protective layer with transfer materials when the moulding product are peeled off the matrix sheet material, removes from protective layer with the matrix sheet material for being transferred to moulding product surfaces.As the remover that is used to form release layer, for example can use melamine resin is that releasing agent, silicone resin are that releasing agent, fluoro-resin are that releasing agent, cellulose-derived system releasing agent, urea resin are releasing agent, polyolefin releasing agent, paraffin series releasing agent, their compound releasing agent etc.As the method that forms release layer, can enumerate coating methods such as intaglio plate coating method, rolling method, spraying method, dip coating (lip coating), curtain formula curtain coating, print processes such as woodburytype, silk screen print method.
After coating transfer printing on the substrate sheets is with curable resin composition, make its drying.Drying can be undertaken by for example heating.By this heating, when coating contained organic solvent with active energy ray-curable resin composition, organic solvent was removed.Heating temperature is generally 55～160 ℃, is preferably 100～140 ℃.Be generally 30 seconds heat-up time～30 minutes, be preferably 1～10 minute, more preferably 1～5 minute.
For the B-rank resin layer on the transfer materials of the present invention,, be preferably in the state that the stage before the irradiation active energy beam cannot not be in stickingly from can be easily brushing other layer and batch transfer materials and consider at this resin layer.
Also can form patterned layer on the transfer materials.Patterned layer is on the resin layer of B-rank, forms as printed layers usually.Material as printed layers, can use with polyethylene-based resin, polyamide-based resin, polyester based resin, polyacrylic resin, polyurethane series resin, polyvinyl acetal be resin, polyester urethane be resin, cellulose ester be resins such as resin, Synolac as binding agent, contain the pigment of appropriate color or dyestuff coloring printing ink as tinting material.As the method that forms patterned layer, for example can use print processes commonly used such as adherography, woodburytype, silk screen print method etc.Particularly manifest suitable adherography and the woodburytype of using in order to carry out polychrome printing and tone.In addition, under monochromatic situation, also can adopt coating methods such as intaglio plate coating method, rolling method, comma coating method, dip coating.For patterned layer,, the situation and the local situation about being provided with of comprehensive setting arranged according to the pattern of wanting to manifest.In addition, patterned layer can be formed or is combined to form by printed layers and metal evaporation layer by the metal evaporation layer.
In addition, when protective layer and patterned layer have enough cementabilities to the moulding product, adhesive linkage can be set, also can form adhesive linkage as required.Adhesive linkage is a bonding layer with transfer materials of above-mentioned each layer on moulding product surface.Adhesive linkage is formed at wants to carry out bonding part on protective layer or the patterned layer.That is, be full surface if want bonding part, then form adhesive linkage all sidedly.If it is partial wanting bonding part, then form adhesive linkage partly.As adhesive linkage, suitable use is suitable for the thermo-sensitivity or the pressure-sensitive resin of moulding product material.For example, when the material of moulding product is the polyacrylic resin, can use the polyacrylic resin.In addition, when the material of moulding product is polyphenylene oxide polystyrene resin, polycarbonate-based resin, styrene copolymerized system resin, polystyrene blending resin, use the polyacrylic resin good, polystyrene resin, polyamide-based resin etc. to get final product with these resin affinities.In addition, when the material of moulding product is acrylic resin, can use chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, thermoprene, ancient Malong indene resin.As the formation method of adhesive linkage, can enumerate coating methods such as intaglio plate coating method, rolling method, comma coating method, print processes such as woodburytype, silk screen print method.
Also have; the formation of transfer materials is not limited only to above-mentioned form; for example using just to the own form that presents moulding product and the transparency, carrying out under the situation of transfer materials of surface protection processing; can on the matrix sheet material, the order according to B-rank resin layer and adhesive linkage form these layers, from transfer materials, omit patterned layer.
