CN101928436B - 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 PDF

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CN101928436B
CN101928436B CN201010211717.2A CN201010211717A CN101928436B CN 101928436 B CN101928436 B CN 101928436B CN 201010211717 A CN201010211717 A CN 201010211717A CN 101928436 B CN101928436 B CN 101928436B
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methyl
slurry
acrylic acid
acid polymer
dispersion
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CN101928436A (en
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谷本洋一
渡边泰之
山田雅生
新井久由
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Mixers Of The Rotary Stirring Type (AREA)

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

Manufacture method, energy ray curable resin composition and the film of silica dispersion
Technical field
Manufacture method, the energy ray curable resin composition that contains the dispersion obtaining by this manufacture method of the dispersion of the package stability excellence that the present invention relates to silicon dioxide microparticle to be dispersed in active energy ray-curable composition and form, have that the said composition of making is solidified the film of the cured layer obtaining, reactive medium and the reactive dispersion agent of silicon dioxide microparticle of disperseing for silicon dioxide microparticle.
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 to the method in active energy ray-curable resin composition.Silicon dioxide microparticle has the colloid silica of manufacturing by wet method, the aerosil of manufacturing by dry method.Silica particle surface has silanol base, and silicon dioxide microparticle is hydrophilic.Therefore, with composition as active energy ray curable monomer, oligopolymer etc. in the affinity of organic phase of principal constituent poor.In addition, the proportion of silicon dioxide microparticle is larger than organic phase.Therefore; make silicon dioxide microparticle in active energy ray-curable resin composition, reach long-time stable dispersion normally difficulty; if the active energy ray-curable resin composition that contains silicon dioxide microparticle is placed for a long time; can there is aggegation and sedimentation etc. in silicon dioxide microparticle, package stability is poor.In addition, silicon dioxide microparticle conventionally can be because aggegation consumingly occurs for the intermolecular forces and the electrostatic force etc. that act between initiating particle, and this also produces detrimentally affect to package stability.
As making silicon dioxide microparticle stably be dispersed in the method in active energy ray-curable resin composition, for example record the reactive silane coupling agent that there is hydrophobic group by use silicon dioxide microparticle has been carried out to surface treatment, by the method for silica particle surface hydrophobization (for example, referring to patent documentation 1), but, the dispersion stabilization of the silicon dioxide microparticle obtaining by the method for recording in patent documentation 1 in active energy ray-curable resin composition is still not enough, if at room temperature preserve one week, will produce the sediment of silicon dioxide microparticle.In addition, also need to heat up in a steamer and use that silane coupling agent carries out by product after surface treatment, the solvent that carries out for giving package stability is concentrated 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 is to provide silicon dioxide microparticle is dispersed in active energy ray-curable composition and the manufacture method of the dispersion of the package stability excellence that forms, contains the dispersion that obtains by this manufacture method and silicon dioxide microparticle and can keep for a long time the energy ray curable resin composition of stable dispersion state and have the cured layer of this energy ray curable resin composition as the film of hard coat.
The means of dealing with problems
In order to address the above problem, the inventor conducts in-depth research, found that, be 200～600g/eq as silicon dioxide microparticle (F) is dispersed in molecular structure thering is (methyl) acryl and hydroxyl and (methyl) acryl equivalent, 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 uniformly mixed in this wet-type ball mill inside, make the silicon dioxide microparticle (F) in slurry pulverize and be dispersed in (methyl) acrylic acid polymer (B), by centrifugal action, slurry is separated in impeller type separator portion with medium simultaneously, thereby the dispersion of obtaining, by making the silica dispersion that can easily and easily manufacture in this way package stability excellence etc., thereby complete the present invention.
; the present invention relates to the manufacture method of dispersion; this manufacture method is characterised in that; (methyl) acrylic acid polymer (B) that to have (methyl) acryl and hydroxyl and (methyl) acryl equivalent by containing in molecular structure and be 200～600g/eq, hydroxyl value be 90～280mgKOH/g and the slurry of silicon dioxide microparticle (F) are provided in stator from the described slurry supplying opening of the wet-type ball mill that comprises following structure
1) inside be filled with medium round tube type stator,
2) be arranged at said stator lower end slurry supplying opening,
3) be positioned at the axle center of said stator, and its top be provided with hollow form liquid discharge channel the turning axle that is rotated driving,
4) with above-mentioned turning axle carry out coaxial rotating driving rotor and
5) be arranged at above-mentioned turning axle top with coaxial shape, and discharge the impeller type separator that is rotated driving that parting liquid form forms to be communicated with above-mentioned hollow form liquid discharge channel,
In stator, rotarily actuate above-mentioned rotor, medium and slurry are uniformly mixed, make the silicon dioxide microparticle (F) in slurry pulverize and be dispersed in (methyl) acrylic acid polymer (B), simultaneously by centrifugal action, slurry is separated in the separator portion rotariling actuate with medium, the shape discharge-channel discharge by the slurry that attracted to position, separator axle center from the hollow in above-mentioned turning axle.
The invention still further relates to energy ray curable resin composition, it is characterized in that containing the dispersion obtaining by above-mentioned manufacture method.
The invention still further relates to a kind of film, it is characterized in that having the cured layer that above-mentioned energy ray curable resin composition is solidified and obtain on membranaceous base material.
The invention still further relates to the reactive medium that disperses for a kind of silicon dioxide microparticle; it is characterized in that, contain in molecular structure that to have (methyl) acryl and hydroxyl and (methyl) acryl equivalent be (methyl) acrylic acid polymer (B) that 200～600g/eq, hydroxyl value are 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 molecular structure that to have (methyl) acryl and hydroxyl and (methyl) acryl equivalent be (methyl) acrylic acid polymer (B) that 200～600g/eq, hydroxyl value are 90～280mgKOH/g.
Invention effect
According to the present invention, can easily and easily manufacture the silica dispersion of package stability excellence silicon dioxide microparticle being dispersed in active energy ray-curable composition and form.In addition, can also provide the energy ray curable resin composition that can make silicon dioxide microparticle keep for a long time stable dispersion state.In addition, the present invention can also provide the film with the cured layer that hardness is high.In addition, the present invention can also provide the reactive dispersion agent that is applicable to 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 using in dispersion manufacture method of the present invention.
Fig. 2 is the longitudinal section of the above-mentioned wet-type ball mill that uses in dispersion manufacture method of the present invention.
The longitudinal section of supplying opening when Fig. 3 is the above-mentioned wet-type ball mill supply slurry using in dispersion manufacture method of the present invention.
The longitudinal section of supplying opening when Fig. 4 is medium discharge.
Fig. 5 is the longitudinal section of another example of the above-mentioned wet-type ball mill that uses in 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.
Working of an invention mode
(methyl) acrylic acid polymer (B) using in the present invention is to be used as for making the reactivity that silicon dioxide microparticle (F) disperses disperse medium or for making silicon dioxide microparticle (F) be dispersed in the material of (methyl) described later acrylic acid polymer (B) compound with (methyl) acryl in addition; it is characterized in that; in molecular structure, there is (methyl) acryl and hydroxyl, and (methyl) acryl equivalent is that 200～600g/eq, hydroxyl value are 90～280mgKOH/g.Herein, (methyl) acryl equivalent refers to the solid substance weight (g/eq) of (methyl) acryloyl acid based polymer (B) of every 1 mole of (methyl) acryl (referring to acryl and/or methacryloyl).By making (methyl) acryl equivalent within the scope of 200～600g/eq, can realize high crosslink density, result just can reach high rigidity.In addition, (methyl) of the present invention acrylic acid polymer (B) has hydroxyl, and the silanol base existing in this hydroxyl and silica particle surface forms hydrogen bond.By making in the scope of hydroxyl value in 90～280mgKOH/g, can cover thick and fast silica sphere with (methyl) acrylic acid polymer (B), can realize polymolecularity.Can make to be thus scattered in silicon dioxide microparticle 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 making (methyl) acryl and hydroxyl value within the scope of these, the dispersion stabilization excellence of the dispersion obtaining, and use the cured coating film of the active energy ray-curable resin composition that this dispersion obtains to become high rigidity film.
As above-mentioned (methyl) acrylic acid polymer (B), the resultant of reaction (b1) that for example can enumerate (methyl) acrylic acid polymer (a1) that makes to have the monomer (c) of (methyl) acryl and carboxyl and there is epoxy group(ing) to carry out addition reaction and to form, the monomer (d) that makes to have (methyl) acryl and epoxy group(ing) carries out addition reaction with monomer (methyl) acrylic acid polymer (a2) with carboxyl and the resultant of reaction (b2) that forms, and the monomer (e) that makes to have an isocyanate group and (methyl) acryl carries out addition reaction with (methyl) acrylic monomer (a3) with hydroxyl and the resultant of reaction (b3) that forms etc.
As (methyl) acrylic acid polymer (a1) with epoxy group(ing) of use in preparation above-mentioned resultant of reaction (b1), for example can by have (methyl) acryl and epoxy group(ing) polymerizable monomer homopolymerization or obtain with the copolyreaction of other polymerizable monomer.
As the 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 two or more simultaneously.
(methyl) acrylic acid polymer (a1) can be the homopolymer with the polymerizable monomer of (methyl) acryl and epoxy group(ing), can be also the multipolymer with other polymerizable monomer.While forming with the multipolymer of other polymerizability unsaturated monomer; preferably by (thering is the polymerizable monomer of (methyl) acryl and epoxy group(ing)): (other polymerizable monomer) is 25～100 mass parts: the scope of 75～0 mass parts is used, more preferably by 40～100 mass parts: the scope of 60～0 mass parts is used.
As (methyl) acrylic acid polymer (a2) with carboxyl of use in preparation above-mentioned resultant of reaction (b2), for example can by have (methyl) acryl and carboxyl polymerizable monomer homopolymerization or obtain with the copolyreaction of other polymerizable monomer.
As the polymerizable monomer with (methyl) acryl and carboxyl, 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.These monomers can use separately, also can use two or more simultaneously.
(methyl) acrylic acid polymer (a2) can be the homopolymer with the polymerizable monomer of (methyl) acryl and carboxyl, can be also the multipolymer with other polymerizable monomer.While forming with the multipolymer of other polymerizability unsaturated monomer; preferably by (thering is the polymerizable monomer of (methyl) acryl and carboxyl): (other polymerizable monomer) is 25～100 mass parts: the scope of 75～0 mass parts is used, more preferably by 40～100 mass parts: the scope of 60～0 mass parts is used.
