CN103842396A - Active energy beam-curable resin composition, method for producing thereof, coating, coating film, and film - Google Patents
Active energy beam-curable resin composition, method for producing thereof, coating, coating film, and film Download PDFInfo
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- CN103842396A CN103842396A CN201280047944.3A CN201280047944A CN103842396A CN 103842396 A CN103842396 A CN 103842396A CN 201280047944 A CN201280047944 A CN 201280047944A CN 103842396 A CN103842396 A CN 103842396A
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract
Provided are: an active energy beam-curable resin composition having outstanding conservation stability, a cured coating film thereof which exhibits extremely high surface hardness, transparency, curl-resistance and alkali-resistance; a coating containing said resin composition; a coating film made from said coating; and a film having said coating film layer. The composition contains, as essential ingredients, inorganic microparticles (A) having an average particle size within the range of 95-250nm, and an acrylic polymer (X) having a weight-average molecular weight (Mw) that falls within the range of 5,000 to 80,000, and which has a (meth)acryloyl group within the molecular structure. The composition is characterized by containing 35-60 parts by mass of the inorganic microparticles (A) with respect to a total of 100 parts by mass of nonvolatile components.
Description
Technical field
The present invention relates to excellent storage stability and then its cured coating film and demonstrate very high surface hardness, the transparency, resistance to crimp tendency and alkali-proof active energy ray-curable resin composition, the coating that contains this resin combination, the film being formed by this coating, and there is the film of this film layer.
Background technology
Make inorganic microparticle-dispersed in resinous principle and inorganic microparticle-dispersed type active energy ray-curable resin composition compared with the resin combination only being formed by organic material, as realizing the high rigidity of cured coating film, the adjustment of specific refractory power, the type material of giving contour performance-based, new function of electroconductibility, receive much concern in recent years.The purposes of this resin combination is varied; for example; be this feature of high rigidity at performance cured coating film; can not scratch as the surface of protection products formed, indicating meter hard paint time; compared with using the situation of the resin combination only being formed by organic material, can obtain showing the hard paint of the resistance to marring that is much better than it.Wherein, in order to make also excellent hard paint of high rigidity more and resistance to crimp tendency, adding more inorganic particles is effectively, but the resin combination that contains a large amount of inorganic particles easily produce inorganic particles through time precipitation, there is the poor shortcoming of storage stability.In addition,, in the inadequate situation of the dispersion of inorganic particles in resinous principle, resin combination lacks storage stability, and the transparency of film also reduces.
As the hard paint being formed by inorganic microparticle-dispersed type active energy ray-curable resin composition, known a kind of anti-dazzle film resin combination, its contain acrylic polymers addition vinylformic acid to glycidyl methacrylate and the silicon dioxide microparticle (referring to patent documentation 1) of polymkeric substance, Viscoat 295, polyfunctional carbamate acrylate and the median size scope that is 297～540nm.This dispersion is compared with the hard paint only being formed by organic, although can obtain the film of high rigidity, but in the nonvolatile component of resin combination, only contain the silicon dioxide microparticle of 17% left and right, therefore do not reach requirement level of market demand higher surface hardness, in recent years.In addition, owing to being the resin combination of anti-dazzle film purposes, therefore the particle diameter of contained silicon dioxide microparticle is very large, does not realize transparent high cured coating film.In addition; the reactive dispersion of known one; it contains acryl equivalent is that 214g/eq, hydroxyl value are alumina particulate, the zirconium white particulate (referring to patent documentation 2) of 262mgKOH/g, the weight-average molecular weight acrylic polymers that is 40,000 and the median size scope that is 55～90nm.This dispersion is compared with the hard paint only being formed by organic, although can obtain the film of high rigidity, but the median size of the inorganic particles in dispersion is little, therefore can not get for the desired level of the hardness of film recently day by day improving is sufficient hardness of film.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-62539 communique
Patent documentation 2: TOHKEMY 2007-289943 communique
Summary of the invention
the problem that invention will solve
The problem to be solved in the present invention is to provide excellent storage stability and then its cured coating film to demonstrate very high surface hardness, the transparency, resistance to crimp tendency and alkali-proof active energy ray-curable resin composition, the coating that contains this resin combination, the film being formed by this coating, and there is the film of this film layer.
for the scheme of dealing with problems
The inventor etc. conduct in-depth research in order to address the above problem, found that, the excellent storage stability of active energy ray-curable resin composition as described below, and surface hardness and the transparency that the film being formed by this resin combination performance is very high, thereby complete the present invention, described active energy ray-curable resin composition is characterised in that, its inorganic particles (A) and weight-average molecular weight (Mw) that contains the scope that the median size that records based on dynamic light scattering method is 95～250nm is 5, 000～80, 000 scope, and in molecular structure, there is the acrylic polymers (X) of (methyl) acryl as neccessary composition, in its nonvolatile component 100 mass parts, contain aforementioned inorganic particles (A) with the scope of 35～60 mass parts.
; the present invention relates to a kind of active energy ray-curable resin composition; it is characterized in that; its inorganic particles (A) and weight-average molecular weight (Mw) that contains the scope that the median size that records based on dynamic light scattering method is 95～250nm is 5; 000～80; in 000 scope and molecular structure, there is the acrylic polymers (X) of (methyl) acryl as neccessary composition, in its nonvolatile component 100 mass parts, contain aforementioned inorganic particles (A) with the scope of 35～60 mass parts.
The invention still further relates to a kind of manufacture method of active energy ray-curable resin composition, it is characterized in that, use has the container that is filled with medium in inside, turning axle, there is the agitating vane rotating with the turning axle of aforementioned rotating shaft coaxle and by the rotary actuation of aforementioned turning axle, be arranged at the supplying opening of the raw material of aforementioned container, be arranged at aforementioned container dispersion relief outlet and be disposed in the wet-type ball mill that aforementioned turning axle runs through the gland seal device of the part of container, aforementioned axis seal apparatus has 2 mechanical seal unit, and the structure that the sealing with these 2 mechanical seal unit is sealed by outside seal liquid, from the aforementioned supplying opening of described wet-type ball mill to aforementioned supply for receptacles inorganic particles (A) with weight-average molecular weight (Mw) 5, 000～80, in 000 scope and molecular structure, there is the acrylic polymers (X) of (methyl) acryl as the resinous principle of neccessary composition, in aforementioned container, make turning axle and agitating vane rotation, be uniformly mixed medium and raw material, carry out thus pulverizing and the dispersion of this inorganic particles (A) in aforementioned resin composition of aforementioned inorganic particles (A), then, discharge from aforementioned relief outlet.
The invention still further relates to the coating that contains aforementioned active energy ray-curable resin composition.
The invention still further relates to the film being formed by aforementioned coating.
The invention still further relates to the laminate film at the single or double of plastics film with aforementioned film.
the effect of invention
According to the present invention, can provide excellent storage stability and then its cured coating film to demonstrate very high surface hardness, the transparency, resistance to crimp tendency and alkali-proof active energy ray-curable resin composition, this resin combination, the coating that contains this resin combination, the film being formed by this coating, and there is the film of this film layer.
Brief description of the drawings
Fig. 1 is the longitudinal diagram of operable wet-type ball mill in the time manufacturing resin combination of the present invention.
Fig. 2 is the longitudinal diagram of the gland seal device of operable wet-type ball mill in the time manufacturing resin combination of the present invention.
Embodiment
Inorganic particles (A) and weight-average molecular weight (Mw) that active energy ray-curable resin composition of the present invention contains the scope that the median size that records based on dynamic light scattering method is 95～250nm are 5; in 000～80,000 scope and molecular structure, there is the acrylic polymers (X) of (methyl) acryl as neccessary composition.
Active energy ray-curable resin composition of the present invention, by containing aforementioned inorganic particles (A), can obtain the cured coating film that surface hardness is higher.The scope that the median size (dynamic light scattering method) of aforementioned inorganic particles (A) is 95～250nm, in the time that median size is less than 95nm, the surface hardness of gained film reduces, and in the time exceeding 250nm, the transparency of gained film reduces.Wherein, can have hardness and transparent aspect concurrently with higher level from gained film, the scope that preferably median size is 100～180nm.
In addition, the median size recording based on dynamic light scattering method of the aforementioned inorganic particles (A) in the present invention refers to according to " ISO13321 " and measures, the value calculating by the Cumulant Method Using (cumulant method), be specially following value: active energy ray-curable resin composition MIBK is diluted, after making the MIBK solution of concentration 5%, " ELSZ-2 " that uses this MIBK solution particle size determination device (Otsuka Electronics Co., Ltd. to manufacture) value that records.