In addition, when transfer materials has patterned layer and adhesive linkage on the resin layer of B-rank, also can between these layers, back-up coat be set.Back-up coat is the binding property that is used to improve these interlayers; protection moulding product and patterned layer are avoided the resin layer of chemical reagent infringement, and for example can use liquid two-pack solidified nature urethane resin, trimeric cyanamide is that resin, epoxy are thermoplastic resins such as thermosetting resin, vinyl chloride copolymer resin such as resin.Formation method as forming back-up coat has coating methods such as intaglio plate coating method, rolling method, comma coating method, print processes such as woodburytype and silk screen print method.
In order to use above-mentioned transfer materials to form the protective layer of moulding product, for example, will as the B rank resin layer of above-mentioned transfer materials and moulding product carry out bonding after, shine active energy beam resin layer curing got final product.Specifically, can enumerate, for example will be bonded in moulding product surface as the B-rank resin layer of transfer materials, to be transferred to as the B-rank resin layer of transfer materials on the moulding product surface by the base sheet material of peeling off transfer materials then, making it to carry out energy-ray by the active energy beam irradiation afterwards solidifies, thereby carry out the method (transfer printing) of the crosslinking curing of resin layer, and with in the above-mentioned transfer materials insertion forming mould, injection is full of resin in die cavity, bonding in its surface transfer materials when obtaining synthetic resin, thereby peeling off the matrix sheet material is transferred on the moulding product, carry out energy-ray by the irradiation active energy beam then and solidify, thereby carry out the method (transfer printing of moulding simultaneously) etc. of the crosslinking curing of resin layer.
Also have; crosslinking curing and transfer printing process for resin layer; preferably transfer materials is bonded on the moulding product surface shown in as stated above; be transferred to moulding product surface by peeling off the matrix sheet material then; carry out the operation of the order of active energy beam irradiation afterwards, but also can be after transfer materials is bonded to moulding product surface, from matrix sheet material one side irradiation active energy beam; protective layer is solidified, then peel off the matrix sheet material and carry out the operation of the order of transfer printing.
As above-mentioned moulding product, material is restriction not, for example can enumerate synthetic resin, carpenter work, their composite product etc.These moulding product can be any in transparent, translucent, opaque.In addition, the moulding product can be painted, also can be uncoloured.As resin, can enumerate versatility resins such as polystyrene resin, polyolefin-based resins, ABS resin, AS resin.In addition, also can use polyphenylene oxide polystyrene resin, polycarbonate-based resin, polyacetal is general engineering resins such as resin, acrylic resin, polycarbonate modified polyphenylene oxide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyvinyl resin with super-high molecular weight, and polysulfone resin, polyphenylene sulfide are that resin, polyphenylene oxide are that resin, polyacrylate resin, polyetherimide resin, polyimide resin, liquid-crystal polyester resin, poly-aryl are super engineering resins such as heat stable resin.In addition, can also use the compound resin of strongtheners such as having added glass fibre and mineral filler.
The active energy beam that uses in the formation method as the protective layer of moulding product of the present invention for example can be enumerated electron beam, ultraviolet ray, gamma-rays etc.Illuminate condition can be determined with the composition of curable resin composition according to the transfer materials that uses for the layer that is protected, and is 50～5000mj/cm according to making the accumulation light quantity preferably usually
2Shining, is 50～2000mj/cm according to making the accumulation light quantity more preferably
2Shine.
Below the method that forms the protective layer of moulding product by above-mentioned transfer printing is specifically described.At first, on the moulding product with the adhesive linkage side under mode dispose transfer materials.Then, use to possess anti-rubber-like elastic body, transfer machines such as the roll-type transfer machine of organo-silicone rubber, reversible transfer machine for example are by being set at 80～260 ℃ of temperature, pressure 50～200kg/m
2The heat resistant rubber shape elastomerics of condition, apply heat and/or pressure from matrix sheet material one side of transfer materials.Just adhesive linkage is bonded in moulding product surface in this way.Then, if after cooling, peel off the matrix sheet material, then peel off on the interface of matrix sheet material and resin layer.In addition, when on the matrix sheet material release layer being set,, then peel off on the interface of release layer and resin layer if peel off the matrix sheet material.At last,, make the complete crosslinking curing of the resin layer that is transferred on the moulding product, formed protective layer by the irradiation active energy beam.Also have, the operation of irradiation active energy beam also can be carried out before peeling off matrix sheet material operation.