As (methyl) acrylic acid polymer (a3) with hydroxyl of use in preparation above-mentioned resultant of reaction (b3), for example can by have (methyl) acryl and hydroxyl polymerizable monomer homopolymerization or obtain with the copolyreaction of other polymerizable monomer.
As the 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 two or more simultaneously.
(methyl) acrylic acid polymer (a3) can be the homopolymer with the polymerizable monomer of (methyl) acryl and hydroxyl, can be also the multipolymer with other polymerizable monomer.While forming with the multipolymer of other polymerizability unsaturated monomer; preferably by (thering is the polymerizable monomer of (methyl) acryl and hydroxyl): (other polymerizable monomer) is 25～100 mass parts: the scope of 75～0 mass parts is used, 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 as preparation (methyl) acrylic acid polymer (a1), (a2) and (a3) time, for example, can enumerate 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) aliphatic acrylate, (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 benzoxy ethyl ester, (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 polyalkylene glycol base has the esters of acrylic acid of hydroxyalkyl;
(5) the unsaturated dicarboxylic acid ester class 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) the styrene derivatives class such as vinylbenzene, alpha-methyl styrene, chloro-styrene;
(7) diene compound such as divinyl, isoprene, piperylene, dimethylbutadiene;
(8) halogen ethene and the 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) the vinyl cyanide class such as vinyl cyanide, methacrylonitrile, vinylidene dicyanide;
(13) acrylamide and alkyd substituted amide class thereof;
(14) the N-substituted maleimide such as N-phenylmaleimide, N-N-cyclohexylmaleimide;
(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 is the fluorine-containing ethylene unsaturated monomer classes such as (entirely) fluoroalkyl (methyl) esters of acrylic acid of 1 to 18;
(16) (methyl) esters of acrylic acid that gamma-methyl allyl acyloxypropyl trimethoxysilane etc. contains silyl;
(17) N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate or N, the N such as N-diethylamino propyl group (methyl) acrylate, N-dialkyl aminoalkyl (methyl) acrylate etc.
These preparations (methyl) acrylic acid polymer (a1), (a2) and other polymerizability unsaturated monomer that carries out copolymerization (a3) time, can use separately, also can be with using two or more.
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 not particularly limited.Can under the existence of catalyzer (polymerization starter), manufacture by addition polymerization, can be any in random copolymers, segmented copolymer, graft copolymer etc.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 the 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, diη-propyl ketone, diisobutyl ketone, pimelinketone, sym.-diisopropylideneacetone;
The 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);
The ester series solvents such as 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-3-ethoxy-c acid esters;
The alcohol series solvents such as methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, diacetone alcohol, 3-MP, 3-methoxyl group-n-butyl alcohol, 3-methyl-3-methoxybutanol;
The 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 two or more simultaneously.
The solvent as (methyl) acrylic acid polymer (a1) or (a2) using when polymerization, because the reacting of (methyl) acrylic acid polymer (a1) of the follow-up subordinate phase reaction as these polymerizations and monomer (c), (methyl) acrylic acid polymer (a2) are preferred while carrying out under the high temperature of 100～150 DEG C with reacting of monomer (d) on reaction efficiency, therefore it is more than 100 DEG C preferably using boiling point, the preferably solvent of 100～150 DEG C.The solvent using during as (methyl) acrylic acid polymer (a3) polymerization, due to (methyl) acrylic acid polymer (a3) of the follow-up subordinate phase reaction as this polymerization and monomer (e) to react in the time that the scope of 50～120 DEG C is carried out be preferred on reaction efficiency, therefore it is more than 60 DEG C preferably using boiling point, the preferably solvent of 60～150 DEG C.
In addition, as above-mentioned catalyzer, can use the known material that is used as radical polymerization initiator conventionally, for example can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2,4-methyl pentane nitrile), 2, the azo-compounds such as 2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile); Benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide pivalate, t-butyl peroxy ethylhexoate, 1, organo-peroxide and the hydrogen peroxide etc. such as 1 '-bis-(tert-butyl peroxide) hexanaphthene, peroxidation tert-pentyl-2-ethylhexanoate, the tertiary hexyl-2-ethylhexanoate of peroxidation.
While using superoxide as catalyzer, also superoxide can be used together with reductive agent, form oxidation-reduction type initiator.
Above-mentioned resultant of reaction (b1) makes (methyl) acrylic acid polymer (a1) with epoxy group(ing) as above react and obtain with the monomer (c) with (methyl) acryl and carboxyl.As the monomer (c) with (methyl) acryl and carboxyl, 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), also after can using multifunctional (methyl) acrylate monomer that the acid anhydrides such as succinyl oxide and maleic anhydride contain hydroxyl with pentaerythritol triacrylate etc. to react, multifunctional (methyl) acrylate monomer that contains carboxyl of formation.The monomer (c) with (methyl) acryl and carboxyl can be distinguished use separately, also can use two or more simultaneously.
The reaction of (methyl) acrylic acid polymer (a1) and above-mentioned monomer (c), normally by two kinds of compositions are mixed, is heated to 80～120 DEG C of left and right and carries out.For the usage quantity of (methyl) acrylic acid polymer (a1) and monomer (c); as long as in the scope of (methyl) acryl equivalent that makes the resultant of reaction (b1) obtaining in 200～600g/eq; have no particular limits; conventionally 1 mole of the epoxy group(ing) in preferably relative (methyl) acrylic acid polymer (a1), makes the mole number of the carboxyl in monomer (c) in the scope of 0.4～1.1 mole.
Above-mentioned resultant of reaction (b2) makes (methyl) acrylic acid polymer (a2) with carboxyl as above react and obtain with the monomer (d) with (methyl) acryl and epoxy group(ing).As the monomer (d) 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 two or more simultaneously.
The reaction of (methyl) acrylic acid polymer (a2) and above-mentioned monomer (d), normally by two kinds of compositions are mixed, is heated to 80～120 DEG C of left and right and carries out.For the usage quantity of (methyl) acrylic acid polymer (a2) and monomer (d); as long as in the scope of (methyl) acryl equivalent that makes the resultant of reaction (b2) obtaining in 200～600g/eq; have no particular limits; conventionally 1 mole of the carboxyl in preferably relative (methyl) acrylic acid polymer (a2), makes the mole number of the epoxy group(ing) in monomer (d) in the scope of 0.4～1.1 mole.
Above-mentioned resultant of reaction (b3) makes (methyl) acrylic acid polymer (a3) with hydroxyl as above react and obtain with the monomer (e) with an isocyanate group and (methyl) acryl.As the monomer (e) with an isocyanate group and (methyl) acryl, for example can enumerate have an isocyanate group and (methyl) acryl monomer, have an isocyanate group and two (methyl) acryls monomer, have an isocyanate group and three (methyl) acryls monomer, have an isocyanate group and four (methyl) acryls monomer, there is monomer of an isocyanate group and five (methyl) acryls etc.As this monomer, for example, can preferably illustrate the compound that following general formula 1 represents.
In general formula (1), R 1for hydrogen atom or methyl.R 2for carbonatoms is 2 to 4 alkylidene group.N represents 1～5 integer.These compounds can be enumerated, for example 2-(methyl) acryloxy ethyl isocyanate, 1,1-bis-(acryloyl-oxy ylmethyl) ethyl isocyanate etc., there are specifically the commodity such as Karenz AOI, Karenz MOI, Karenz BEI (trade(brand)name, clear and electrician's (strain) system).As other example, there is the reaction adducts of diisocyanate cpd and hydroxy acrylate etc., as diisocyanate cpd, known material can be used without particular limitation herein, for example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. can be enumerated.As hydroxy acrylate; as long as thering is the compound of hydroxyl and (methyl) acryl; be not particularly limited; known material can be used, for example, 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. can be enumerated.Wherein, consider preferably in molecule as such a in KarenzBEI, there is the material of two above (methyl) acryls from improving cross-linking density.These compounds can use separately, also can be with using two or more.
(methyl) acrylic acid polymer (a3) is not particularly limited with the method that monomer (e) reacts, can adopts known method.Specifically, for example, can in (methyl) acrylic acid polymer (a3), drip monomer (e), be heated to 50～120 DEG C, more preferably 60～90 DEG C are reacted.Also have; for the usage quantity of (methyl) acrylic acid polymer (a3) and monomer (e); as long as in the scope of (methyl) acryl equivalent that makes the resultant of reaction (b3) obtaining in 200～600g/eq; have no particular limits; conventionally 1 mole of the hydroxyl in preferably relative (methyl) acrylic acid polymer (a3), makes the mole number of the isocyanate group in monomer (e) in the scope of 0.8～1.2 mole.
The above-mentioned reaction that there is (methyl) acrylic acid polymer (a1) of epoxy group(ing) and there is the monomer (c) of (methyl) acryl and carboxyl, there is (methyl) acrylic acid polymer (a2) of carboxyl and there is the reaction of the monomer (d) of (methyl) acryl and epoxy group(ing), and there is (methyl) acrylic acid polymer (a3) of hydroxyl and there is an isocyanate group and the reaction of the monomer (e) of (methyl) acryl also can be undertaken by for example following methods.
Method 1: by solution polymerization process polymerization (methyl) acrylic acid polymer (a1), add the monomer (c) with (methyl) acryl and carboxyl to react in reaction system.
Method 2: by solution polymerization process polymerization (methyl) acrylic acid polymer (a2), add the monomer (d) with (methyl) acryl and epoxy group(ing) to react in reaction system.
Method 3: by solution polymerization process polymerization (methyl) acrylic acid polymer (a3), add the monomer (e) with an isocyanic ester and (methyl) acryl to react in reaction system.
In addition, (methyl) acrylic acid polymer (B) using in the present invention preferably the monomer in each molecule with a polymerizability unsaturated double-bond is carried out to polymerization and the structure that obtains as the polymkeric substance of main framing, but can in the time of polymerization, not occur to use the monomer with more than two polymerizability unsaturated double-bond in the scope of gelation simultaneously yet.
As (methyl) acrylic acid polymer (B) using in the present invention; be preferably that the monomer (c) that makes to have (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, wherein more preferably make (methyl) vinylformic acid and (methyl) acrylic acid polymer with epoxy group(ing) being obtained by the polymerizable monomer polymerization that contains (methyl) glycidyl acrylate carry out addition reaction and the resultant of reaction that forms.