The contained aforementioned inorganic particles (A) of active energy ray-curable resin composition of the present invention can be by making the inorganic particles (a) as raw material be dispersed in the contained resinous principle of active energy ray-curable resin composition of the present invention, obtain in the resinous principle of neccessary composition using aforementioned acrylic polymers (X).Aforementioned inorganic particles (a) for example can list: the particulates such as silicon-dioxide, aluminum oxide, zirconium white, titanium dioxide, barium titanate, antimonous oxide.These can distinguish use separately, also can be used in combination two or more.
In the middle of these inorganic particles (a), from easily obtaining and aspect easy and simple to handle, preferably silicon dioxide microparticle.Silicon dioxide microparticle for example can list: wet method silicon dioxide microparticle, dry method silicon dioxide microparticle etc.Aforementioned wet method silicon dioxide microparticle for example can list: the silicon dioxide microparticle that the neutralization of water glass mineral acid is obtained.While using wet method silicon dioxide microparticle as aforementioned inorganic particles (a), from easily the median size of the inorganic particles gained resin combination (A) being adjusted to the aspect of aforementioned preferred value, preferably using median size is the wet method silicon dioxide microparticle of the scope of 95～250nm.Aforementioned dry method silicon dioxide microparticle for example can list: the silicon dioxide microparticle obtaining by the silicon tetrachloride that burns in oxygen or hydrogen flame.While using dry method silicon dioxide microparticle as aforementioned inorganic particles (a), from easily the median size of the inorganic particles gained resin combination (A) being adjusted to the aspect of aforementioned preferred value, preferably use average primary particle diameter to assemble at 3～100nm, the dry method silicon dioxide microparticle that is preferably the scope of 5～50nm the second particle forming.
In the middle of aforementioned silicon dioxide microparticle, from obtaining the aspect of the cured coating film that surface hardness is higher, preferably dry method silicon dioxide microparticle.
In the present invention, can use various silane coupling agents to import functional group on the surface of aforementioned inorganic particles (a).Surface by this inorganic particles (a) imports functional group, make its with molecular structure in there is the organic composition such as acrylic polymers (X) of (methyl) acryl miscibility improve, storage stability raising.
For aforementioned silane coupling agent, for example, can list: vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-triethoxysilicane, to styryl Trimethoxy silane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxyl silane, 3-acryloxy 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-Ding pitches base) propyl group amine, N-phenyl-3-TSL 8330, the hydrochloride of N-(vinyl benzyl)-2-amino-ethyl-3-TSL 8330, special aminosilane, 3-urea groups 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, the vinyl-based silane coupling agents such as vinyl three (2-methoxy ethoxy) silane,
The silane coupling agent of the epoxiess such as 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;
To the silane coupling agent of the styrenics such as styryl Trimethoxy silane;
The silane coupling agent of (methyl) acryloyl-oxy base class such as 3-methacryloxypropyl methyl dimethoxysilane, 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxyl silane;
The silane coupling agent of the aminos such as 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-Ding pitches base) propyl group amine, N-phenyl-3-TSL 8330;
The silane coupling agent of the urea groups classes such as 3-urea groups propyl-triethoxysilicane;
The silane coupling agent of the chloropropyl classes such as 3-r-chloropropyl trimethoxyl silane;
The silane coupling agent of the sulfydryl classes such as 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl trimethoxy silicane;
The silane coupling agent of two (triethoxysilylpropyltetrasulfide) tetrasulfide sulfides class;
The isocyanates silane coupling agents such as 3-isocyanate group propyl-triethoxysilicane.These silane coupling agents can be distinguished use separately, also can be used in combination two or more.In the middle of these; from can obtain with molecular structure there is the high and transparent also aspect of excellent cured coating film of miscibility excellence, the surface hardness of the organic composition such as acrylic polymers (X) of (methyl) acryl; the preferably silane coupling agent of (methyl) acryloyl-oxy base class, more preferably 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl trimethoxy silane.
Active energy ray-curable resin composition of the present invention contain weight-average molecular weight (Mw) be in 5,000～80,000 scope and molecular structure, there is (methyl) acryl acrylic polymers (X) as resinous principle.
The acrylic polymers (X) in aforementioned molecular structure with (methyl) acryl is 5 by making its weight-average molecular weight (Mw); 000～80; 000 scope, can stably disperse aforementioned inorganic particles (A), and therefore the storage stability of resin combination improves.Be less than at 5,000 o'clock in weight-average molecular weight (Mw), the dispersiveness of aforementioned inorganic particles (A) reduces, and therefore the transparency of the storage stability of resin combination, cured coating film reduces.In addition, exceed at 80,000 o'clock in weight-average molecular weight (Mw), viscosity raises, and becomes and is difficult to process as coating purposes.Wherein, from the dispersiveness of aforementioned inorganic particles (A), more excellent and active energy ray-curable resin composition becomes the aspect that is suitable for the viscosity applying, and weight-average molecular weight (Mw) is preferably 8,000～50,000 scope, more preferably 10,000～45,000 scope.
In addition, in the present invention, weight-average molecular weight (Mw) is the value that uses gel permeation chromatography (GPC) to record according to following condition.
Determinator: TOSOH Co., Ltd manufactures HLC-8220
Chromatographic column: TOSOH Co., Ltd manufactures guard column HXL-H
+ TOSOH Co., Ltd manufactures TSKgel G5000HXL
+ TOSOH Co., Ltd manufactures TSKgel G4000HXL
+ TOSOH Co., Ltd manufactures TSKgel G3000HXL
+ TOSOH Co., Ltd manufactures TSKgel G2000HXL
Detector: RI(differential refractometer)
Data processing: TOSOH Co., Ltd manufactures SC-8010
Condition determination: 40 DEG C of column temperatures
Solvents tetrahydrofurane
Flow velocity 1.0ml/ minute
Standard: polystyrene
Sample: (100 μ l) by the solution that is scaled the tetrahydrofuran solution micro-strainer filtration of 0.4 % by weight by resin solid composition and obtain
In addition; the also aspect of excellent cured coating film of resistance to crimp tendency from can obtain thering is high surface hardness, while solidifying; (methyl) acryl equivalent in aforementioned molecular structure with the acrylic polymers (X) of (methyl) acryl is preferably the scope of 220g/eq～1650g/eq, the more preferably scope of 240g/eq～1100g/eq.And then from obtaining the aspect of active energy ray-curable resin composition of ageing stability excellence, the more preferably scope of 350g/eq～800g/eq, is particularly preferably the scope of 380g/eq～650g/eq.
The acrylic polymers (X) in aforementioned molecular structure with (methyl) acryl for example can list: the compound (y) that makes to have reactive functional groups and (methyl) acryl carry out polymerization as neccessary composition and acrylic polymers (Y) react with the compound (z) with functional group that the reactive functional groups that can have with aforesaid compound (y) react and (methyl) acryl and the polymkeric substance that obtains.
More specifically, can list: the compound (y1) that makes to have epoxy group(ing) and (methyl) acryl carry out polymerization as neccessary composition and acrylic polymers (Y1) react with the compound (z1) with carboxyl and (methyl) acryl and must acrylic polymers (X1); The compound (y2) that makes to have carboxyl and (methyl) acryl carry out polymerization as neccessary composition and acrylic polymers (Y2) react with the compound (z2) with epoxy group(ing) and (methyl) acryl and must acrylic polymers (X2); The compound (y3) that makes to have hydroxyl and (methyl) acryl carry out polymerization as neccessary composition and acrylic polymers (Y3) react with the compound (z3) with isocyanate group and (methyl) acryl and must acrylic polymers (X3) etc.
First, aforementioned acrylic polymers (X1) is described.
Can be the homopolymer of the aforementioned compound (y1) with epoxy group(ing) and (methyl) acryl as the aforementioned acrylic polymers (Y1) of the raw material of aforementioned acrylic polymers (X1), can be also the multipolymer with other polymerizable compounds (v1).
For the compound (y1) with epoxy group(ing) and (methyl) acryl of the material composition as aforementioned acrylic polymers (Y1), for example can list: (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 butyl ester, (methyl) vinylformic acid-4, 5-epoxy pentyl ester, (methyl) vinylformic acid-6, 7-epoxy pentyl ester, α-ethyl (methyl) vinylformic acid-6, 7-epoxy pentyl ester, (methyl) senecioate-methyl glycidyl ester, (methyl) vinylformic acid-3, 4-epoxy cyclohexyl, interior ester modified (methyl) vinylformic acid-3, 4-epoxy cyclohexyl, vinyl cyclohexene oxide compound etc.These can distinguish use separately, also can be used in combination two or more.In the middle of these; from easily (methyl) acryl equivalent of gained acrylic polymers (X1) being adjusted to the aspect of aforesaid preferable range; preferably (methyl) glycidyl acrylate, α-ethyl (methyl) glycidyl acrylate and α-n-propyl (methyl) glycidyl acrylate, more preferably (methyl) glycidyl acrylate.