Below, to being specifically described by the method for using injection molding while moulding transfer printing to form moulding product protective layer.At first, in the mold for forming of forming by movable mold and fixed mould, use adhesive linkage, put into transfer materials according to the mode that makes matrix sheet material contact fixed mould in a word as the inboard.At this moment, also can put into the transfer materials sheet one by one, also can intermittently put into the essential part of overlength transfer materials.When using the overlength transfer materials, use to have the e Foerderanlage that mechanism is determined in the position, make the orientation of the patterned layer of transfer materials and mold for forming reach consistent and get final product.In addition, when intermittently putting into transfer materials, by sensor detecting behind the position of transfer materials, if with movable mold and fixed mould stationary transfer material, usually transfer materials can be fixed on identical position, the position of patterned layer can not departed from, and is easily therefore.After closing mold for forming, to mould, inject the filling molten resin, when forming the moulding product, transfer materials is bonded on its surface from the cast gate that movable mold is provided with.After the synthetic resin cooling, open mold for forming and take out synthetic resin.At last, peel off the matrix sheet material after, make the complete crosslinking curing of resin layer by the irradiation active energy beam, thereby form protective layer.In addition, also can behind the irradiation active energy beam, peel off the matrix sheet material.
Also have, transfer materials of the present invention not only can form transfer materials manufacturing composition with curable resin composition, can also pass through coating methods such as above-mentioned intaglio plate coating method, rolling method, comma coating method, print processes such as woodburytype and silk screen print method, spraying method etc. are coated with on the moulding product such as being contained in film, sheet material, forming composition.
Below the sheet material bonding method is described.As the sheet material bonding method; for example can enumerate and form with the matrix sheet material and the moulding product of sheet material ready-made protective layer bonding; make it thermofixation by heating then; thereby carry out the method (back bonding method) of the crosslinking curing of B-rank resin layer; and above-mentioned protective layer formed with sheet material insert in the forming mould; injection is full of resin in die cavity; its surface is formed with protective layer carries out bonding with sheet material; make it thermofixation by heating then, thereby carry out the method (simultaneously moulding bonding method) etc. of the crosslinking curing of resin layer.
Above-mentioned protective layer form can be by for example making above-mentioned transfer materials with sheet material method etc. make.At this moment, on the matrix sheet material during application curable resin composition, under the insufficient situation of the bonding force of matrix sheet material and curable resin composition, also can 1, on the face of the application curable resin composition of matrix sheet material primer coating, and be coated with curable resin composition thereon, 2, the cementability of matrix sheet material and curable resin composition is provided by the methods such as surface of activation matrix sheet materials such as corona discharge.As priming paint above-mentioned 1, middle use, for example can use liquid two-pack solidified nature urethane resin, trimeric cyanamide is that resin, epoxy are thermosetting resins such as resin, vinyl chloride copolymer resin, the thermoplastic resins of being made up of acrylic resin such as water based emulsion.As the sticky cloth method of caking agent, for example can enumerate coating methods such as intaglio plate coating method, rolling method, comma coating method, print processes such as woodburytype, silk screen print method.
In the method for above-mentioned manufacturing transfer materials, with active energy ray-curable resin composition be coated be contained on the base sheet material after, the irradiation active energy beam.Utilize this active energy beam to make (methyl) acryl in the curable resin composition carry out bonding, form three-dimensional cross-linkedly, curable resin composition is solidified by Raolical polymerizable.
As actinic energy ray curable resion composition, use when containing the active energy ray-curable resin composition of organic solvent, also can after being applied on the matrix sheet material, remove organic solvent.Removing of organic solvent for example can be carried out behind the irradiation active energy beam, also can carry out before the irradiation active energy ray curable.As the method for removing, can directly place and wait for volatilization, also can use drying machine etc. to carry out drying, but the temperature when preferably removing organic solvent usually is 70～130 ℃, carries out about 10 seconds～10 minutes.
Also have; the formation that protective layer forms with sheet material is not limited to above-mentioned form; for example application target be to present the moulding product the form own and the transparency, carry out protective layer that surface protection handles and form when using sheet material; can on the matrix sheet material, form solidified resin layer and adhesive linkage successively, omit and form the patterned layer of forming with sheet material by protective layer.