As the epoxy equivalent (weight) of above-mentioned (methyl) acrylic acid polymer (a1) with epoxy group(ing), be preferably 140～500g/eq, more preferably 140～300g/eq.In addition, as the second-order transition temperature of (methyl) acrylic acid polymer (a1) with epoxy group(ing), be preferably more than 30 DEG C more preferably 30～100 DEG C.
It should be noted that, the epoxy equivalent (weight) in the present invention is the value being defined by JIS-K-7236.
In the present invention, the mensuration of weight-average molecular weight and number-average molecular weight is to use gel permeation chromatography (GPC), measures by following condition.
Determinator: the HLC-8220 processed of TOSOH Co., Ltd
Post: the Guide Column processed H of TOSOH Co., Ltd xL-H
The TSKgel G5000HXL processed of+TOSOH Co., Ltd
The TSKgel G4000HXL processed of+TOSOH Co., Ltd
The TSKgel G3000HXL processed of+TOSOH Co., Ltd
The TSKgel G2000HXL processed of+TOSOH Co., Ltd
Detector: RI (differential refractometer)
Data processing: the SC-8010 processed of TOSOH Co., Ltd
Condition determination: 40 DEG C of column temperatures
Solvents tetrahydrofurane
Flow velocity 1.0ml/ minute
Standard specimen: polystyrene
Sample: be that the tetrahydrofuran solution micro-filter of 0.4 % by weight filters the sample obtaining (100 μ l) by being converted into resin solid substance
From the viewpoint of cure shrinkage effect and levelling property, the weight-average molecular weight of (methyl) acrylic acid polymer (B) using in the present invention is preferably 5,000～100, and 000, more preferably 5,000～50,000.
(methyl) acrylic acid polymer (B) using in the present invention has hydroxyl.The hydroxyl that (methyl) acrylic acid polymer (B) has also can react with the isocyanate group of the monomer with an isocyanate group and (methyl) acryl in the scope of not damaging effect of the present invention.Thus, can suitably regulate (methyl) acryl equivalent and hydroxyl equivalent.
As the above-mentioned monomer with an isocyanate group and (methyl) acryl, for example can enumerate have an isocyanate group and (methyl) acryl monomer, have an isocyanate group and two (methyl) acryls monomer, have an isocyanate group and three (methyl) acryls monomer, have an isocyanate group and four (methyl) acryls monomer, there is the monomer an of isocyanate group and five (methyl) acryls.As this monomer, for example, can preferably illustrate the compound that following general formula 1 represents.
In general formula (1), R 1for hydrogen atom or methyl.R 2for carbonatoms is 2 to 4 alkylidene group.N represents 1～5 integer.These compounds can be enumerated, for example 2-(methyl) acryloxy ethyl isocyanate, 1,1-bis-(acryloyl-oxy ylmethyl) ethyl isocyanate etc., there are specifically the commodity such as Karenz AOI, Karenz MOI, Karenz BEI (trade(brand)name, clear and electrician's (strain) system).As other example, there is the reaction adducts of diisocyanate cpd and hydroxy acrylate etc., as diisocyanate cpd, known material can be used without particular limitation herein, for example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. can be enumerated.As hydroxy acrylate; as long as thering is the compound of hydroxyl and (methyl) acryl; be not particularly limited; known material can be used, for example, 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. can be enumerated.Wherein, consider preferably in molecule as such a in KarenzBEI, there is the material of two above (methyl) acryls from improving cross-linking density.
(methyl) acrylic acid polymer (B) using in the present invention and have an isocyanate group and the method for the monomer reaction of (methyl) acryl is not particularly limited, can adopt known method.Specifically; for example can in (methyl) of the present invention acrylic acid polymer (B), drip the monomer with an isocyanate group and (methyl) acryl; be heated to 50～120 DEG C, more preferably 60～90 DEG C are reacted.Also have; for (methyl) acrylic acid polymer (B) with there is an isocyanate group and the usage quantity of the monomer of (methyl) acryl; conventionally the hydroxyl of (methyl) acrylic acid polymer (B) (mole): have the monomer an of isocyanate group and (methyl) acryl isocyanate group (mole) be 1: 0.1～1: 0.9, be 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 is for example for by the silicon dioxide microparticle that makes silicon tetrachloride burn and obtain in oxygen or hydrogen flame.In addition, wet silicon dioxide is for example the silicon dioxide microparticle with obtaining with water glass in mineral acid.Manufacturing method according to the invention, in the situation that using any silicon dioxide microparticle, the dispersion obtaining all can keep good dispersion stabilization for a long time.In addition, this dispersion is added to while preparing active energy ray-curable resin composition in carbamate (methyl) acrylate, epoxy (methyl) acrylate isoreactivity energy ray-curable oligopolymer or active energy ray curable monomer, and in this active energy ray-curable resin composition, silicon dioxide microparticle also can keep stable dispersion for a long time.
As the silicon dioxide microparticle using in the present invention (F), the particulate that preferably average initial particle is 10nm～300nm, the particulate that more preferably average initial particle is 10nm～200nm.
In the present invention, silicon dioxide microparticle (F) is dispersed in above-mentioned (methyl) acrylic acid polymer (B), thus preparation dispersion.In the dispersion obtaining, the content of each composition is not particularly limited, 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 dispersion and silicon dioxide microparticle (F) by the present invention is preferably scaled solid substance, more preferably 1～30 quality %.
The slurry using in the present invention contains (methyl) acrylate copolymer (B) and silicon dioxide microparticle (F); except these compositions, can also contain (methyl) acrylate copolymer (B) compound with (methyl) acryl in addition.As (methyl) acrylate copolymer (B) compound with (methyl) acryl in addition, for example, can enumerate active energy ray curable monomer (M) and/or active energy ray curable oligopolymer (O) etc.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; while using the compound with (methyl) acryl in addition of (methyl) acrylate copolymer (B), (methyl) acrylate copolymer (B) can be used as and make silicon dioxide microparticle (F) be scattered in the 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 using except the raw material as (methyl) acrylate copolymer (B) etc., 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 butylene glycol two (methyl) acrylate, BDO 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 in 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 the epoxy alkane to 1～20 mole of these compound addition and the hydroxy-containing compounds that forms etc. has the compound of more than 3 hydroxyl and 3 above (methyl) acrylic molecules and forms compounds that ester bond obtains etc.
As above-mentioned active energy ray curable oligopolymer (O), for example, can enumerate more than one (methyl) acrylic compound that are selected from acryl (methyl) acrylate in addition 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 forming.As isocyanate compound used herein, for example, can enumerate aliphatics or the ester ring type diisocyanate cpds such as hexamethylene diisocyanate, isophorone diisocyanate, Xylene Diisocyanate, hydrogenated xylene diisocyanate, dicyclohexyl methane diisocyanate, norbornene alkyl diisocyanate; Tolylene diisocyanate, 4, the aromatic diisocyanates such as 4 '-diphenylmethanediisocyanate; As the trimeric isocyanuric acid ester type of diisocyanate cpd isocyanate prepolymer etc.In addition, while manufacturing this carbamate (methyl) acrylate, also can replace and carry out polymerization by a part for the compound of (methyl) acrylate of 2 yuan～4 yuan alcohol and/or the polyol compound pair hydroxyl reacting with isocyanate compound.
As above-mentioned polyester (methyl) acrylate, can enumerate and make to be selected from ethylene glycol, propylene glycol, Diethylene Glycol, neopentyl glycol, dihydroxyphenyl propane, Hydrogenated Bisphenol A, ethoxylation dihydroxyphenyl propane, ethoxylation Hydrogenated Bisphenol A, propoxylated bisphenol, more than one materials in propoxylation Hydrogenated Bisphenol A and polyvalent alcohol more than 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 anhydride etc. obtains for more than one materials in the polyprotonic acid of representative carry out esterification the ester polyol that contains hydroxyl, multifunctional ester (methyl) acrylate that again this ester polyol is carried out to (methyl) acroleic acid esterification and form etc.
As above-mentioned epoxy acrylate, for example, can enumerate that bicyclic oxygen compounds such as making the triglycidyl group etherate of (methyl) vinylformic acid to 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 propanes carries out addition and divalence epoxy (methyl) acrylic compound that obtains; The trivalent alcohols such as TriMethylolPropane(TMP), ethoxylated trimethylolpropane, propoxylation TriMethylolPropane(TMP), glycerine are carried out epoxidation and obtain epoxy compounds, then make (methyl) acrylate and this epoxy compounds carry out addition and epoxy three (methyl) acrylic compound of average 3 the above free-radical polymerised unsaturated double-bonds of having of obtaining; Make glycidyl ether react and form epoxy compounds with polyphenol or its alkylene oxide adduct with at least one aromatic nucleus, then make (methyl) acrylate and this epoxy compounds carry out addition reaction and the multifunctional aromatic epoxies acrylate such as phenol linear phenolic resin, cresols linear phenolic resin that obtains; As the multifunctional ester ring type epoxy acrylate of the hydrogenated version of these multifunctional aromatic epoxies acrylate; An isocyanic ester of the secondary hydroxyl existing in by molecule and diisocyanate cpd carries out after urethane, the isocyanate group of residual single end and (methyl) acrylate of hydroxyl is reacted and urethane-modified epoxy acrylate of obtaining etc.
In these compounds, there is the excelling in abrasion resistance of average 3 above polyester (methyl) acrylate of free-radical polymerised unsaturated double-bond and the cured coating film of carbamate (methyl) acrylate, be therefore particularly preferred.
In the slurry using in the present invention, also can add as required organic solvent.In preferred slurries, contain organic solvent (S).
As the organic solvent using in the present invention (S), for example can enumerate acetone, methyl ethyl ketone (MEK), the ketones such as methyl iso-butyl ketone (MIBK), tetrahydrofuran (THF) (THF), the ring-type ethers such as dioxolane, ritalin, vinyl acetic monomer, the ester classes such as N-BUTYL ACETATE, toluene, the fragrant same clan such as dimethylbenzene, Trivalin SF, cellosolve, methyl alcohol, Virahol, butanols, the alcohols such as propylene glycol monomethyl ether, these solvents can use individually or simultaneously, wherein, volatility and solvent recuperation during from the viewpoint of coating, preferably as the methyl ethyl ketone of the synthetic of reactive dispersion agent.