For manufacturing other polymerizable compounds (v1) that aforementioned acrylic polymers can polymerization together with the aforementioned compound (y1) with epoxy group(ing) and (methyl) acryl when (Y1), for example can list: (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) vinylformic acid dodecane ester, (methyl) vinylformic acid tetradecane ester, (methyl) vinylformic acid n-Hexadecane ester, (methyl) stearyl acrylate ester, (methyl) vinylformic acid octadecane ester, (methyl) vinylformic acid docosane ester etc. has (methyl) acrylate of the alkyl of carbon number 1～22,
(methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid two encircle pentyl ester, (methyl) vinylformic acid two cyclopentenes oxygen base ethyl esters etc. and have (methyl) acrylate of ester ring type alkyl;
(methyl) vinylformic acid benzoyloxy ethyl ester, (methyl) benzyl acrylate, (methyl) vinylformic acid phenyl chlorocarbonate, (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid phenoxy group binaryglycol ester, (methyl) vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester etc. have (methyl) acrylate of aromatic nucleus;
(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 acrylate of hydroxyalkyl;
The unsaturated dibasic acid esters 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;
The styrene derivativess such as vinylbenzene, alpha-methyl styrene, chloro-styrene;
The dienes compounds such as divinyl, isoprene, m-pentadiene (piperylene), dimethylbutadiene;
Halogen ethene, the vinylidene halides such as vinylchlorid, bromine ethene;
The beta-unsaturated ketones such as methyl vinyl ketone, butyl vinyl ketone;
The vinyl acetate such as vinyl acetate, vinyl butyrate;
The vinyl ether such as methylvinylether, butyl vinyl ether;
The vinyl cyanides such as vinyl cyanide, methacrylonitrile, vinylidene dicyanide;
Acrylamide, its alkyd substituted amide;
The N-substituted maleimide amine such as N-phenylmaleimide, N-N-cyclohexylmaleimide;
The fluorine-containing alpha-olefin of vinyl fluoride, vinylidene fluoride, trifluoro-ethylene, chlorotrifluoroethylene, bromotrifluoethylene, five fluorine propylene or R 1216 and so on;
(entirely) fluoroalkyl perfluoroalkyl vinyl ether that the carbon number of (entirely) fluoroalkyl of trifluoromethyl trifluoro vinyl ether, pentafluoroethyl group trifluoro vinyl ether or seven fluoropropyl trifluoro vinyl ethers and so on is 1～18;
(methyl) vinylformic acid-2,2,2-trifluoro ethyl ester, (methyl) vinylformic acid-2,2,3,3-tetrafluoro propyl ester, (methyl) vinylformic acid-1H, 1H, 5H-octafluoro pentyl ester, (methyl) vinylformic acid-1H, 1H, 2H, (entirely) fluoroalkyl (methyl) acrylate that the carbon number of (entirely) fluoroalkyl of 2H-17 fluorine esters in the last of the ten Heavenly stems or (methyl) vinylformic acid perfluor ethoxy ethyl ester and so on is 1～18;
3-methacryloxypropyl trimethoxy silane etc. are containing silyl (methyl) acrylate;
(methyl) vinylformic acid-N, N-dimethylamino ethyl ester, (methyl) vinylformic acid-N, N-diethylamino ethyl ester or (methyl) vinylformic acid-N, (methyl) vinylformic acid-N such as N-diethylamino propyl ester, N-dialkyl amido alkane ester etc.These can distinguish use separately, also can be used in combination two or more.In the middle of these; from easily (methyl) acryl equivalent of gained acrylic polymers (X1) being adjusted to aforesaid preferable range and gained cured coating film is high rigidity and the aspect that is rich in toughness; preferably there is (methyl) acrylate and (methyl) acrylate with ester ring type alkyl of the alkyl of carbon number 1～22, more preferably there is (methyl) acrylate of the alkyl of carbon number 1～22.Especially, particularly preferably (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate and (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate.
Aforementioned acrylic polymers (Y1) as previously mentioned; can be the homopolymer of the aforementioned compound (y1) with epoxy group(ing) and (methyl) acryl, can be also aforementioned have epoxy group(ing) and the compound (y1) of (methyl) acryl and the multipolymer of aforementioned other polymerizable compounds (v1).In the middle of these; from easily (methyl) acryl equivalent of gained acrylic polymers (X1) being adjusted to suitable scope, can obtain having high surface hardness and the also aspect of excellent cured coating film of resistance to crimp tendency when curing; both mass ratio [thering is the compound (y1) of epoxy group(ing) and (methyl) acryl] during preferably taking copolymerization: the ratio of [other polymerizable compounds (v1)] scope as 10/90～90/10 is carried out the polymkeric substance that copolymerization obtains, more preferably 15/85～80/20 scope.And then from obtaining the aspect of active energy ray-curable resin composition of ageing stability excellence, more preferably 20/80～50/50 scope, is particularly preferably 25/75～45/55 scope.
Aforementioned acrylic polymers (Y1) has the epoxy group(ing) from aforesaid compound (y1); and from easily the acryl equivalent of gained acrylic polymers (X1) being adjusted to the aspect of the scope of 220～1650g/eq; the epoxy equivalent (weight) of this acrylic polymers (Y1) is preferably the scope of 150～1600g/eq; the more preferably scope of 170～1100g/eq; the more preferably scope of 270～750g/eq, is particularly preferably the scope of 300～550g/eq.
Aforementioned acrylic polymers (Y1) for example can be by under the existence of polymerization starter, make aforesaid compound (y1) carry out separately polymerization or be used in combination aforesaid compound (y1) and aforesaid compound (v1) to carry out addition polymerization and manufacture the temperature province of 60 DEG C～150 DEG C, can list random copolymers, segmented copolymer, graft copolymer etc.The method of polymerization for example can list: mass polymerization, solution polymerization process, suspension polymerization, emulsion polymerization etc.In the middle of these; from carrying out continuously the aspect of reacting of the manufacture of aforementioned acrylic polymers (Y1) and aforementioned acrylic polymers (Y1) subsequently and the aforementioned compound (z1) with carboxyl and (methyl) acryl, preferred solution polymerization.
If consider temperature of reaction, the solvent using when carry out the manufacture of aforementioned acrylic polymers (Y1) taking solution polymerization process is that boiling point is more than 80 DEG C solvent, for example, can list: the ketone solvents such as methylethylketone, methyl n-propyl ketone, methyl isopropyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, methyl n hexyl ketone, metacetone, ethyl normal-butyl ketone, diη-propyl ketone, diisobutyl ketone, pimelinketone, sym.-diisopropylideneacetone;
The ether solvents such as n-butyl ether, diisoamyl ether, diox;
Ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol bisthioglycolate ethyl ether, ethylene glycol list propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, TC, diethylene glycol diethyl ether, Diethylene Glycol monoisopropyl ether, Diethylene Glycol single-butyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol list propyl ether, propylene glycol single-butyl ether, DPGME, the glycol ether solvents such as dipropylene glycol dimethyl ether,
The ester solvents such as n-propyl acetate, Iso Butyl Acetate, n-butyl acetate, n-Amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic ester, TC acetic ester, propylene glycol monomethyl ether acetate, ethyl-3-ethoxy-c acid esters;
The alcoholic solvents such as Virahol, propyl carbinol, isopropylcarbinol, diacetone alcohol, 3-MP, 3-methoxyl group-n-butyl alcohol, 3-methyl-3-methoxybutanol;
The hydrocarbon solvents such as toluene, dimethylbenzene, Solvesso100, Solvesso150, Swazole1800, Swazole310, Isopar E, Isopar G, No. 5, Exxon petroleum naphtha, No. 6, Exxon petroleum naphtha.These may be used singly or in combination of two or more.
In the middle of aforementioned solvents, from the aspect of the solvability excellence of gained acrylic polymers (Y1), the preferably ketone solvent such as methylethylketone, methyl iso-butyl ketone (MIBK), the glycol ether solvents such as propylene glycol monomethyl ether.
The catalyzer using in the manufacture of aforementioned acrylic polymers (Y1) for example can list: 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo is two-(2,4-methyl pentane nitrile), 2,2 '-azo is two-azo-compounds such as (4-methoxyl group-2,4-methyl pentane nitriles); Organo-peroxide and the hydrogen peroxide etc. such as benzoyl peroxide, lauroyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, the peroxidation thylhexoic acid tert-butyl ester, 1,1 '-bis-(tert-butyl hydroperoxide) hexanaphthene, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, the tertiary own ester of peroxidation-2 ethyl hexanoic acid.
In the time using superoxide as catalyzer, superoxide can be used as together with reductive agent to oxidation-reduction type initiator.