In addition; when having resin layer on the patterned layer of protective layer formation with sheet material; also can back-up coat be set at these interlayers; back-up coat is the fusible resin layer that is used to improve these interlayers, and for example can use liquid two-pack solidified nature urethane resin, trimeric cyanamide is that resin, epoxy are thermoplastic resins such as thermosetting resin, vinyl chloride copolymer resin such as resin.Formation method as forming back-up coat has coating methods such as intaglio plate coating method, rolling method, comma coating method, print processes such as woodburytype and silk screen print method.
As the moulding product that use in the sheet material bonding method, for example can use illustrative moulding product in above-mentioned transfer printing.
Form the method for using sheet material as bonding forming product and protective layer in the bonding method of back, for example can be set forth in protective layer and form matrix sheet material and/or the surperficial coating adhesive of going up of moulding product of using sheet material, protective layer be formed with the matrix sheet material and the moulding product surface of sheet material carry out bonding method; On protective layer forms with two faces on the matrix sheet material of sheet material and/or moulding product surface behind the stickup self adhesive tape, peel off the demoulding screening glass of two self adhesive tapes on the face, expose adhesive face, protective layer is formed with the matrix sheet material and the moulding product surface of sheet material carry out bonding method; After protective layer forms with coating adhesive formation bonding plane on the matrix sheet material of sheet material; making in advance with peeling off screening glass has protected the protective layer of bonding plane to form sheet material; peel off the screening glass of peeling off that this protective layer forms sheet material, bonding method etc. is carried out on the bonding plane and the moulding product surface of matrix sheet material.At the same time in the moulding bonding method, the heat when not using caking agent in-molded makes the fusion of matrix sheet material, and protective layer is formed become one with sheet material and moulding product, thus can bonding protective layer formation usefulness sheet material and moulding product.Herein, as the caking agent that uses in the bonding method of above-mentioned back, for example can enumerate carbamate is that caking agent, epoxy are that caking agent, ester are caking agent, acrylic acid series caking agent and hot-melting type caking agent etc.
Below, the method that forms the protective layer of moulding product by above-mentioned back bonding method is specifically described.At first, on the moulding product with the adhesive linkage side under mode configuration protection layer form and to use sheet material.Then, use to possess heat resistant rubber shape elastomerics, transfer machine such as the roll-type transfer machine of organo-silicone rubber, up down transfer machine for example is by being set at 80～260 ℃ of temperature, pressure 50～200kg/m
2The heat resistant rubber shape elastomerics of condition, protective layer one side that forms with sheet material from protective layer applies heat and/or pressure.Just adhesive linkage is bonded in moulding product surface in this way.At last, make the moulding product go up the complete crosslinking curing of resin layer that forms, form protective layer by heating.
Below, to being specifically described by the method for using injection molding while moulding transfer printing to form moulding product protective layer.At first, in the mold for forming of forming by movable mold and fixed mould, use adhesive linkage, put into protective layer formation sheet material according to the mode that makes matrix sheet material contact fixed mould in a word as the inboard.At this moment, also can put into the transfer materials sheet one by one, also can intermittently put into the essential part of overlength transfer materials.Use the protective layer of overlength to form when use sheet material, use to have the e Foerderanlage that mechanism is determined in the position, make protective layer formation reach consistent and get final product with the orientation of the patterned layer of sheet material and mold for forming.In addition; intermittently putting into protective layer forms when using sheet material; form with behind the position of sheet material to protective layer by sensor detecting; if with movable mold and fixed mould fixedly protective layer form and use sheet material; usually protective layer can be formed and be fixed on identical position with sheet material; the position of patterned layer can not departed from, and is easily therefore.After closing mold for forming, to mould, inject the filling molten resin, when forming the moulding product, protective layer formation is bonded on its surface with sheet material from the cast gate that movable mold is provided with.After the synthetic resin cooling, open mold for forming and take out synthetic resin.At last, heat with hot air type baking oven etc., thereby make the complete crosslinking curing of resin layer, thereby form protective layer.