As the usage quantity of above-mentioned organic solvent, be preferably 150～500 mass parts with respect to total 100 mass parts of (methyl) acrylic acid polymer (B) and silicon dioxide microparticle (F), when while being wherein 200～300 mass parts, ball mill operates, slurry separates good with medium, and the operation short period of time of slurry when concentrated can complete, be therefore preferred.
While preparing slurry, preferably in above-mentioned (methyl) acrylic acid polymer (B), add organic solvent and obtaining after organic solvent solution, add silicon dioxide microparticle (F).
In the slurry that also can use in the present invention as required, add various additives.
As the various additives that use in 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-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy triethoxyl silane, to styryl Trimethoxy silane, 3-methacryloxypropyl methyl dimethoxysilane, 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)-APTES, 3-TSL 8330, APTES, 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, 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, trieline base silane, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane.
Be silane coupling agent as epoxy, for example can enumerate diethoxy (glycidoxy propyl group) methyl-monosilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-triethoxysilicane etc.
As polystyrene silane coupling agent, for example, can enumerate styryl Trimethoxy silane etc.
Be silane coupling agent as methacryloxy, for example, can illustrate 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.
Be silane coupling agent as amino, for example can enumerate N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-APTES, 3-TSL 8330, APTES, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propyl group amine, N-phenyl-3-TSL 8330 etc.
Be silane coupling agent as uride, for example, can enumerate 3-uride propyl-triethoxysilicane etc.
Be silane coupling agent as chloropropyl, for example, can illustrate 3-r-chloropropyl trimethoxyl silane.
Be silane coupling agent as sulfydryl, 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 isocyanate-based silane coupling agent, for example, can enumerate 3-isocyanate group propyl-triethoxysilicane etc.
Be coupling agent as aluminium, for example, can enumerate acetyl aluminum alkoxide diisopropanol compound etc.
Dispersion manufacture method of the present invention is characterised in that, above-mentioned slurry is provided to and is comprised from slurry supplying opening
1) inside be filled with medium round tube type stator,
2) be arranged at said stator lower end slurry supplying opening,
3) be positioned at the axle center of said stator, and its top be provided with hollow form liquid discharge channel the turning axle that is rotated driving,
4) with above-mentioned turning axle carry out coaxial rotating driving rotor and
5) be arranged at above-mentioned turning axle top with coaxial shape, and discharge the impeller type separator that is rotated driving that parting liquid form forms to be communicated with above-mentioned hollow form liquid discharge channel
The stator of wet-type ball mill in, in stator, rotarily actuate above-mentioned rotor, medium and slurry are uniformly mixed, make the silicon dioxide microparticle (F) in slurry pulverize and be dispersed in (methyl) acrylic acid polymer (B), by centrifugal action, slurry is separated in the separator portion rotariling actuate with medium simultaneously, the slurry that attracted to position, separator axle center is discharged from the hollow bleed passage in above-mentioned turning axle.
Below, utilize accompanying drawing to be elaborated to the manufacture method of the present invention that uses wet-type ball mill as above.
In Fig. 1, by the slurry of extracting out from the head tank 1 of storage slurry with feedstock pump 2, be provided to wet-type ball mill 3 from supplying opening 16.About this wet-type ball mill, can enumerate particularly the round tube type stator 7 in Fig. 2.In this stator 7, be filled with medium, by the rotor 11 rotariling actuate, slurry and medium are uniformly mixed, make the silicon dioxide microparticle (F) in slurry pulverize and be dispersed in (methyl) acrylic acid polymer (B), utilize the impeller type separator 4 rotariling actuate by centrifugal action, slurry to be separated with medium simultaneously.Now, heavy medium radially flies out outwardly, on the other hand, 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 tank 1 via pump 64, thereby carry out the circulation pulverizing of silicon dioxide microparticle.The granularity of suitably measuring slurry in the process of pulverizing in circulation, stops while reaching desired value.
In manufacture method of the present invention, by feedstock pump, slurry is supplied with to the circular flow of wet-type ball mill 3, with respect to every 1 liter of inner capacities of wet-type ball mill 3, be generally 30～100L/ hour, be preferably 50～80L/ hour.By making circular flow within the scope of this, the residence time of slurry in wet-type ball mill 3 reaches optimum condition, and dispersion efficiency increases.Now, the time that dispersion spends is preferably 5～60 minutes, more preferably 10～40 minutes conventionally.
As the medium of filling in 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.
For the particle diameter of medium, from separator 4 slurry and medium separate good, and in rotor 11 pulverizing of silicon dioxide microparticle also good, disperse required time be also difficult for elongated, to the impact of silicon dioxide microparticle can be excessively not strong, be not easy to produce because silicon dioxide microparticle is damaged the consideration of dispersion phenomenon aspect, preferably taking the median size of median particle diameter as 15～300 μ m, more preferably 15～50 μ m.
The above-mentioned dispersion phenomenon of crossing refers to that silicon dioxide microparticle breakage causes new active surface to generate, and occurs the phenomenon of aggegation again.If cross dispersion, dispersion liquid becomes gelatin.
In stator, the filling ratio of medium is preferably 80～90 volume % of stator internal volume conventionally.Be 80～90 volume % of stator internal volume by making filling ratio, the needed power of goods slurry that obtains unit weight is minimum., can pulverize most effectively.
Order when slurry is supplied with to stator 7 is as follows.After the interior filled media of stator 7 of wet-type ball mill 3, at valve-off 58,59 and 60 and open under the state of valve 61,62 and 64 first drivingmotor 12, then drive feedstock pump 2.Rotarily actuate rotor 11 and separator 4 by the driving of the former electric motor 12, driving by the latter's feedstock pump 2 is by each a certain amount of the introducing port 27 of the feed slurry in head tank 1 being sent into supplying opening 16 on the other hand, and the slit forming between the edge by valve seat 24 and valve body 25 is thus supplied in wet-type ball mill.
Drivingmotor 12, when rotor 11 and separator 4 are rotated, the larger circumferential speed of revolution is larger, and suffered centrifugal force is larger, and in addition, impact when medium and silicon dioxide microparticle clash into is also larger.As medium, when to use particle diameter be the medium of 15 μ m, preferred circumferential speed is for more than 15m/sec.As medium, when to use particle diameter be the medium of 30 μ m, preferred circumferential speed is for more than 8m/sec.
Further, the wet-type ball mill 3 shown in Fig. 1 possesses the conveying end 19 for making slurry discharge after having disperseed, 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, slurry granularity reaches desired value, and the order while stopping disperseing is as follows.
First, there is no the situation of conveying end 9 for wet-type ball mill 3, can enumerate following methods: temporarily stop feedstock pump 2, then stop electric motor 12, thereby wet-type ball mill 3 is shut down, stop pulverizing.Afterwards, after valve-off 61, open valve 59.Then again start by feedstock pump 2, the goods slurry in head tank 1 is delivered to goods tank 67 from relief outlet 66.On the other hand, in order to extract goods slurry residual in stator out, valve-off 59 in stopping feedstock pump 2.Then, the pipeline conversion that turns back to head tank 1 via valve 64 is connected on goods tank 67.In empty head tank 1, fill the solvent as raw material to becoming, according to operating to supplying with the order that slurry is identical in stator 7 with above-mentioned, drivingmotor 12 again, drives feedstock pump again, and goods slurry residual in stator 7 is recovered in goods tank.
Have the situation of conveying end 9 for wet-type ball mill 3, the order while 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.Then open valve 58 and 59, valve-off 61,62 and 64 simultaneously, and again start feedstock pump 2 and electric motor 12, then open valve 60.Thus, the goods slurry in head tank 1 is extracted out by feedstock pump 2 and is transported to goods tank 67 from relief outlet 66.On the other hand, the goods slurry in wet-type ball mill 3, because the rotation of rotor 7 is stirred, also relies on by valve 60 and hollow form liquid discharge channel 9 pressurized air or the N that are supplied in wet-type ball mill 3 simultaneously 2gas and being extruded by screen cloth 18, is transported to goods tank 67 from relief outlet 65 through conveying end 19.As above, the goods slurry in head tank 1 and in wet-type ball mill 3 is recycled in goods tank 67.
Further, use while thering is the wet-type ball mill of conveying end 19, while reclaiming goods, make rotor 7 rotations be due to, when mixing, there will not be the lower floor position that is present in unevenly wet-type ball mill 3 because of medium sedimentation, thereby prevent the clogging of screen of screen cloth 18.And in order to eliminate clogging of screen, also can open valve 63 and import suitable pressurized air or N from conveying end 19 2gas, thus screen cloth 18 is carried out to counterflush.
Based on Fig. 1～Fig. 4, the device using in manufacture method of the present invention is illustrated in greater detail.
As above-mentioned wet-type ball mill 3, as shown in Fig. 2 in detail, for longitudinal round shape, 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 turning axle that is rotated driving 5 that the axle center of stator and its top are provided with the hollow form liquid discharge channel 9 being communicated with head tank 1, what arrange towards radially giving prominence at above-mentioned turning axle end portion carries out the needle-like of coaxial rotating driving or the rotor of plate-like 11 with turning axle, be fixed on 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 arranged on the swivel joint 15 of the opening end of turning axle upper end, and be fixed on the separator 4 for separating of medium on turning axle 5 near being positioned at stator internal upper part.In addition, when stator bottom has above-mentioned conveying end 19, this conveying end 19 is disposed at the eccentric position of stator bottom, specifically, is made up of reticulation screen cloth support 17 and the screen cloth 18 for separating of medium being installed on this screen cloth support 17.
Separator 4 forms with the blade 22 that is connected two disks 21 by existing at regular intervals on turning axle 5 with fixing pair of discs 21, form impeller, carry out coaxial rotating with above-mentioned turning axle 5, make medium and slurry to entering between disk apply 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.