Use as the raw material of aforementioned acrylic polymers (X1), the compound (z1) with carboxyl and (methyl) acryl for example can list: (methyl) vinylformic acid, (acryloxy) acetic acid, vinylformic acid-2-carboxyl ethyl ester, vinylformic acid-3-carboxyl propyl ester, succsinic acid-1-[2-(acryloxy) ethyl ester], phthalic acid-1-(2-acryloxy ethyl ester), the unsaturated monocarboxylics such as hexahydrophthalic acid hydrogen-2-(acryloxy) ethyl ester and their lactone modifier, the unsaturated dicarboxylic acids such as toxilic acid, make hydroxyl multifunctional (methyl) acrylate monomers such as the acid anhydrides such as succinyl oxide, maleic anhydride and pentaerythritol triacrylate react gained containing carboxyl multifunctional (methyl) acrylate etc.These may be used singly or in combination of two or more.In the middle of these; from easily (methyl) acryl equivalent of aforementioned acrylic polymers (X1) being adjusted to the aspect of aforesaid preferable range; preferably (methyl) vinylformic acid, (acryloxy) acetic acid, vinylformic acid-2-carboxyl ethyl ester, vinylformic acid-3-carboxyl propyl ester, particularly preferably (methyl) vinylformic acid.
Aforementioned acrylic polymers (X1) makes aforementioned acrylic polymers (Y1) react and obtain with the compound (z1) with carboxyl and (methyl) acryl.This reaction method for example can list: with solution polymerization process by acrylic polymers (Y1) polymerization; in this reaction system, add the compound (z1) with carboxyl and (methyl) acryl; in the temperature range of 60～150 DEG C, suitably use the method for the catalyzer such as triphenylphosphine etc.(methyl) acryl equivalent of acrylic polymers (X1) is preferably the scope of 220～1650g/eq, and this can regulate by aforementioned acrylic polymers (Y1) and the reactive ratio of the aforementioned compound (z1) with carboxyl and (methyl) acryl.Conventionally; 1 mole of the epoxy group(ing) having with respect to aforementioned acrylic polymers (Y1); the carboxyl being had taking aforesaid compound (z1) reacts as the mode of the scope of 0.8～1.1 mole, thereby easily (methyl) acryl equivalent of gained acrylic polymers (X1) is adjusted into above-mentioned preferable range.
The acrylic polymers (X1) so obtaining has the hydroxyl generating with reacting of carboxyl by epoxy group(ing) in its molecular structure.For the object that the acryl equivalent of acrylic polymers (X1) is adjusted into suitable scope, can make as required this hydroxyl and the compound (w) with isocyanate group and (methyl) acryl carry out addition reaction.The acrylic polymers that so obtains (X1 ') also same with aforementioned acrylic polymers (X1), can be used as acrylic polymers of the present invention (X).
The aforementioned compound (w) with isocyanate group and (methyl) acryl for example can list the compound shown in following general formula 1, can list: have 1 isocyanate group and 1 (methyl) acryl monomer, have 1 isocyanate group and 2 (methyl) acryls monomer, have 1 isocyanate group and 3 (methyl) acryls monomer, have 1 isocyanate group and 4 (methyl) acryls monomer, there is the monomer etc. of 1 isocyanate group and 5 (methyl) acryls.
In general formula (1), R1 is hydrogen atom or methyl.R2 is the alkylidene group of carbonatoms 2～4.N represents 1～5 integer.
There is the example of the specific product of the compound (w) of isocyanate group and (methyl) acryl as these; can list: 2-acryloxy ethyl isocyanate (trade(brand)name: " the Karenz AOI " that Showa Denko K. K manufactures etc.), 2-methacryloxyethyl isocyanic ester (trade(brand)name: " the Karenz MOI " that Showa Denko K. K manufactures etc.), 1, two (acryloyl-oxy ylmethyl) ethyl isocyanates of 1-(trade(brand)name: " the Karenz BEI " that Showa Denko K. K manufactures etc.).
As other examples of aforesaid compound (w), can list 1 of diisocyanate cpd isocyanate group addition hydroxyl (methyl) acrylic compound and compound.The diisocyanate cpd using in this reaction can list: butane-1,4-vulcabond, hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2, the aliphatic diisocyanates such as 4,4-trimethyl hexamethylene diisocyanate, xylylene vulcabond, a tetramethyl-benzene dimethyl vulcabond;
Hexanaphthene-1,4-vulcabond, isophorone diisocyanate, lysinediisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, 1, the ester ring type vulcabond such as two (isocyanic ester methyl) hexanaphthenes of 3-, methylcyclohexane diisocyanate;
1,5-naphthalene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 4,4 '-phenylbenzene dimethylmethane vulcabond, 4,4 '-dibenzyl vulcabond, dialkyl group diphenylmethanediisocyanate, tetraalkyl diphenylmethanediisocyanate, 1, the aromatic diisocyanates such as 3-phenylene diisocyanate, Isosorbide-5-Nitrae-phenylene diisocyanate, tolylene diisocyanate etc.These can distinguish use separately, also can be used in combination two or more.
In addition, for the hydroxyl using in this reaction (methyl) acrylic compound, can list: aliphatics (methyl) acrylic compound such as 2-Hydroxy ethyl acrylate, vinylformic acid-2-hydroxy ester, vinylformic acid-4-hydroxyl butyl ester, glycerine diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, Dipentaerythritol five acrylate;
In vinylformic acid-4-hydroxylphenyl ester, senecioate-hydroxybenzene ethyl ester, vinylformic acid-4-hydroxybenzene ethyl ester, vinylformic acid-1-phenyl-2-hydroxyl ethyl ester, vinylformic acid-3-hydroxyl-4-ethanoyl phenyl ester, vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester equimolecular structure, there is (methyl) acrylic compound of aromatic nucleus etc.These can distinguish use separately, also can be used in combination two or more.
Aforementioned acrylic polymers (X1) can wait by the following method and carry out with for example the reacting of compound (w) with isocyanate group and (methyl) acryl: add the aforementioned compound (w) with isocyanate group and (methyl) acryl to having manufactured with preceding method in acrylic polymers (X1) system afterwards, be heated to 50～120 DEG C.
For aforementioned acrylic polymers (X1) and (X1 '), from molecule, contain more hydroxyl, make the dispersive ability of inorganic particles (A) improve by the interaction of this hydroxyl and inorganic particles (A) preferred aforementioned acrylic polymers (X1).
Then, aforementioned acrylic polymers (X2) is described.
Can be the homopolymer of the aforementioned compound (y2) with carboxyl and (methyl) acryl as the aforementioned acrylic polymers (Y2) of the raw material of aforementioned acrylic polymers (X2), can be also the multipolymer of itself and other polymerizable compound (v2).
As the material composition of aforementioned acrylic polymers (Y2), the compound (y2) with carboxyl and (methyl) acryl for example can list: (methyl) vinylformic acid, (acryloxy) acetic acid, vinylformic acid-2-carboxyl ethyl ester, vinylformic acid-3-carboxyl propyl ester, succsinic acid-1-[2-(acryloxy) ethyl ester], phthalic acid-1-(2-acryloxy ethyl ester), the unsaturated monocarboxylics such as hexahydrophthalic acid hydrogen-2-(acryloxy) ethyl ester and their lactone modifier, the unsaturated dicarboxylic acids such as toxilic acid, make hydroxyl multifunctional (methyl) acrylate monomers such as the acid anhydrides such as succinyl oxide, maleic anhydride and pentaerythritol triacrylate react gained containing carboxyl multifunctional (methyl) acrylate etc.These may be used singly or in combination of two or more.In the middle of these; from easily (methyl) acryl equivalent of aforementioned acrylic polymers (X1) being adjusted to the aspect of aforesaid preferable range; preferably (methyl) vinylformic acid, (acryloxy) acetic acid, vinylformic acid-2-carboxyl ethyl ester, vinylformic acid-3-carboxyl propyl ester, particularly preferably (methyl) vinylformic acid.
For manufacturing other polymerizable compounds (v2) that aforementioned acrylic polymers can polymerization together with the aforementioned compound (y2) with carboxyl and (methyl) acryl when (Y2), for example, can list as aforesaid compound (v1) and illustrative various compound.These can distinguish use separately, also can be used in combination two or more.Wherein, from easily (methyl) acryl equivalent of gained acrylic polymers (X2) being adjusted to aforesaid preferable range and gained cured coating film is high rigidity and the aspect that is rich in toughness; preferably there is (methyl) acrylate and (methyl) acrylate with ester ring type alkyl of the alkyl of carbon number 1～22, more preferably there is (methyl) acrylate of the alkyl of carbon number 1～22.Especially, particularly preferably (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate and (methyl) tert-butyl acrylate.