Embodiment
Below enumerate embodiment and comparative example, the present invention is described more specifically.Unless part and % in the example specialize, and all are based on quality.
Embodiment 1
In the reaction unit of having equipped whipping appts, cooling tube, dropping funnel and nitrogen ingress pipe, the adding glycidyl methacrylate (below, brief note is for " GMA ") 250g, methyl iso-butyl ketone (MIBK) (below, brief note is for " MIBK ") 1000g and tert-butyl peroxide ethylhexoate (below, brief note is for " P-O ") behind the 10g, under nitrogen gas stream, made the temperature in the system be warmed up to about 90 ℃, be incubated 1 hour with about 1 hour.Then, from having added in advance by GMA750g, the dropping funnel of the mixed solution that P-O30g forms dripped mixed solution with about 2 hours in system under nitrogen gas stream, and insulation is 3 hours under uniform temp.Then, be warmed up to 120 ℃, be incubated 2 hours.After being cooled to 60 ℃, nitrogen ingress pipe is replaced to air leading-in conduit, add after vinylformic acid (below, note by abridging be " AA ") 507g, p methoxy phenol 2.3g and triphenyl phosphine 9.3g mix, blast down, be warmed up to 110 ℃ at air.After 8 hours, add p methoxy phenol 1.6g in insulation under the identical temperature, cooling, it is 50% that interpolation MIBK makes nonvolatile component, obtains the solution of silicon dioxide microparticle with reactive dispersion agent (A-1).The acryl equivalent of this reactivity dispersion agent (A-1) is about 214g/eq, and hydroxyl value is about 262mgKOH/g, weight-average molecular weight about 30,000.
Embodiment 2
Use the reaction unit identical with embodiment 1, adding GMA125g, methyl methacrylate (below, note by abridging be " MMA ") 125g behind MIBK1000g and the P-O10g, made the temperature in the system be warmed up to about 90 ℃ with about 1 hour under nitrogen gas stream, was incubated 1 hour.Then, from having added the dropping funnel of the mixed solution of being made up of GMA375g, MMA375g, P-O30g in advance, dripped mixed solution with about 2 hours in system under nitrogen gas stream, insulation is 3 hours under uniform temp.Then, be warmed up to 120 ℃, be incubated 2 hours.After being cooled to 60 ℃, nitrogen ingress pipe is replaced to air leading-in conduit, after adding AA254g, p methoxy phenol 2.3g and triphenyl phosphine 9.3g mix, blast down, be warmed up to 110 ℃ at air.After 8 hours, add p methoxy phenol 1.6g in insulation under the identical temperature, cooling, it is 50% that interpolation MIBK makes nonvolatile component, obtains the solution of silicon dioxide microparticle with reactive dispersion agent (A-2).The acryl equivalent of this reactivity dispersion agent (A-1) is about 356g/eq, and hydroxyl value is about 158mgKOH/g, weight-average molecular weight about 40,000.
Embodiment 3
Use the reaction unit identical with embodiment 1, adding GMA75g, MMA175g behind MIBK1000g and the P-O8g, made the temperature in the system be warmed up to about 90 ℃ with about 1 hour under nitrogen gas stream, was incubated 1 hour.Then, from having added the dropping funnel of the mixed solution of being made up of GMA300g, MMA700g, P-O23g in advance, dripped mixed solution with about 2 hours in system under nitrogen gas stream, insulation is 3 hours under uniform temp.Then, be warmed up to 120 ℃, be incubated 2 hours.After being cooled to 60 ℃, nitrogen ingress pipe is replaced to air leading-in conduit, after adding AA152g, p methoxy phenol 2.3g and triphenyl phosphine 5.6g mix, blast down, be warmed up to 110 ℃ at air.After 8 hours, add p methoxy phenol 1.6g in insulation under the identical temperature, cooling, it is 50% that interpolation MIBK makes nonvolatile component, obtains the solution of silicon dioxide microparticle with reactive dispersion agent (A-3).The acryl equivalent of this reactivity dispersion agent (A-1) is about 545g/eq, and hydroxyl value is about 103mgKOH/g, weight-average molecular weight about 70,000.