As the supplying opening 16 of feed slurry, as shown in Fig. 3 in detail, by be formed at stator bottom valve seat 24, be liftably embedded in the reverse frustoconic valve body 25 of valve seat 24, give prominence to from stator bottom and be formed with having round-ended cylinder body 26 and giving prominence to and possess pressurized air or N from this cylinder of feed slurry introducing port 27 downwards downwards 2conductance entrance 29 have a round-ended cylinder 28, liftably be entrenched in the piston 31 on cylinder 28, connect the bar 32 of piston 31 and valve body 25, be installed on the piston in cylinder 28 and in the time depressing piston 31 valve body 25 spring 33 of downward reactive force conventionally, with protrude from cylinder 28 and be screwed into the end of bar and the composition of the nut 34 that install adjustably position, if valve body 25 is pressed to due to the supply of feed slurry, and between valve seat 24 form annular slot, feed slurry is just fed in ball mill thus, but the width in above-mentioned gap can tightening by nut 34, loosen and adjust, even come to a dead end on cylinder 28 and form maximum width thereby this width can be set as to nut 34 in the time of base feed, medium still can not pass.Valve body 25 when base feed is pressed and is resisted pressure in wet-type ball mill 3 and the effect of spring 33 is risen owing to sending into the supply of the feed slurry in cylinder 26, and form gap between valve seat 24, but the wavelength width of a slit forming 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, therefore slightly rich amount also between the cylinder 28 of nut 34.
In being fed into the feed slurry in ball mill, contain coarse particle passing through the gap forming between valve seat 24 and valve body 25, can expect it can sandwich between valve seat and valve body and produce and stop up, while having there is obstruction because sandwiching, supply with pressure by raising and make valve body 25 rise to the limit, it is maximum that wavelength width of a slit reaches.Therefore the coarse particle sandwiching flows out, and stops up and eliminates.Eliminate if stopped up, supply with drops, valve body 25 falls.
In order to eliminate the obstruction at gap place, in illustrated example, elliptical pressurized air or N in recycling diagram 2source of the gas passes into pressurized air or N in setter 23 2gas, and be supplied to cylinder 28 from introducing port 29 through electromagnetic switching valve 30, by repeatedly carry out ON-OFF switching in compared with short period, thereby supply with discontinuously pressurized air or N 2gas, valve body 25 repeatedly rises to the knee-action of upper limit position in compared with short period thus, can eliminate the problem of sandwiching.
The vibration of this valve body 25 can be carried out always, or carries out contain a large amount of coarse particle in feed slurry time, in addition, while the supply of feed slurry being pressed rise, also can link with it due to obstruction.
After pulverizing and stopping, the medium after stirring is taken out together with goods slurry, or extracting out while taking out after goods slurry, the installation site that reduces as shown in the figure nut 34.Electromagnetic switching valve is switched to ON.Thus, the pressurized air importing from introducing port 29 or N 2gas makes more than valve body 25 rises to the edge of valve seat 24.
In the above-described embodiment, rotor 11 and separator 4 are all fixed in axle rotation 5, but are fixed in other embodiments on the different rotary axle of arranged coaxial, are rotated respectively driving.Be installed in the above-mentioned embodiment on same turning axle at rotor and separator, drive unit has a set of, therefore simple in structure, on the other hand, be installed in 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 the wet type agitating ball mill shown in presentation graphs 5.
The turning axle 43 of the ball mill shown in Fig. 5 is made step shaft, embed separator 44 from turning axle lower end, then alternately embed dividing plate 45 and discoid or needle-like rotor 46, then fix stopper 47 in turning axle lower end with screw 48, 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 respectively blade embedded groove 51 on the apparent surface of inner side, the annular baffle 56 that makes two disks keep certain intervals and to be formed with the hole 55 that is communicated with discharge-channel 54 forms, form impeller.
In dispersion manufacture method of the present invention, use wet-type ball mill.As wet-type ball mill, for example, can enumerate the ball mill ス タ mono-ミ Le (trade(brand)name) that Ashizawa Finetech (strain) manufactures; MSC-MILL, SC-MILL, the Attritor MA01SC that manufacture 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; The commodity such as Apex Mill, Ultra Apex Mill, Super ApexMill that longevity industry (strain) is manufactured.Wherein preferred Ultra Apex Mill.
In addition, the ball mill ト タ mono-ミ Le that also preferably uses Ashizawa Finetech (strain) to manufacture in manufacture method of the present invention.This ball mill ス タ mono-ミ Le is following medium stirring-type shredding unit, it possesses one end and has slurry inlet cylindrical container, the stir shaft rotating freely configuring in longitudinally extension mode in said vesse, with the drive unit being connected with above-mentioned stir shaft in said vesse outside, above-mentioned stir shaft has mixing component, space between above-mentioned stir shaft and said vesse internal surface has added crushing medium, importing slurry from above-mentioned slurry inlet on one side utilizes above-mentioned drive unit to rotarily actuate 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, on above-mentioned stir shaft, form the gap that this hollow space is communicated with the above-mentioned space between above-mentioned stir shaft and said vesse internal surface, along with near the medium mobile above-mentioned the other end that arrives said vesse of slurry enters into the above-mentioned hollow space of above-mentioned stir shaft from above-mentioned slurry inlet, carry out returning from above-mentioned gap the cyclic motion in the above-mentioned space between above-mentioned stir shaft and said vesse internal surface.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, rotarilys actuate above-mentioned screen cloth.
In above-mentioned medium stirring-type shredding unit, owing to being rotated by driving for the screen cloth of isolating medium from slurry, arrive near the slurry of screen cloth and medium and also brought out and rotatablely moved, this rotatablely move cause from power be also medium side higher than slurry side, therefore in medium, just produced the power that departs from separating from slurry.Therefore, medium is just kept off screen cloth and is circulated.Thereby can effectively from slurry, remove medium.
The dispersion being obtained by manufacture method of the present invention can be by adding appropriate solvent, solvent evaporates is adjusted to be suitable for the concentration of coating process.As the solvent adding, can enumerate above-mentioned organic solvent (S).
The dispersion being obtained by manufacture method of the present invention itself can be used as active energy ray-curable resin composition and uses, and 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 }-2-hydroxy phenyl]-4, 6-bis-(2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-[4-{ (2-hydroxyl-3-tridecyl oxygen propyl group) oxygen }-2-hydroxy phenyl]-4, 6-bis-(2, 4-3,5-dimethylphenyl)-1, 3, the 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-4-of 2-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, melamine series 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 separately any, also can use two or more simultaneously.
As the usage quantity of various additives as above, consider and give full play to its effect, and will be in not hindering the scope of ultraviolet curing, preferably with respect to active energy ray-curable resin composition 100 mass parts for this injection molding polymerization, respectively in the scope in 0.01～40 mass parts.
As the Photoepolymerizationinitiater initiater that can add in dispersion of the present invention, for example can enumerate benzophenone, 3,3 '-dimethyl-4-methoxy benzophenone, 4,4 '-bis-dimethylamino benzophenone, 4,4 '-bis-diethylamino benzophenone, 4,4 '-dichloro benzophenone, michaelis ketone, 3,3 ', the benzophenones such as 4,4 '-tetra-(t-butyl peroxy carbonyl) benzophenone, xanthone, thioxanthone, 2-methyl thioxanthone, CTX, 2, xanthone, the thioxanthene ketones such as 4-diethyl thioxanthone, the acyloin ethers such as bitter almond oil camphor, benzoin methyl ether, ethoxybenzoin, bitter almond oil camphor isopropyl ether, α-the diones such as benzil, di-acetyl, tetramethyl-thiuram disulfide, to thioether classes such as toluene disulfides, the benzoic acids such as 4-dimethylamino M-nitro benzoic acid, 4-dimethylamino ethyl benzoate, 3,3 '-carbonyl-bis-(7-diethylamino) tonka bean camphor, 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, TMDPO, two (2,4,6-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, benzil dimethyl ketal, benzil-'beta '-methoxy ethyl acetals, o-benzoyl base M-nitro benzoic acid methyl, two (4-dimethylaminophenyl) ketone, to dimethylamino benzoylformaldoxime, α, α,α-dichloro-4-phenoxy acetophenone, amyl group-4-dimethylaminobenzoic acid ester, 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole quinoline dipolymer, two (ethoxy carbonyl methyl) amino of the two trichloromethyl-6-[of 2,4-] phenyl-S-triazine, two trichloromethyl-6-(4-oxyethyl group) phenyl-S-triazines of 2,4-, two trichloromethyl-6-(the bromo-4-oxyethyl group of the 3-) phenyl-S-triazine anthraquinones of 2,4-, 2-tertiary butyl anthraquinone, 2-amyl anthraquinone, β-chloroanthraquinone etc.
Above-mentioned Photoepolymerizationinitiater initiater can use separately or two or more is used in combination.Its consumption is not particularly limited, but in order to keep good light sensitivity, prevent crystallization, coating characteristic variation etc., be preferably 0.05～20 mass parts with respect to active energy ray-curable resin composition 100 mass parts, wherein particularly preferably use by the scope of 0.1～10 mass parts.
As above-mentioned Photoepolymerizationinitiater initiater, be selected from 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, 6-trimethylbenzoyl) phenyl phosphine oxide, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone, a kind of or two or more mixed system in 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone can obtain the coating active energy ray-curable resin composition that solidified nature is high, therefore be particularly preferred.
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 company system), Lucirin TPO (BASFF company 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 the cementability to film base material, for active energy ray-curable resin composition, can use other resin simultaneously.
As above-mentioned other resin, for example, can enumerate the acrylic resin such as methyl-methacrylate resin, methyl methacrylate based copolymer; Polystyrene, Methyl Methacrylate-Styrene based copolymer; Vibrin; Urethane resin; The polybutadiene such as polyhutadiene and butadiene-acrylonitrile based copolymer; The epoxy resin such as bisphenol-type epoxy resin, phenoxy resin and novolac epoxy etc.
Use the active energy ray-curable resin composition of the dispersion that obtained by manufacture method of the present invention to there is following characteristics: while being particularly applied on the film like plastic basis material of film base material etc., also can obtain hardness, and when curing, there is low contraction, the warpage (curling) of film can not occur.In addition, therefore go for the coating of film base material.
Glue spread when being coated with on above-mentioned film base material preferably on various film base materials, is for example 0.1～30g/m by weight after dry 2scope, be preferably 1～20g/m 2scope be coated with.In addition, about the thickness of cured layer, be the hardness that more than 3% film easily reaches hard coat with respect to the thickness of membranaceous base material, be therefore preferred.Wherein, about the thickness of cured layer, more preferably the film in 3～100% scopes with respect to the thickness of membranaceous base material, further the thickness of preferred consolidation layer with respect to the thickness of membranaceous base material in 5～100% scopes, particularly preferably the thickness of cured layer with respect to the thickness of membranaceous base material in 5～50% scopes.