Aforementioned acrylic polymers (Y2) as previously mentioned; can be the homopolymer of the aforementioned compound (y2) with carboxyl and (methyl) acryl, can be also aforementioned have carboxyl and the compound (y2) of (methyl) acryl and the multipolymer of aforementioned other polymerizable compounds (v2).In the middle of these; from easily (methyl) acryl equivalent of gained acrylic polymers (X2) being adjusted to the aspect of suitable scope; both mass ratioes during preferably with copolymerization [thering is the compound (y2) of carboxyl and (methyl) acryl]: the polymkeric substance that the ratio copolymerization of [other polymerizable compounds (v2)] scope 10/90～90/10 obtains; more preferably 15/85～80/20 scope; more preferably 20/80～50/50 scope, is particularly preferably 25/75～45/55 scope.
Aforementioned acrylic polymers (Y2) for example can, by under the existence of polymerization starter, make aforesaid compound (y2) carry out separately polymerization or be used in combination aforesaid compound (y2) and aforesaid compound (v2) carries out addition polymerization and manufactures the temperature province of 60 DEG C～150 DEG C, can list: random copolymers, segmented copolymer, graft copolymer etc.For the method for polymerization, for example, can list: mass polymerization, solution polymerization process, suspension polymerization, emulsion polymerization etc.In the middle of these; from carrying out continuously the aspect of reacting of the manufacture of aforementioned acrylic polymers (Y2) and back to back aforementioned acrylic polymers (Y2) and the aforementioned compound (z2) with epoxy group(ing) and (methyl) acryl, preferred solution polymerization.
For the solvent using when carry out the manufacture of aforementioned acrylic polymers (Y2) with solution polymerization process, can list as the solvent using when carry out the manufacture of aforementioned acrylic polymers (Y1) with solution polymerization process and illustrative all kinds of SOLVENTS.These may be used singly or in combination of two or more.Wherein, from the aspect of the solvability excellence of gained acrylic polymers (Y2), the preferably ketone solvent such as methylethylketone, methyl iso-butyl ketone (MIBK).
For the catalyzer using in the manufacture of aforementioned acrylic polymers (Y2), can list as the catalyzer using in the manufacture of aforementioned acrylic polymers (Y1) and illustrative various catalyzer.
Use as the raw material of aforementioned acrylic polymers (X2), the compound (z2) with epoxy group(ing) and (methyl) acryl for example can list: (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 butyl ester, (methyl) vinylformic acid-4, 5-epoxy pentyl ester, (methyl) vinylformic acid-6, 7-epoxy pentyl ester, α-ethyl (methyl) vinylformic acid-6, 7-epoxy pentyl ester, (methyl) senecioate-methyl glycidyl ester, (methyl) vinylformic acid-3, 4-epoxy cyclohexyl, interior ester modified (methyl) vinylformic acid-3, 4-epoxy cyclohexyl, vinyl cyclohexene oxide compound etc.These can distinguish use separately, also can be used in combination two or more.In the middle of these; from easily (methyl) acryl equivalent of gained acrylic polymers (X2) being adjusted to the aspect of aforementioned preferable range, particularly preferably (methyl) glycidyl acrylate, α-ethyl (methyl) glycidyl acrylate and α-n-propyl (methyl) glycidyl acrylate.
Aforementioned acrylic polymers (X2) makes aforementioned acrylic polymers (Y2) react and obtain with the compound (z2) with epoxy group(ing) and (methyl) acryl.This reaction method for example can list following method etc.: make acrylic polymers (Y2) polymerization with solution polymerization process; in this reaction system, add the compound (z2) with epoxy group(ing) and (methyl) acryl; in the temperature range of 60～150 DEG C, suitably use the method for the catalyzer such as triphenylphosphine.(methyl) acryl equivalent of acrylic polymers (X2) is preferably the scope of 220～1650g/eq, and this can regulate by aforementioned acrylic polymers (Y2) and the reactive ratio of the aforementioned compound (z2) with epoxy group(ing) and (methyl) acryl.Conventionally; 1 mole of the carboxyl having with respect to aforementioned acrylic polymers (Y2); the epoxy group(ing) being had taking aforesaid compound (z2) is reacted as the mode of the scope of 0.9～1.25 mole, thereby easily (methyl) acryl equivalent of gained acrylic polymers (X2) is adjusted into above-mentioned preferable range.
The acrylic polymers (X2) so obtaining has the hydroxyl generating with reacting of epoxy group(ing) by carboxyl in its molecular structure.For the object that the acryl equivalent of acrylic polymers (X2) is adjusted to suitable scope, can make as required this hydroxyl and the aforementioned compound (w) with isocyanate group and (methyl) acryl carry out addition reaction.The acrylic polymers that so obtains (X2 ') also same with aforementioned acrylic polymers (X2), can be used as acrylic polymers of the present invention (X).
Aforementioned acrylic polymers (X2) can wait by the following method and carry out with for example the reacting of compound (w) with isocyanate group and (methyl) acryl: add the aforementioned compound (w) with isocyanate group and (methyl) acryl to having manufactured with preceding method in acrylic polymers (X2) system afterwards, be heated to 50～120 DEG C.
For aforementioned acrylic polymers (X2) and (X2 '), from molecule, contain more hydroxyl, make the dispersive ability of inorganic particles (A) improve by the interaction of this hydroxyl and inorganic particles (A) preferred aforementioned acrylic polymers (X2).
Then, aforementioned acrylic polymers (X3) is described.
Can be the homopolymer of the aforementioned compound (y3) with hydroxyl and (methyl) acryl as the aforementioned acrylic polymers (Y3) of the raw material of aforementioned acrylic polymers (X3), can be also the multipolymer of itself and other polymerizable compound (v3).
Compound (y3) material composition, that have hydroxyl and (methyl) acryl as aforementioned acrylic polymers (Y3) for example can list: 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, vinylformic acid-4-hydroxyl butyl ester, vinylformic acid-2; 3-dihydroxyl propyl ester, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, methacrylic acid-4-hydroxyl butyl ester, methacrylic acid-2,3-dihydroxyl propyl ester etc.These may be used singly or in combination of two or more.In the middle of these; from easily (methyl) acryl equivalent of aforementioned acrylic polymers (X3) being adjusted to aforesaid preferable range and hydroxyl value is high, can obtain the aspect of the aforementioned acrylic polymers (X3) of the excellent dispersion of aforementioned inorganic particles (A), preferably 2-Hydroxy ethyl acrylate and 2-hydroxypropyl acrylate.
For manufacturing other polymerizable compounds (v3) that aforementioned acrylic polymers can polymerization together with the aforementioned compound (y3) with hydroxyl and (methyl) acryl when (Y3), for example, can list as aforesaid compound (v1) and illustrative various compound.These can distinguish use separately, also can be used in combination two or more.Wherein, from easily (methyl) acryl equivalent of gained acrylic polymers (X3) being adjusted to aforesaid preferable range and gained cured coating film is high rigidity and the aspect that is rich in toughness; preferably there is (methyl) acrylate and (methyl) acrylate with ester ring type alkyl of the alkyl of carbon number 1～22, more preferably there is (methyl) acrylate of the alkyl of carbon number 1～22.Especially, particularly preferably (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate and (methyl) tert-butyl acrylate.
Aforementioned acrylic polymers (Y3) as previously mentioned, can be the homopolymer with the compound (y3) of hydroxyl and (methyl) acryl, can be also the multipolymer of itself and other polymerizable compound (v3).In the middle of these; for (methyl) acryl equivalent of gained acrylic polymers (X3) is adjusted into suitable scope; both mass ratioes during preferably with copolymerization [thering is the compound (y3) of hydroxyl and (methyl) acryl]: the ratio of [other polymerizable compounds (v3)] scope 10/90～90/10 is carried out the polymkeric substance that copolymerization obtains; more preferably 15/85～80/20 scope; more preferably 20/80～50/50 scope, is particularly preferably 25/75～45/55 scope.
Aforementioned acrylic polymers (Y3) for example can, by under the existence of polymerization starter, make aforesaid compound (y3) carry out separately polymerization or be used in combination aforesaid compound (y3) and aforesaid compound (v3) carries out addition polymerization and manufactures the temperature province of 60 DEG C～150 DEG C, can list random copolymers, segmented copolymer, graft copolymer etc.Copolymerization process can utilize mass polymerization, solution polymerization process, suspension polymerization, emulsion polymerization etc.In the middle of these; from carrying out continuously the aspect of reacting of the manufacture of aforementioned acrylic polymers (Y3) and aforementioned acrylic polymers (Y3) subsequently and the aforementioned compound (z3) with isocyanate group and (methyl) acryl, preferred solution polymerization.
For the solvent using when carry out the manufacture of aforementioned acrylic polymers (Y3) with solution polymerization process, can list as the solvent using when carry out the manufacture of aforementioned acrylic polymers (Y1) with solution polymerization process and illustrative all kinds of SOLVENTS.These may be used singly or in combination of two or more.Wherein, from the aspect of the solvability excellence of gained acrylic polymers (Y3), the preferably ketone solvent such as methylethylketone, methyl iso-butyl ketone (MIBK).