Embodiment 4
To count reactive dispersion agent (A-1), dipentaerythritol acrylate (DPHA) 25g, silicon dioxide microparticle (" Aerosil 200 " that Japanese AEROSIL (strain) makes of 25g by solid substance, the average about 12nm of initial particle) 50g and MIBK200g mix, and obtain mixture.
The Ultra Apex Mill " UAM015 " that uses longevity industry (strain) to make disperses the silicon dioxide microparticle in this mixture.The Ultra Apex Mill " UAM015 " that herein uses has diameter of stator bore to be 50mm φ, internal volume is 0.17 liter, the diameter of separator is 40mm φ, and the rotating disk of separator is set to the device of the wet-type ball mill of 5mm (among Fig. 2, not possessing the type of conveying end 19).When making dispersion, in wet-type ball mill being that to fill median particle diameter be the zirconium oxide bead of 30 μ m for the amount of 50 volume % with respect to the wet-type ball mill volume.
Said mixture in the head tank is provided to the wet-type ball mill from supplying opening with pump.Make rotor have the constant speed of rotation wet-type ball mill that turns round (circumferential speed of rotor front end is 8m/sec), with the flow of per minute 200ml to the mixture pulverizing that circulates.The circulation of carrying out 30 minutes is pulverized, and obtains in the mixture that silicon dioxide microparticle is dispersed in reactive dispersion agent (A-1), DPHA and MIBK and the dispersion that forms.Remove the MIBK in the dispersion that obtains with vaporizer, obtain nonvolatile component concentration and be 50% reactive dispersion.
In 100 parts of this reactivity dispersions, add 2 parts of light triggers " Irgacure-184 ", obtain active energy ray-curable resin composition.Active energy ray-curable resin composition preservation under room temperature (25 ℃) was not produced sediment in 2 months yet, and package stability is good.In addition, make cured coating film under the following conditions, when measuring pencil hardness, be 5H.
The measuring method of pencil hardness
1, the making method of cured coating film
With line rod coating machine active energy ray-curable resin composition is coated on cellulosetri-acetate (TAC) film (thickness 40um) and goes up (thickness 10 μ m),, under nitrogen, make high pressure mercury vapour lamp by 250mJ/cm 70 ℃ of dryings 1 minute
2Irradiation dose is passed through, and is cured, thereby obtains having the test film of cured coating film.
2, the evaluation method of cured coating film
According to JIS K 5400, be the curing overlay film of the pencil drawing thread test evaluation higher level test film of 500g by load.
Except the mixing shown in carry out table 1, make reactive dispersion by the mode identical with embodiment 4.The reactive dispersion that use obtains obtains active energy ray-curable resin composition by the mode identical with embodiment 4.Measure the pencil hardness of package stability and cured coating film by the mode identical with embodiment 4, it the results are shown in the table 1.
Table 1
The footnote of table 1
Aerosil 200: the silicon dioxide microparticle that Japanese AEROSIL (strain) makes.Initial particle 17nm.
Aerosil 50: the silicon dioxide microparticle that Japanese AEROSIL (strain) makes.Initial particle 30nm.
The EMIX-100:(strain) silicon dioxide microparticle of imperial gloomy manufacturing.Initial particle 100nm.
The EMIX-300:(strain) silicon dioxide microparticle of imperial gloomy manufacturing.Initial particle 300nm.
Disperse stability no sedimentation in zero: 2 month.
Comparative example 1
Use silicon dioxide microparticle (Japanese AEROSIL (strain) system, Aerosil 50, the average about 30nm of initial particle) 50g, (DIC (strain) makes bisphenol A epoxy acrylate, UNIDIC V-5500) 50g, MIBK200 part, in addition obtaining nonvolatile component concentration by the mode identical with embodiment 4 is 50% the reactive dispersion of compare.
With adding 2 parts of Irgacure-184 in 100 parts of the reactive dispersions, obtain the compare active energy ray-curable resin composition in this compare.Compare does not produce sediment with active energy ray-curable resin composition in the moment that room temperature (25 ℃) was preserved 1 hour down.In addition, make cured coating film, when measuring pencil hardness, be 2H by the mode identical with embodiment 4.