As the membranaceous base material of coating active energy ray-curable resin composition, can use various known base materials.Specifically, can enumerate the such as membranaceous base material of plastics etc.As the membranaceous base material of plastics, for example, can enumerate the film base materials such as polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefine, epoxy resin, melamine resin, cellulosetri-acetate resin, ABS resin, AS resin, norbornene resin, cyclic olefin, polyimide resin etc.
As the coating process of active energy ray-curable resin composition, can use without particular limitation known method, for example can enumerate line rod coating method, the excellent coating method of silk with, airblade coating method with, intaglio plate coating method, reversion intaglio plate coating method, adherography, flexographic printing method, silk screen print method etc.
As the active energy beam irradiating, for example, can enumerate ultraviolet ray or electron beam.While 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 as required light quantity, light source configuration etc., in the situation that using high pressure mercury vapour lamp, conventionally preferably with respect to the lamp of light quantity with 80～160W/cm, be cured by the transfer rate of 5～50m/ minute.On the other hand, while being cured with electron beam, conventionally, preferably with the electron beam booster machinery with 10～300kV acceleration voltage, be cured by the transfer rate of 5～50m/ minute.
As mentioned above, when above-mentioned active energy ray-curable resin composition solidifies, shrinkability is little, and hardness is high.Therefore, by using said composition, can be provided in the film that on film base material, the cured layer of said composition is set and form.This film is suitable for the backing coat of for example various protective membranes, antireflection film, scattering film and the plasma panel taking the optical article such as polarization board protective film, touch pad hard coating film as representative etc.
In addition, above-mentioned active energy ray-curable resin composition is not only suitable for the protective membrane of the plane article such as above-mentioned protection Polarizer, touch pad, is also applicable to for example be used for protecting the surface of the products formeds such as family's electrical article and bumper such as portable phone.
For using active energy ray-curable resin composition to form the method for the protective layer on protection products formed surface, can enumerate finishing, transfer printing, sheet material bonding method etc.
Finishing is that the coating agent being made up of active energy ray-curable resin composition is sprayed, or on products formed, paint after external coating (EC) with printing press such as curtain formula curtain coater, roller coating machine, intaglio plate coating machines, irradiate active energy beam and make the crosslinked method of external coating (EC).
Transfer printing is to be bonded in molding surface by be coated with the transfer materials that active energy ray-curable resin composition forms on the matrix sheet material with release property, then by peeling off matrix sheet material, external coating (EC) is transferred on products formed surface, then irradiate active energy beam and make crosslinked film, or this transfer materials is bonded on products formed surface, then irradiate active energy beam and make crosslinked film, then by peeling off matrix sheet material, external coating (EC) is transferred to the lip-deep method of products formed.
Sheet material bonding method is that the screening glass of the decorative layer that has protective layer and use if desired on matrix sheet material is bonded on plastic molded article, thereby forms the method for protective layer on products formed surface.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 to protective layer with transfer printing, first make transfer materials.Transfer materials can pass through, for example active energy ray-curable resin composition is coated in substrate sheets separately or after coordinating, mix with polyfunctional isocyanate, makes curable resin composition carry out semicure (B-rank) by heating and manufacture.
As the polyfunctional isocyanate who uses with active energy ray-curable resin composition simultaneously, be not particularly limited, can use known various polyfunctional isocyanate.For example can use isophorone diisocyanate, Xylene Diisocyanate, hydrogenated xylene diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, 1, the prepolymer that trimer, polyvalent alcohol and the above-mentioned di-isocyanate reaction of 6-hexane diisocyanate, above-mentioned substance forms etc., hydroxyl contained in polymkeric substance reacted with polyfunctional isocyanate's isocyanate group and carry out B-rank.
For active energy ray-curable resin composition and polyfunctional isocyanate's usage ratio, conventionally preferably the ratio of the hydroxyl of 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 there is 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, preferably plastic sheet, wherein more preferably polyester chips.
In order to manufacture transfer materials, first in substrate sheets, be coated with active energy ray-curable resin composition.This resin combination, in protective layer formation method described later, forms the outermost layer on products formed surface, is that the patterned layer on protection products formed and products formed is avoided reagent and the layer of the infringement that rubs.Method as coating transfer materials with curable resin composition, for example can enumerate the coating methods such as intaglio plate coating method, rolling method, spraying method, dip coating (lip coating), curtain formula curtain coating, the print processes such as woodburytype, silk screen print method etc.When coating, considering from forming good wearability and reagent resistance, is preferably that the mode of 0.5～30 μ m is coated with according to making protective layer thickness, is more preferably wherein that the mode of 1～6 μ m is coated with according to making protective layer thickness.
When above-mentioned protective layer is good to the separability of matrix sheet material; protective layer is directly set on matrix sheet material and is coated with curable resin composition for transfer printing; but in order to improve the separability of protective layer to matrix sheet material; also, before can protective layer being set on matrix sheet material, form release layer comprehensively.As release layer, in the protective layer formation method of products formed described later, for the protective layer transfer of transfer materials, is removed from protective layer when products formed is peeled off matrix sheet material to products formed surface together with matrix sheet material.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 the coating methods such as intaglio plate coating method, rolling method, spraying method, dip coating (lip coating), curtain formula curtain coating, the print processes such as woodburytype, silk screen print method.
In substrate sheets, be coated with transfer printing with after curable resin composition, make it dry.Dry can being undertaken by for example heating.By this heating, when coating contains organic solvent with active energy ray-curable resin composition, organic solvent is removed.Heating temperature is generally 55～160 DEG C, is preferably 100～140 DEG C.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 transfer materials of the present invention, from can easily brushing other layer and batch transfer materials and consider at this resin layer, be preferably in the stage of irradiating before active energy beam in not sticky state.
On transfer materials, also can form patterned layer.Patterned layer is on the resin layer of B-rank, forms usually used as printed layers.As the material of printed layers, can use using 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 the resin such as resin, Synolac as binding agent, the pigment that contains appropriate color or dyestuff are as the coloring printing ink of tinting material.As the method that forms patterned layer, for example, can use the conventional print processes such as adherography, woodburytype, silk screen print method etc.Particularly manifest suitable use adherography and woodburytype in order to carry out polychrome printing and tone.In addition, in monochromatic situation, also can adopt the coating methods such as intaglio plate coating method, rolling method, comma coating method, dip coating.For patterned layer, according to the pattern of wanting to manifest, there is situation and the local situation about arranging of comprehensive setting.In addition, patterned layer can be formed or is combined to form by printed layers and metal steam coating by metal steam coating.
In addition, in the time that protective layer and patterned layer have enough cementabilities to products formed, adhesive linkage can be set, also can form as required adhesive linkage.Adhesive linkage is the layer of the bonding transfer materials with above-mentioned each layer on products formed surface.Adhesive linkage is formed at wants to carry out bonding part in protective layer or patterned layer.That is, be full surface if want bonding part, form all sidedly adhesive linkage.If it is local wanting bonding part, form partly adhesive linkage.As adhesive linkage, suitable use is suitable for thermo-sensitivity or the pressure-sensitive resin of products formed material.For example, when the material of products formed is polyacrylic resin, can use polyacrylic resin.In addition, when the material of products formed is polyphenylene oxide polystyrene resin, polycarbonate-based resin, styrene copolymerized system resin, polystyrene blending resin, use the polyacrylic resin good with these resin affinities, polystyrene resin, polyamide-based resin etc.In addition, when the material of products formed 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 the coating methods such as intaglio plate coating method, rolling method, comma coating method, the 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 in the case of use just to present products formed form own and the transparency, carry out the transfer materials of surface protection processing; can on matrix sheet material, form these layers according to the order of B-rank resin layer and adhesive linkage, 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 for improving these interlayers; protection products formed and patterned layer are avoided the resin layer of chemical reagent infringement, and for example can use liquid two-pack solidified nature urethane resin, melamine series resin, epoxy is the thermoplastic resins such as thermosetting resin, vinyl chloride copolymer resin such as resin.As the formation method that forms back-up coat, there are the coating methods such as intaglio plate coating method, rolling method, comma coating method, the print processes such as woodburytype and silk screen print method.
In order to use above-mentioned transfer materials to form the protective layer of products formed, for example, using carry out as the B rank resin layer of above-mentioned transfer materials and products formed bonding after, irradiate active energy beam and make resin layer curing.Specifically, can enumerate, for example the B-rank resin layer as transfer materials is bonded in to products formed surface, then by the base sheet material of peeling off transfer materials, the B-rank resin layer as transfer materials is transferred on products formed surface, afterwards by active energy beam irradiate make it to carry out energy-ray solidify, thereby carry out the method (transfer printing) of the crosslinking curing of resin layer, and above-mentioned transfer materials is inserted in forming mould, be full of resin at mould intracavitary administration, bonding transfer materials in its surface in obtaining synthetic resin, thereby peeling off matrix sheet material is transferred on products formed, then carrying out energy-ray by irradiation active energy beam solidifies, thereby carry out the method (transfer printing of moulding simultaneously) of the crosslinking curing of resin layer etc.
Also have; for crosslinking curing and the transfer printing process of resin layer; preferably transfer materials is bonded on products formed surface shown in as stated above; then be transferred to products formed surface by peeling off matrix sheet material; carry out afterwards the operation of the order of active energy beam irradiation, but can be also that transfer materials is bonded to behind products formed surface, irradiate active energy beam from matrix sheet material one side; protective layer is solidified, then peel off matrix sheet material and carry out the operation of the order of transfer printing.
As above-mentioned products formed, material is restriction not, for example, can enumerate synthetic resin, carpenter work, their composite product etc.These products formeds can be any in transparent, translucent, opaque.In addition, products formed can be painted, can be also uncoloured.As resin, can enumerate the 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 the 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, Polyphony Ether resin, polyacrylate resin, polyetherimide resin, polyimide resin, liquid-crystal polyester resin, poly-aryl are the Super Engineering resins such as heat stable resin.In addition, can also use the compound resin that has added the strongthener such as glass fibre and mineral filler.
The active energy beam using in formation method as the protective layer of products formed of the present invention, for example, can enumerate electron beam, ultraviolet ray, gamma-rays etc.Illuminate condition can, according to determining for the composition that obtains the transfer materials curable resin composition that protective layer uses, be preferably 50～5000mj/cm according to making accumulated light conventionally 2irradiating, is more preferably 50～2000mj/cm according to making accumulated light 2irradiate.