For the catalyzer using in the manufacture of aforementioned acrylic polymers (Y3), can list as the catalyzer using in the manufacture of aforementioned acrylic polymers (Y1) and illustrative various catalyzer.
The compound (z3) that use, that have isocyanate group and (methyl) acryl for raw material as aforementioned acrylic polymers (X3), for example, can list as the aforementioned compound (w) with isocyanate group and (methyl) acryl and illustrative various compound.These can distinguish use separately, also can be used in combination two or more.In the middle of these; become from gained acrylic polymers (X3) and there is more multi-functional compound, can obtain the more aspect of the film of high rigidity; preferably in 1 molecule, there is the compound of 2 above (methyl) acryls; particularly; preferably 1, two (acryloyl-oxy ylmethyl) ethyl isocyanates of 1-.
Aforementioned acrylic polymers (X3) makes aforementioned acrylic polymers (Y3) react and obtain with the compound (z3) with isocyanate group and (methyl) acryl.This reaction for example can wait by the following method and carry out: with solution polymerization process by acrylic polymers (Y3) polymerization; in this reaction system, add the compound (z3) with isocyanate group and (methyl) acryl; in the temperature range of 50～120 DEG C, suitably use the catalyzer such as stannous octoate (II).(methyl) acryl equivalent of acrylic polymers (X3) is preferably the scope of 220～1650g/eq, and this can regulate by aforementioned acrylic polymers (Y3) and the reactive ratio of the aforementioned compound (z3) with isocyanate group and (methyl) acryl.Conventionally; 1 mole of the hydroxyl having with respect to aforementioned acrylic polymers (Y3); the isocyanate group being had taking aforesaid compound (z3) is reacted as the mode of the scope of 0.7～0.9 mole, thereby easily (methyl) acryl equivalent of gained acrylic polymers (X3) is adjusted into above-mentioned preferable range.
In the middle of aforementioned acrylic polymers (X), from the aspect of good, the dispersions obtained storage stability excellence of the affinity of aforementioned inorganic particles (A), preferred aforementioned acrylic polymers (X1) and (X2).Herein, from the more excellent aspect of dispersiveness of aforementioned inorganic particles (A), aforementioned acrylic polymers (X1) and hydroxyl value (X2) are preferably the scope of 35～250mgKOH/g, the more preferably scope of 50～230mgKOH/g, the more preferably scope of 65～160mgKOH/g, is particularly preferably the scope of 80～150mgKOH/g.And then, from synthetic easier aspect, preferred aforementioned acrylic polymers (X1), the acrylic polymers that more preferably uses (methyl) glycidyl acrylate to obtain as aforesaid compound (z1) as aforesaid compound (y1), use (methyl) vinylformic acid.
Active energy ray-curable resin composition of the present invention, using aforementioned inorganic particles (A) and aforementioned acrylic polymers (X) as neccessary composition, contains aforementioned inorganic particles (A) with the scope of 35～60 mass parts in their summation 100 mass parts.In the time that the content of aforementioned inorganic particles (A) is less than 35 mass parts, the resistance to crimp tendency while solidifying reduces.In addition,, in the time that the content of aforementioned inorganic particles (A) exceedes 60 mass parts, the storage stability of active energy ray-curable resin composition reduces.In the middle of, from the excellent storage stability of resin combination and can obtain having concurrently the aspect of the cured coating film of high surface hardness and the transparency, resistance to crimp tendency, more preferably in their summation 100 mass parts, contain inorganic particles (A) with the scope of 40～55 mass parts.
Active energy ray-curable resin composition of the present invention has on the basis of acrylic polymers (X) of (methyl) acryl in aforementioned molecular structure, can also contain acrylic polymers (X) compound (c) in addition, that have (methyl) acryl in molecular structure.In the present invention, from forming the aspect of viscosity active energy ray-curable resin composition lower, that easily use as coating purposes, preferably use this compound (c).Now, from obtaining the aspect of the cured coating film that resistance to crimp tendency and toughness are more excellent, in summation 100 mass parts of aforementioned inorganic particles (A), aforementioned acrylic polymers (X) and aforesaid compound (c), the content of aforementioned acrylic polymers (X) is preferably the scope of 35～60 mass parts, the more preferably scope of 40～50 mass parts.In addition,, from obtaining the also aspect of excellent cured coating film of the higher and scuff resistance of surface hardness, be preferably the scope of 5～35 mass parts, the more preferably scope of 10～25 mass parts.
The compound (c) in aforementioned molecular structure with (methyl) acryl for example can list: various (methyl) acrylate monomer, carbamate (methyl) acrylate.
Aforementioned (methyl) acrylate monomer for example can list: (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxyl butyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) glycidyl acrylate, acryloyl morpholine, NVP, tetrahydrofurfuryl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) isobornyl acrylate, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, (methyl) aliphatic acrylate, (methyl) stearyl acrylate ester, (methyl) benzyl acrylate, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 3-methoxyl group butyl ester, (methyl) vinylformic acid ethyl carbitol ester, phosphoric acid (methyl) acrylate, oxyethane modified phosphate (methyl) acrylate, phenoxy group (methyl) acrylate, oxyethane modification phenoxy group (methyl) acrylate, epoxy pronane modification phenoxy group (methyl) acrylate, nonylphenol (methyl) acrylate, oxyethane modification nonylphenol (methyl) acrylate, epoxy pronane modification nonylphenol (methyl) acrylate, methoxyl group Diethylene Glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, MPEG (methyl) acrylate, 2-(methyl) acryloxy ethyl-2-hydroxypropyl phthalic ester, (methyl) vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester, 2-(methyl) acrylyl oxy-ethyl hydrogen phthalic ester, 2-(methyl) acryloxy propyl group hydrogen phthalic ester, 2-(methyl) acryloxy propyl group hexahydrophthalic acid ester, 2-(methyl) acryloxy propyl group tetrahydrophthalic acid ester, (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid tetrafluoro propyl ester, (methyl) vinylformic acid hexafluoro propyl ester, (methyl) vinylformic acid octafluoro propyl ester, (methyl) vinylformic acid octafluoro propyl ester, single (methyl) acrylate such as single (methyl) vinylformic acid adamantane esters,
Butyleneglycol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, ethoxylation hexylene glycol two (methyl) acrylate, propoxylation hexylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethoxylation neopentyl glycol two (methyl) acrylate, two (methyl) acrylate such as hydroxypivalic acid neopentyl glycol two (methyl) acrylate,
Three (methyl) acrylate such as trimethylolpropane tris (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, three-2-hydroxyethyl isocyanuric acid ester three (methyl) acrylate, glycerine three (methyl) acrylate;
Tetramethylolmethane three (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, two (TriMethylolPropane(TMP)) three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, two (TriMethylolPropane(TMP)) four (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, two (TriMethylolPropane(TMP)) five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, 4 officials such as two (TriMethylolPropane(TMP)) six (methyl) acrylate can be above (methyl) acrylate,
And the alkyl for a part of above-mentioned various multifunctional (methyl) acrylate, 6-caprolactone are replaced and (methyl) acrylate etc.
Aforementioned carbamate (methyl) acrylate for example can list: polyisocyanate compound is reacted with hydroxyl (methyl) acrylic compound and carbamate (methyl) acrylate.
The aforementioned polyisocyanate compound that is used for the raw material of aforementioned carbamate (methyl) acrylate can list: in various diisocyanate monomers, molecule, have the urea acid esters type polyisocyanate compound of isocyanuric acid ester ring structure etc.
Aforementioned diisocyanate monomer for example can list: butane-1,4-vulcabond, hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2, the aliphatic diisocyanates such as 4,4-trimethyl hexamethylene diisocyanate, xylylene vulcabond, a tetramethyl-benzene dimethyl vulcabond;
Hexanaphthene-1,4-vulcabond, isophorone diisocyanate, lysinediisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, 1, the ester ring type vulcabond such as two (isocyanic ester methyl) hexanaphthenes of 3-, methylcyclohexane diisocyanate;
1,5-naphthalene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 4,4 '-phenylbenzene dimethylmethane vulcabond, 4,4 '-dibenzyl vulcabond, dialkyl group diphenylmethanediisocyanate, tetraalkyl diphenylmethanediisocyanate, 1, the aromatic diisocyanates such as 3-phenylene diisocyanate, Isosorbide-5-Nitrae-phenylene diisocyanate, tolylene diisocyanate etc.