Comparative example 2
50 parts of silicon dioxide microparticles (Aerosil 50, the average about 30nm of initial particle), DPHA50 part, MIBK200 part are joined in the vial with zirconium oxide bead 600 parts (bead diameter 0.3mm), in PAINT SHAKER, mixed 2 hours, after the taking-up, remove MIBK with vaporizer, obtain nonvolatile component concentration and be 50% the reactive dispersion of compare.
With adding 2 parts of Irgacure-184 in 100 parts of the reactive dispersions, obtain the compare active energy ray-curable resin composition in this compare.The moment in 1 week of preservation does not produce sediment to compare down in room temperature (25 ℃) with active energy ray-curable resin composition.In addition, make cured coating film, when measuring pencil hardness, be 3H by the mode identical with embodiment 4.
Comparative example 3
In dry air, for the solution of forming by sulfydryl propyl trimethoxy silicane 221g, dibutyl tin laurate 1g, dripped isophorone diisocyanate 222g while stirring with 1 hour at 50 ℃, stirred 3 hours at 60 ℃ then.30 ℃ with 1 hour to wherein dripping ARONIX M-305[East Asia synthetic (strain) system, pentaerythritol triacrylate/tetramethylol methane tetraacrylate=60/40 (weight %)] 549g, then 60 ℃ of following heated and stirred 10 hours, thereby obtain organic compound.Under nitrogen gas stream, with organic compound 3.0g, methyl ethyl ketone silicon sol (daily output chemical industry (strain) system, trade(brand)name: MEK-ST, number average bead diameter 22nm, silica concentration 30%) mixed solution of 89.9g, ion exchanged water 0.1g 60 ℃ down stir 4 hours after, add original acid A ester 1.4g, again heated and stirred 1 hour under same temperature, desolventizing then obtains nonvolatile component concentration and is 30% the reactive dispersion of compare.
Add this compare with 2 parts of 100 parts of reactive dispersions, DPHA40 part, Irgacure-184 (light trigger), obtain the compare active energy ray-curable resin composition.The moment in 1 week of preservation does not produce sediment to compare down in room temperature (25 ℃) with active energy ray-curable resin composition.In addition, make cured coating film, when measuring pencil hardness, be 2H by the mode identical with embodiment 1.
Symbol description
1...... head tank, 2...... feedstock pump, 3...... grind type wet type agitating ball mill, 4...... separator, 5...... rotating shaft, 6...... chuck, 7...... stator, 9...... discharge-channel, 11...... rotor, 12...... motor, 13...... belt pulley, 14...... belt pulley, 15...... swivel joint, 16...... supply port, 17...... screen cloth support, 18...... screen cloth, 19...... conveying end, 21...... rotating disk, 22...... blade, 23...... adjuster, 24...... valve seat, 25...... valve body, 26...... cylinder, 27...... introducing port, 28...... cylinder, 29...... compressed air or N2The conductance entrance, 30...... electromagnetic switching valve, 31...... piston, 32...... bar, 33...... spring, 34...... nut, 43...... rotating shaft, 43a...... the step of rotating shaft 43,44...... separator, 45...... dividing plate, 46...... rotor, 47...... stopper, 48...... screw, 51...... blade embedded groove, 52...... disk, 53...... blade, 54...... discharge-channel, 55...... hole, 56...... annular baffle, 58...... valve, 59...... valve, 60...... compressed air or N2Air valve, 61...... valve, 62...... compressed air or N2Air valve, 63...... compressed air or N2Air valve, 64...... valve, 65...... outlet, 66...... outlet, 67...... goods tank.