Below the method that forms the protective layer of products formed by above-mentioned transfer printing is specifically described.First, on products formed with adhesive linkage side under mode configure transfer materials.Then, use and possess the transfer machines such as resistance to rubber-like elastic body, the roll-type transfer machine of such as organo-silicone rubber, reversible transfer machine, by being set as 80～260 DEG C 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 this way to products formed surface.Then,, if peel off matrix sheet material after cooling, on the interface of matrix sheet material and resin layer, peel off.In addition, in the time release layer being set on matrix sheet material, if peel off matrix sheet material, on the interface of release layer and resin layer, peel off.Finally, by irradiating active energy beam, make to be transferred to the complete crosslinking curing of resin layer on products formed, formed protective layer.The operation of further, irradiating active energy beam also can be carried out before peeling off matrix sheet material operation.
Below, to being specifically described by the method that uses injection molding while moulding transfer printing to form products formed protective layer.First, in the mold for forming being formed by movable mold and fixed mould, use adhesive linkage as inner side, put into transfer materials according to the mode that makes matrix sheet material contact fixed mould in a word.Now, also can put into one by one transfer materials sheet, also can intermittently put into the essential part of overlength transfer materials.While using overlength transfer materials, use the e Foerderanlage with location positioning mechanism, make the patterned layer of transfer materials and the orientation of mold for forming reach consistent.In addition, while intermittently putting into transfer materials, detected by sensor behind the position of transfer materials, if with movable mold and fixed mould stationary transfer material, conventionally transfer materials can be fixed on to identical position, the position of patterned layer can not be departed from, and is therefore easily.Close after mold for forming, the cast gate arranging from movable mold, to injection fillers molten resin in mould, in forming products formed, bonds to transfer materials on its surface.After synthetic resin is cooling, open mold for forming and take out synthetic resin.Finally, peel off after matrix sheet material, make the complete crosslinking curing of resin layer by irradiating active energy beam, thereby form protective layer.In addition, also can, irradiating after active energy beam, peel off matrix sheet material.
Also have, transfer materials of the present invention not only can form transfer materials manufacture composition with curable resin composition, can also pass through the coating methods such as above-mentioned intaglio plate coating method, rolling method, comma coating method, the paintings such as print process, spraying method such as woodburytype and silk screen print method are contained on the products formeds such as film, sheet material, forming composition.
Below sheet material bonding method is described.As sheet material bonding method, for example can enumerate ready-made protective layer is formed with matrix sheet material and the products formed of sheet material bonding, then make it thermofixation by heating, thereby carry out the method (rear bonding method) of the crosslinking curing of B-rank resin layer, and above-mentioned protective layer is formed with in sheet material insertion forming mould, be full of resin at mould intracavitary administration, in obtaining synthetic resin, make its surface and protective layer formation sheet material carry out bonding, then make it thermofixation by heating, thereby carry out the method (bonding method of moulding simultaneously) of the crosslinking curing of resin layer etc.
Above-mentioned protective layer forms can be manufactured by the method etc. of for example manufacturing above-mentioned transfer materials with sheet material.Now, on matrix sheet material when coated solidified resin combination, in the bonding hypodynamic situation of matrix sheet material and curable resin composition, also can 1, on the face of the coated solidified resin combination of matrix sheet material primer coating, and be coated with curable resin composition thereon, 2, the method such as surface by activation matrix sheet materials such as corona discharges provides the cementability of matrix sheet material and curable resin composition.As priming paint above-mentioned 1, middle use, for example can use liquid two-pack solidified nature urethane resin, melamine series resin, epoxy is the thermosetting resins such as resin, the thermoplastic resin such as vinyl chloride copolymer resin, water based emulsion of being made up of acrylic resin.As the sticky cloth method of caking agent, for example, can enumerate the coating methods such as intaglio plate coating method, rolling method, comma coating method, the print processes such as woodburytype, silk screen print method.
In the method for above-mentioned manufacture transfer materials, after active energy ray-curable resin composition painting is contained on base sheet material, irradiate active energy beam.Utilize this active energy beam to make (methyl) acryl in curable resin composition carry out bonding by Raolical polymerizable, form three-dimensional cross-linked, make curable resin composition solidify.
As actinic energy ray curable resion composition, while using the active energy ray-curable resin composition that contains organic solvent, also can after being applied on matrix sheet material, remove organic solvent.Removing of organic solvent, for example, can carry out after irradiation active energy beam, also can before irradiation active energy ray curable, carry out.As the method for removing, can directly place and wait for volatilization, also can use drying machine etc. to be dried, but the temperature while conventionally preferably removing organic solvent is 70～130 DEG C, carries out about 10 seconds～10 minutes.
Also have; protective layer formation is not limited to above-mentioned form by the formation of sheet material; for example be to present form own and the transparency of products formed at application target, the protective layer that carries out surface protection processing forms while using sheet material; can on matrix sheet material, form successively curing resin layer and adhesive linkage, omit and form by protective layer the patterned layer forming with sheet material.
In addition; when protective layer forms and has resin layer in the patterned layer with sheet material; also can back-up coat be set at these interlayers; back-up coat is the fusible resin layer for improving these interlayers, and for example can use liquid two-pack solidified nature urethane resin, melamine series resin, epoxy is the thermoplastic resins such as thermosetting resin, vinyl chloride copolymer resin such as resin.As the formation method that forms back-up coat, there are the coating methods such as intaglio plate coating method, rolling method, comma coating method, the print processes such as woodburytype and silk screen print method.
As the products formed using in sheet material bonding method, for example, can use illustrative products formed in above-mentioned transfer printing.
Form the method with sheet material as bonding forming product in rear bonding method and protective layer, for example can be set forth in protective layer and form with coating adhesive on the matrix sheet material of sheet material and/or products formed surface, protective layer is formed with carrying out bonding method in matrix sheet material and the products formed surface of sheet material; Form with pasting after self adhesive tape on the matrix sheet material of sheet material and/or two faces on products formed surface at protective layer, peel off the demoulding screening glass of two self adhesive tapes on face, expose adhesive face, protective layer is formed with carrying out bonding method in matrix sheet material and the products formed surface of sheet material; Form with after coating adhesive formation bonding plane on the matrix sheet material of sheet material at protective layer; 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 to matrix sheet material and products formed surface.At the same time in moulding bonding method, the heat when not using caking agent in-molded makes the melting of matrix sheet material, protective layer is formed and become one with sheet material and products formed, thereby can form use sheet material and products formed by bonding protective layer.Herein, as the caking agent using in above-mentioned rear bonding method, 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 products formed by above-mentioned rear bonding method is specifically described.First, on products formed with adhesive linkage side under mode configuration protection layer formation sheet material.Then, use and possess heat resistant rubber shape elastomerics, the transfer machine such as roll-type transfer machine, up down transfer machine of such as organo-silicone rubber, by being set as 80～260 DEG C of temperature, pressure 50～200kg/m 2the heat resistant rubber shape elastomerics of condition, form and apply heat and/or pressure by protective layer one side of sheet material from protective layer.Just adhesive linkage is bonded in this way to products formed surface.Finally, make the complete crosslinking curing of resin layer that forms on products formed by heating, form protective layer.
Below, to being specifically described by the method that uses injection molding while moulding transfer printing to form products formed protective layer.First, in the mold for forming being formed by movable mold and fixed mould, use adhesive linkage as inner side, put into protective layer formation sheet material according to the mode that makes matrix sheet material contact fixed mould in a word.Now, also can put into one by one transfer materials sheet, also can intermittently put into the essential part of overlength transfer materials.Use the protective layer of overlength to form while using sheet material, use the e Foerderanlage with location positioning mechanism, make protective layer the formation patterned layer of sheet material and the orientation of mold for forming reach consistent.In addition; intermittently putting into protective layer forms while using sheet material; detect that by sensor protective layer forms with behind the position of sheet material; if with movable mold and the fixing protective layer formation sheet material of fixed mould; conventionally protective layer formation can be fixed on to identical position with sheet material; the position of patterned layer can not be departed from, and is therefore easily.Close after mold for forming, the cast gate arranging from movable mold is to injection fillers molten resin in mould, in forming products formed, protective layer formed and bonded on its surface with sheet material.After synthetic resin is cooling, open mold for forming and take out synthetic resin.Finally, 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 example specialize, and are all based on quality.
Embodiment 1
Having equipped in the reaction unit of whipping appts, cooling tube, dropping funnel and nitrogen ingress pipe, add glycidyl methacrylate (following, brief note is for " GMA ") 250g, methyl iso-butyl ketone (MIBK) be (following, brief note is for " MIBK ") 1000g and tert-butyl peroxide ethylhexoate (following, brief note is for " P-O ") after 10g, under nitrogen gas stream, make the temperature in system be warmed up to approximately 90 DEG C with approximately 1 hour, be incubated 1 hour.Then,, from having added in advance by GMA750g, the dropping funnel of the mixed solution of P-O30g composition dripped mixed solution with approximately 2 hours under nitrogen gas stream in system, was incubated at the same temperature 3 hours.Then, be warmed up to 120 DEG C, be incubated 2 hours.Be cooled to, after 60 DEG C, nitrogen ingress pipe be replaced to air leading-in conduit, after adding vinylformic acid (following, to note by abridging as " AA ") 507g, p methoxy phenol 2.3g and triphenyl phosphine 9.3g to mix, under air blasts, be warmed up to 110 DEG C.At identical temperature, be incubated after 8 hours, add p methoxy phenol 1.6g, cooling, it is 50% that interpolation MIBK makes nonvolatile component, obtains the solution of reactive dispersion agent for silicon dioxide microparticle (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 approximately 30,000.