The urea acid esters type polyisocyanate compound in aforementioned molecule with isocyanuric acid ester ring structure for example can list: make diisocyanate monomer and monohydroxy-alcohol and/or diol reaction and compound.As the diisocyanate monomer using in this reaction, can list aforesaid various diisocyanate monomer, can distinguish separately and use, also can be used in combination two or more.In addition, the monohydroxy-alcohol using in this reaction can list: hexanol, octanol, nonylcarbinol, n-undecane alcohol, n-dodecane alcohol, positive n-tridecane alcohol, n-tetradecanol, Pentadecane alcohol, n-heptadecane alcohol, Octadecane alcohol, NSC 77136 alcohol etc., for dibasic alcohol, can list: ethylene glycol, Diethylene Glycol, propylene glycol, 1,3-PD, BDO, 1,3-butyleneglycol, 3-methyl isophthalic acid, 3-butyleneglycol, 1,5-PD, neopentyl glycol, 1,6-hexylene glycol etc.These monohydroxy-alcohols, dibasic alcohol can be distinguished use separately, also can be used in combination two or more.
In the middle of these polyisocyanate compounds, from obtaining the aspect of cured coating film of tenacity excellent, preferred aforementioned diisocyanate monomer, more preferably aforementioned aliphatic diisocyanate and aforementioned ester ring type vulcabond.
For aforementioned hydroxyl (methyl) acrylic compound of the raw material as aforementioned carbamate (methyl) acrylate, for example, can list: aliphatics (methyl) acrylic compound such as 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, vinylformic acid-4-hydroxyl butyl ester, glycerine diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, Dipentaerythritol five acrylate;
In vinylformic acid-4-hydroxylphenyl ester, senecioate-hydroxybenzene ethyl ester, vinylformic acid-4-hydroxybenzene ethyl ester, vinylformic acid-1-phenyl-2-hydroxy methacrylate, vinylformic acid-3-hydroxyl-4-ethanoyl phenyl ester, vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester equimolecular structure, there is (methyl) acrylic compound of aromatic nucleus etc.These can distinguish use separately, also can be used in combination two or more.
In the middle of these hydroxyls (methyl) acrylic compound; from obtaining tenacity excellent and there is the aspect of the cured coating film of high surface hardness, in preferably glycerine diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, Dipentaerythritol five acrylate equimolecular structures, there are aliphatics (methyl) acrylic compound of 2 above (methyl) acryls.And then; from obtaining demonstrating the more aspect of the cured coating film of high surface hardness, more preferably in pentaerythritol triacrylate, Dipentaerythritol five acrylate equimolecular structures, there is aliphatics (methyl) acrylic compound of 3 above (methyl) acryls.
The method of manufacturing aforementioned carbamate (methyl) acrylate for example can list following method etc.: the ratio of the scope taking the mol ratio of isocyanate group that aforementioned polyisocyanate compound was had and aforementioned hydroxyl (methyl) hydroxyl that acrylic compound was had [(NCO)/(OH)] as 1/0.95～1/1.05 is used aforementioned polyisocyanate compound and aforementioned hydroxyl (methyl) acrylic compound, in the temperature range of 20～120 DEG C, as required and the method for carrying out with known usual urethane catalyzer.
While manufacturing aforementioned carbamate (methyl) acrylate by (methyl) acrylic compound in aforementioned polyisocyanate compound and aforementioned molecular structure with 1 hydroxyl, its reaction can be carried out with the system that contains the acrylic compound such as tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate.For the carbamate in this way obtaining (methyl) acrylate, specifically can list: make the raw material reaction that contains aforementioned polyisocyanate compound, tetramethylolmethane three (methyl) acrylate and tetramethylolmethane four (methyl) acrylate and carbamate (methyl) acrylate obtaining; Make the raw material reaction that contains aforementioned polyisocyanate compound, Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate and the urethane acrylate obtaining etc.
From with the aspect of the consistency excellence of aforementioned acrylic polymers (X), the weight-average molecular weight (Mw) of the carbamate so obtaining (methyl) acrylate is preferably 800～20,000 scope, more preferably 900～1,000 scope.
These compounds (c) can be distinguished use separately, also can be used in combination two or more.Wherein, from obtaining the more aspect of the film of high rigidity, carbamate (methyl) acrylate that (methyl) acrylate monomer that preferably 3 officials can be above or 3 officials can be above.(methyl) acrylate monomer that can be above as aforementioned 3 officials, preferably tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate.In addition, carbamate (methyl) acrylate that can be above as aforementioned 3 officials, preferably make diisocyanate cpd and glycerine diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, carbamate (methyl) acrylate that there is hydroxyl (methyl) the acrylic compound reaction of 2 above (methyl) acryls in Dipentaerythritol five acrylate equimolecular structures and obtain, more preferably carbamate (methyl) acrylate that makes diisocyanate cpd react with hydroxyl (methyl) acrylic compound with 3 above (methyl) acryls and to obtain.
Active energy ray-curable resin composition of the present invention is at aforementioned inorganic particles (A), in aforementioned molecular structure, have while also containing aforesaid compound (c) on the basis of acrylic polymers (X) of (methyl) acryl, from the excellent storage stability of resin combination, and can obtain having concurrently the aspect of high surface hardness and transparent cured coating film, at aforementioned inorganic particles (A), in summation 100 mass parts of aforementioned acrylic polymers (X) and aforesaid compound (c), preferably with the scope of 35～60 mass parts, more preferably contain inorganic particles (A) with the scope of 40～55 mass parts.
Resin combination of the present invention can contain dispersing auxiliary as required.For this dispersing auxiliary, for example, can list: the phosphate compounds such as sec.-propyl acid phosphoric acid ester, triisodecyl phosphite ester, oxyethane modified phosphate dimethacrylate etc.These can distinguish use separately, also can be used in combination two or more.In the middle of these, from disperseing the aspect of ilities excellence, optimization ethylene oxide modified phosphate dimethacrylate.
For the commercially available product of aforementioned dispersing auxiliary, for example, can list: " KAYAMER PM-21 ", " KAYAMER PM-2 " that Nippon Kayaku K. K manufactures, " the LightEster P-2M " that Kyoeisha Chemical Co., Ltd. manufactures etc.
While using aforementioned dispersing auxiliary, from forming the aspect of the resin combination that storage stability is higher, in resin combination 100 mass parts of the present invention, preferably contain with the scope of 0.5～5.0 mass parts.
In addition, resin combination of the present invention can contain organic solvent.This organic solvent for example, when manufacture aforementioned acrylic polymers (X) with solution polymerization process, can directly contain solvent used at that time, also can further supplement and add other solvent.Or the organic solvent also can be first using during by the manufacture of aforementioned acrylic polymers (X) is removed and is re-used other solvent.The object lesson of the solvent using can list: the ketone solvents such as acetone, methylethylketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK); The cyclic ether solvents such as tetrahydrofuran (THF) (THF), dioxolane; The esters such as ritalin, vinyl acetic monomer, N-BUTYL ACETATE; The aromatic solvent such as toluene, dimethylbenzene; The alcoholic solvents such as Trivalin SF, cellosolve, methyl alcohol, Virahol, butanols, propylene glycol monomethyl ether; The glycol ethers solvents such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol list propyl ether.These can distinguish use separately, also can be used in combination two or more.In the middle of these, the aspect of the resin combination of the coating excellence during from formation excellent storage stability and as coating, preferably ketone solvent, more preferably methyl iso-butyl ketone (MIBK).In addition, also can on the basis of aforementioned ketone solvent, be used in combination glycol ether solvent for improving the deliquescent object of aforementioned ionic liquid (B).
It is the additives such as additive, organic microballon, fluorine class additive, rheology control agent, deaerating agent, releasing agent, static inhibitor, antifogging agent, tinting material, organic solvent, mineral filler that resin combination of the present invention can also contain UV light absorber, antioxidant, silicon.
Aforementioned UV light absorber for example can list: 2-[4-{(2-hydroxyl-3-dodecyloxy propyl group) oxygen }-2-hydroxy phenyl]-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-[4-{(2-hydroxyl-3-tridecane oxygen base propyl group) oxygen }-2-hydroxy phenyl]-4, 6-two (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.
Aforementioned antioxidant for example can list: hindered phenol anti-oxidants, hindered amines antioxidant, organosulfur class antioxidant, phosphate-based antioxidants etc.These can distinguish use separately, also can be used in combination two or more.
Aforementioned silicon is that additive for example can list: dimethyl polysiloxane, methyl phenyl silicone, cyclic dimethyl polysiloxane, methylhydrogenpolysi,oxane, polyether-modified dimethyl polysiloxane multipolymer, polyester modification dimethyl polysiloxane multipolymer, fluorine modification dimethyl polysiloxane multipolymer, amino modified dimethyl polysiloxane multipolymer etc. and so on there is alkyl, the organopolysiloxane of phenyl, there is the polydimethylsiloxane of polyether-modified acryl, there is the polydimethylsiloxane of polyester modification acryl etc.These can distinguish use separately, also can be used in combination two or more.