Claims (13)
1. the manufacture method of a dispersion; this manufacture method is characterised in that, will contain in the molecular structure that to have (methyl) acryl and hydroxyl and (methyl) acryl equivalent be that 200～600g/eq, hydroxyl value are that the slurry of (methyl) acrylic acid polymer (B) of 90～280mgKOH/g and silicon dioxide microparticle (F) is provided in the stator from the described slurry supplying opening of the wet-type ball mill that comprises following structure:
1) inside be filled with medium the round tube type stator,
2) be arranged at described stator lower end the slurry supplying opening,
3) be positioned at the axle center of described stator, and its top be provided with the hollow form liquid discharge channel the turning axle that is rotated driving,
4) with described turning axle carry out rotor that coaxial rotation drives and
5) be arranged at described turning axle top with coaxial shape, and discharge the impeller type separator that is rotated driving that the parting liquid form constitutes to be communicated with described hollow form liquid discharge channel,
Drive described rotor at the stator internal rotation, medium and slurry are mixed, make the silicon dioxide microparticle (F) in the slurry pulverize and be dispersed in (methyl) acrylic acid polymer (B), the separator portion that drives in rotation makes slurry separate with medium by centrifugal action simultaneously, and the slurry that is attracted to position, separator axle center is discharged from the hollow form discharge-channel in the described turning axle.
2. according to the manufacture method of the dispersion described in the claim 1, wherein, (methyl) acryl equivalent of described (methyl) acrylic acid polymer (B) is 200～400g/eq, and hydroxyl value is 140～280mgKOH/g.
3. according to the manufacture method of the dispersion described in the claim 1, wherein, the weight-average molecular weight of described (methyl) acrylic acid polymer (B) is 5,000～100,000.
4. according to the manufacture method of the dispersion described in the claim 1, wherein, the initial particle of described silicon dioxide microparticle (F) is 10nm～300nm.
5. according to the manufacture method of the dispersion described in the claim 1; it is characterized in that; described (methyl) acrylic acid polymer (B) is to make monomer (c) with (methyl) acryl and carboxyl and (methyl) acrylic acid polymer (a1) with epoxy group(ing) carry out addition reaction and the resultant of reaction (b1) that forms, or makes monomer (d) with (methyl) acryl and epoxy group(ing) and monomer (methyl) acrylic acid polymer (a2) with carboxyl carry out addition reaction and the resultant of reaction (b2) that forms.
6. according to the manufacture method of the dispersion described in the claim 1, wherein, described (methyl) acrylic acid polymer (B) is to make (methyl) vinylformic acid and (methyl) acrylic acid polymer with epoxy group(ing) carry out addition reaction and the resultant of reaction that forms, described (methyl) acrylic acid polymer with epoxy group(ing) make with (methyl) glycidyl acrylate serve as must monomer component the polymerizable monomer polymerization obtain.
7. according to the manufacture method of the dispersion described in the claim 1, wherein, described medium is that the median size by median particle diameter is the zirconium white particulate of 15～300 μ m.
8. an energy ray curable resin composition is characterized in that, contains the dispersion that is obtained by each described manufacture method in the claim 1～7.
9. a film is characterized in that, has the energy ray curable resin composition curing that makes described in the claim 8 and the cured layer that obtains on membranaceous base material.
10. according to the film described in the claim 9, wherein, described membranaceous base material is selected from more than one in the membranaceous base material of polyethylene terephthalate resin (PET), the membranaceous base material of polycarbonate resin and the membranaceous base material of cellulose acetate resin.
11. according to the film described in the claim 9, wherein, the thickness of described cured layer is 3～100% with respect to the thickness of membranaceous base material.
12. a silicon dioxide microparticle disperses media with reactivity; it is characterized in that, contain in the molecular structure that to have (methyl) acryl and hydroxyl and (methyl) acryl equivalent be that 200～600g/eq, hydroxyl value are (methyl) acrylic acid polymer (B) of 90～280mgKOH/g.
13. reactive dispersion agent of silicon dioxide microparticle; it is characterized in that, contain in the molecular structure that to have (methyl) acryl and hydroxyl and (methyl) acryl equivalent be that 200～600g/eq, hydroxyl value are (methyl) acrylic acid polymer (B) of 90～280mgKOH/g.
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20100138790A (en) | 2010-12-31 |
| CN101928436B (en) | 2014-09-24 |
| JP2011026561A (en) | 2011-02-10 |
| TW201127480A (en) | 2011-08-16 |
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