Embodiment 2
Use the reaction unit identical with embodiment 1, add GMA125g, methyl methacrylate is (following, brief note is " MMA ") 125g, after MIBK1000g and P-O10g, under nitrogen gas stream, make the temperature in system be warmed up to approximately 90 DEG C with approximately 1 hour, be incubated 1 hour.Then, from having added in advance the dropping funnel of the mixed solution being formed by GMA375g, MMA375g, P-O30g, under nitrogen gas stream, in system, drip mixed solution with approximately 2 hours, be incubated at the same temperature 3 hours.Then, be warmed up to 120 DEG C, be incubated 2 hours.Be cooled to, after 60 DEG C, nitrogen ingress pipe be replaced to air leading-in conduit, after adding AA254g, p methoxy phenol 2.3g and triphenyl phosphine 9.3g to mix, under air blasts, be warmed up to 110 DEG C.At identical temperature, be incubated after 8 hours, add p methoxy phenol 1.6g, cooling, it is 50% that interpolation MIBK makes nonvolatile component, obtains the solution of reactive dispersion agent for silicon dioxide microparticle (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 approximately 40,000.
Embodiment 3
Use the reaction unit identical with embodiment 1, add GMA75g, MMA175g after MIBK1000g and P-O8g, made the temperature in system be warmed up to approximately 90 DEG C with approximately 1 hour under nitrogen gas stream, was incubated 1 hour.Then, from having added in advance the dropping funnel of the mixed solution being formed by GMA300g, MMA700g, P-O23g, under nitrogen gas stream, in system, drip mixed solution with approximately 2 hours, be incubated at the same temperature 3 hours.Then, be warmed up to 120 DEG C, be incubated 2 hours.Be cooled to, after 60 DEG C, nitrogen ingress pipe be replaced to air leading-in conduit, after adding AA152g, p methoxy phenol 2.3g and triphenyl phosphine 5.6g to mix, under air blasts, be warmed up to 110 DEG C.At identical temperature, be incubated after 8 hours, add p methoxy phenol 1.6g, cooling, it is 50% that interpolation MIBK makes nonvolatile component, obtains the solution of reactive dispersion agent for silicon dioxide microparticle (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 approximately 70,000.
Embodiment 4
Reactive dispersion agent (A-1), dipentaerythritol acrylate (DPHA) 25g, silicon dioxide microparticle (" Aerosil 200 " that Japanese AEROSIL (strain) manufactures of 25g will be counted by solid substance, the average about 12nm of initial particle) 50g and MIBK200g mix, and obtains mixture.
The Ultra Apex Mill " UAM015 " that uses longevity industry (strain) to manufacture disperses the silicon dioxide microparticle in this mixture.Ultra Apex Mill used herein " UAM015 " is that to have diameter of stator bore 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 (in Fig. 2, not possessing the type of conveying end 19).Manufacture when dispersion, in wet-type ball mill to fill the zirconium oxide bead of median particle diameter as 30 μ m with respect to wet-type ball mill volume as the amount of 50 volume %.
From supplying opening, the said mixture in head tank is provided to wet-type ball mill with pump.Make rotor there is 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 mixture that silicon dioxide microparticle is dispersed in reactive dispersion agent (A-1), DPHA and MIBK and the dispersion forming.Remove the MIBK in the dispersion obtaining 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 is not produced to sediment for 2 months lower preservation of room temperature (25 DEG C) yet, and package stability is good.In addition, making under the following conditions cured coating film, while measuring pencil hardness, is 5H.
The measuring method of pencil hardness
1, the making method of cured coating film
Above (thickness 10 μ m) with line rod coating machine, active energy ray-curable resin composition to be coated on to cellulosetri-acetate (TAC) film (thickness 40um), be dried 1 minute at 70 DEG C, under nitrogen, make high pressure mercury vapour lamp by 250mJ/cm 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, the curing overlay film of the pencil drawing thread test evaluation higher level test film that is 500g by load.
Embodiment 5～10
Except the mixing shown in carry out table 1, manufacture 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.The pencil hardness of measuring package stability and cured coating film by the mode identical with embodiment 4, the results are shown in table 1.
Table 1
The footnote of table 1
The silicon dioxide microparticle that Aerosil 200: Japanese AEROSIL (strain) manufactures.Initial particle 17nm.
The silicon dioxide microparticle that Aerosil 50: Japanese AEROSIL (strain) manufactures.Initial particle 30nm.
EMIX-100:(strain) silicon dioxide microparticle of imperial gloomy manufacture.Initial particle 100nm.
EMIX-300:(strain) silicon dioxide microparticle of imperial gloomy manufacture.Initial particle 300nm.
Disperse stability zero: 2 month without sedimentation.
Comparative example 1
Use silicon dioxide microparticle (Japanese AEROSIL (strain) system, Aerosil 50, the average about 30nm of initial particle) 50g, bisphenol A epoxy acrylate (DIC (strain) system, 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.
Add 2 parts of Irgacure-184 in this compare with in 100 parts of reactive dispersions, obtain compare active energy ray-curable resin composition.Compare does not produce sediment with active energy ray-curable resin composition in the lower moment of preserving 1 hour of room temperature (25 DEG C).In addition, making cured coating film by the mode identical with embodiment 4, while measuring pencil hardness, is 2H.
Comparative example 2
Together with 50 parts of silicon dioxide microparticles (Aerosil 50, the average about 30nm of initial particle), DPHA50 part, MIBK200 part and zirconium oxide bead 600 parts (bead diameter 0.3mm), join in vial, in PAINT SHAKER, mix 2 hours, after taking-up, remove MIBK with vaporizer, obtain nonvolatile component concentration and be 50% the reactive dispersion of compare.
Add 2 parts of Irgacure-184 in this compare with in 100 parts of reactive dispersions, obtain compare active energy ray-curable resin composition.Compare does not produce sediment with active energy ray-curable resin composition in the lower moment of preserving 1 week of room temperature (25 DEG C).In addition, making cured coating film by the mode identical with embodiment 4, while measuring pencil hardness, is 3H.
Comparative example 3
In dry air, for the solution being formed by sulfydryl propyl trimethoxy silicane 221g, dibutyl tin laurate 1g, dripped while stirring isophorone diisocyanate 222g at 50 DEG C with 1 hour, then stir 3 hours at 60 DEG C.Dripping wherein ARONIX M-305[East Asia synthetic (strain) at 30 DEG C with 1 hour makes, pentaerythritol triacrylate/tetramethylol methane tetraacrylate=60/40 (% by weight)] 549g, then heated and stirred 10 hours at 60 DEG C, thus organic compound obtained.Under nitrogen gas stream, by 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 stirs after 4 hours at 60 DEG C, adds original acid A ester 1.4g, then under same temperature heated and stirred 1 hour, then desolventizing, obtains nonvolatile component concentration and is 30% the reactive dispersion of compare.
Add 2 parts of 100 parts of reactive dispersions for this compare, DPHA40 part, Irgacure-184 (light trigger), obtain compare active energy ray-curable resin composition.Compare does not produce sediment with active energy ray-curable resin composition in the lower moment of preserving 1 week of room temperature (25 DEG C).In addition, making cured coating film by the mode identical with embodiment 1, while measuring pencil hardness, is 2H.
Nomenclature
1...... head tank, 2...... feedstock pump, 3...... grind type wet type agitating ball mill, 4...... separator, 5...... turning axle, 6...... chuck, 7...... stator, 9...... discharge-channel, 11...... rotor, 12...... electric motor, 13...... belt pulley, 14...... belt pulley, 15...... swivel joint, 16...... supplying opening, 17...... screen cloth support, 18...... screen cloth, 19...... conveying end, 21...... rotating disk, 22...... blade, 23...... setter, 24...... valve seat, 25...... valve body, 26...... cylinder, 27...... introducing port, 28...... cylinder, 29...... pressurized air or N 2conductance entrance, 30...... electromagnetic switching valve, 31...... piston, 32...... bar, 33...... spring, 34...... nut, 43...... turning axle, the step of 43a...... turning axle 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...... pressurized air or N 2air valve, 61...... valve, 62...... pressurized air or N 2air valve, 63...... pressurized air or N 2air valve, 64...... valve, 65...... relief outlet, 66...... relief outlet, 67...... goods tank.

Claims (11)

1. the manufacture method of a dispersion; this manufacture method is characterised in that, (methyl) acrylic acid polymer (B) that to have (methyl) acryl and hydroxyl and (methyl) acryl equivalent by containing in molecular structure and be 200～600g/eq, hydroxyl value be 90～280mgKOH/g and the slurry of silicon dioxide microparticle (F) are provided in stator from the described slurry supplying opening of the wet-type ball mill that comprises following structure:
1) inside be filled with medium round tube type stator,
2) be arranged at described stator lower end slurry supplying opening,
3) be positioned at the axle center of described stator, and its top be provided with hollow form liquid discharge channel the turning axle that is rotated driving,
4) with described turning axle carry out coaxial rotating driving rotor and
5) be arranged at described turning axle top with coaxial shape, and discharge the impeller type separator that is rotated driving that parting liquid form forms to be communicated with described hollow form liquid discharge channel,
In stator, rotarily actuate described rotor, medium and slurry are uniformly mixed, make the silicon dioxide microparticle (F) in slurry pulverize and be dispersed in (methyl) acrylic acid polymer (B), by centrifugal action, slurry is separated in the separator portion rotariling actuate with medium simultaneously, will attract the slurry to position, separator axle center to discharge from the hollow form discharge-channel in described turning axle.
2. according to the manufacture method of the dispersion described in 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 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 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 claim 1, it is characterized in that, described (methyl) acrylic acid polymer (B) is that the monomer (c) that makes to have (methyl) acryl and carboxyl carries out addition reaction with (methyl) acrylic acid polymer (a1) with epoxy group(ing) and the resultant of reaction (b1) that forms, or the monomer (d) that makes to have (methyl) acryl and epoxy group(ing) carries out addition reaction with monomer (methyl) acrylic acid polymer (a2) with carboxyl and the resultant of reaction (b2) that forms.
6. according to the manufacture method of the dispersion described in 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 in there is epoxy group(ing) (methyl) acrylic acid polymer be to make to obtain taking (methyl) glycidyl acrylate as polymerizable monomer polymerization that must monomer component.
7. according to the manufacture method of the dispersion described in claim 1, wherein, described medium is to be the zirconium white particulate of 15～300 μ m by the median size of median particle diameter.
8. an energy ray curable resin composition, is characterized in that, contains the dispersion being obtained by the manufacture method described in any one in claim 1～7.
9. a film, is characterized in that, has the cured layer that the energy ray curable resin composition described in claim 8 is solidified and obtain on membranaceous base material.
10. according to the film described in 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 claim 9, and wherein, the thickness of described cured layer is 3～100% with respect to the thickness of membranaceous base material.
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