Aforementioned organic microballon for example can list: polymethylmethacrylate microballon, polycarbonate microballon, polystyrene microbeads, polyacrylic acid vinylbenzene microballon, polysiloxane microballon, glass microballon, vinylformic acid microballon, benzoguanamine resinoid microballon, trimeric cyanamide resinoid microballon, polyolefin resin microballon, polyester resin microballon, polyamide resin microballon, polyimide based resin microballon, polyfluoroethylene resin microballon, polyvinyl resin microballon etc.The preferred value of the median size of these organic microballons is the scope of 1～10 μ m.These can distinguish use separately, also can be used in combination two or more.
Aforementioned fluorine class additive for example can list " Megafac " series of Dainippon Ink Chemicals etc.These can distinguish use separately, also can be used in combination two or more.
Aforementioned releasing agent for example can list: " Tegorad2200N ", " Tegorad2300 ", " Tegorad2100 " that Evonik Degussa Corporation manufactures, " UV3500 " that Byk-Chemie Corporation manufactures, Dow Corning Toray Co., " Paintad8526 ", " SH-29PA " etc. that Ltd. manufactures.These can distinguish use separately, also can be used in combination two or more.
Aforementioned static inhibitor for example can list: two (trifyl) imides or two (fluorosulfonyl) imido pyridine, imidazoles, Phosphonium, ammonium or lithium salts.These can distinguish use separately, also can be used in combination two or more.
The consumption of aforementioned various additives is preferably the scope of giving full play to its effect and not damaging ultraviolet curing, particularly, in resin combination 100 mass parts of the present invention, preferably uses with the scope of 0.01～40 mass parts respectively.
Resin combination of the present invention also contains Photoepolymerizationinitiater initiater.This Photoepolymerizationinitiater initiater for example can list: benzophenone, 3,3 '-dimethyl-4-methoxy benzophenone, 4,4 '-bis-dimethylamino benzophenone, 4,4 '-bis-diethylin benzophenone, 4,4 '-dichloro benzophenone, michaelis ketone, 3, the various benzophenone such as 3 ', 4,4 '-tetra-(tert-butyl hydroperoxide carbonyl) benzophenone;
Xanthone, thioxanthone, 2-methyl thioxanthone, CTX, 2, xanthone, the thioxanthene ketones such as 4-diethyl thioxanthone; The various acyloin ethers such as bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether;
α-the diones such as benzil, di-acetyl; Tetramethyl thiuram disulfide, p-methylphenyl disulphide sulfides class; The various phenylformic acid such as 4-dimethylaminobenzoic acid, EDMAB;
3,3 '-carbonyl-bis-(7-diethylin) tonka bean camphor, 1-hydroxycyclohexylphenylketone, 2,2 '-dimethoxy-1,2-diphenylethane-1-ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide, 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, benzyl dimethyl ketal, benzyl-'beta '-methoxy ethyl acetals, methyl o-benzoylbenzoate, two (4-dimethylamino phenyl) ketone, to dimethylamino methyl phenyl ketone, α, α,α-dichloro-4-phenoxy acetophenone, amyl group-4-dimethylaminobenzoic acid ester, 2-Chloro-O-Phenyl-4,5-diphenyl-imidazole dipolymer, two (trichloromethyl)-6-[bis--(ethoxy carbonyl methyl) amino of 2,4-] phenyl s-triazine, two (the trichloromethyl)-6-(4-oxyethyl groups of 2,4-) phenyl s-triazine, 2,4-pair-the bromo-4-oxyethyl group of trichloromethyl-6-(3-) phenyl s-triazine anthraquinone, 2-tertiary butyl anthraquinone, 2-amyl anthraquinone, β-chloroanthraquinone etc.These can distinguish use separately, also can be used in combination two or more.
In the middle of aforementioned Photoepolymerizationinitiater initiater, be selected from 1-hydroxycyclohexylphenylketone by use, 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-Three methyl Benzene formyl diphenyl phosphine oxide, two (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) one kind or two or more mixed system in the group of-butane-1-ketone, can show activity for the light display of the wavelength of wide region more, can obtain the coating that solidified nature is high, so preferably.
The commercially available product of aforementioned Photoepolymerizationinitiater initiater for example can list: " IRGACURE-184 " that Ciba Specialty Chemicals Inc. manufactures, " 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 ", BASF Co., " the Lucirin TPO " that Ltd. manufactures, " KAYACURE-DETX ", " KAYACURE-MBP ", " KAYACURE-DMBI ", " KAYACURE-EPA ", " KAYACURE-OA " that Nippon Kayaku K. K manufactures, " Vicure-10 ", " Vicure-55 " that Stauffer Chemical Company manufactures, " the Trigonal P1 " that Akzo company manufactures, SANDOZ Co., " SANDORAY1000 " that Ltd. manufactures, " DEAP " that APJOHN company manufactures, WARD BLENKINSOPCo., " QUANTACURE-PDO ", " QUANTACURE-ITX ", " QUANTACURE-EPD " etc. that Ltd. manufactures.
The consumption of aforementioned Photoepolymerizationinitiater initiater is preferably the amount that can give full play to as the function of Photoepolymerizationinitiater initiater, and for not producing the scope that crystal is separated out, Physical properties of coating film is deteriorated, particularly, with respect to resin combination 100 mass parts, preferably use with the scope of 0.05～20 mass parts, centrally particularly preferably use with the scope of 0.1～10 mass parts.
Resin combination of the present invention can also use various photosensitizers together with aforementioned Photoepolymerizationinitiater initiater.Photosensitizer for example can list: amine, ureas, sulfocompound, P contained compound, chlorine-containing compound or nitrile or other nitrogenous compounds etc.
The method of manufacturing active energy ray-curable resin composition of the present invention for example can list following method: use the dispersion machine such as dispersion machine, paint shaker, roller mill, ball mill, masher, sand mill, ball mill with the agitating vane such as decollator, turbine blade by aforementioned inorganic particles (a) blending dispersion to the method in aforementioned acrylic polymers (X), or, aforementioned inorganic particles (a) blending dispersion is arrived to the method in the resinous principle being formed by aforementioned acrylic polymers (X) and aforesaid compound (c).When aforementioned inorganic particles (a) is wet method silicon dioxide microparticle, states in the use in the situation of any dispersion machine and all can obtain even and stable dispersion.And aforementioned inorganic particles (a) is while being dry method silicon dioxide microparticle, in order to obtain even and stable dispersion, preferably uses ball mill or ball mill.
The ball mill that can preferably use in the time manufacturing active energy ray-curable resin composition of the present invention for example can list and have container, turning axle, agitating vane, the supplying opening of raw material, the relief outlet of dispersion and the wet-type ball mill of gland seal device, wherein, the inside of described container is filled with medium, described agitating vane has with the axis of rotation of aforementioned rotating shaft coaxle and under the effect of the rotary actuation of aforementioned turning axle and rotates, described supplying opening is arranged at aforementioned container, described relief outlet is arranged at aforementioned container, described gland seal device is disposed in the part that runs through container of aforementioned turning axle, aforementioned axis seal apparatus has 2 mechanical seal unit, and the structure that the sealing with these 2 mechanical seal unit is sealed by outside seal liquid.
, for the method for manufacturing active energy ray-curable resin composition of the present invention, for example can list following method: use and there is container, turning axle, agitating vane, the supplying opening of raw material, the relief outlet of dispersion and the wet-type ball mill of gland seal device, wherein, the inside of container is filled with medium, described agitating vane has with the axis of rotation of aforementioned rotating shaft coaxle and under the effect of the rotary actuation of aforementioned turning axle and rotates, described supplying opening is arranged at aforementioned container, described relief outlet is arranged at aforementioned container, described gland seal device is disposed in the part that runs through container of aforementioned turning axle, aforementioned axis seal apparatus has 2 mechanical seal unit, and the structure that the sealing with these 2 mechanical seal unit is sealed by outside seal liquid, from the aforementioned supplying opening of described wet-type ball mill to the aforementioned inorganic particles of aforementioned supply for receptacles (a) and the resinous principle using aforementioned acrylic polymers (X) as neccessary composition, in aforementioned container, make turning axle and agitating vane rotation, be uniformly mixed medium and raw material, carry out thus the pulverizing of aforementioned inorganic particles (a) and this inorganic particles (a) to the dispersion in aforementioned resinous principle, then, discharge from aforementioned relief outlet.
By showing the accompanying drawing of an example of concrete structure of aforementioned wet-type ball mill, further this manufacture method is elaborated.
Wet-type ball mill shown in Fig. 1 has container (p1), turning axle (q1), agitating vane (r1), the supplying opening (s1) of raw material, the relief outlet (t1) of dispersion and gland seal device (u1), the inside of container (p1) is filled with medium, agitating vane (r1) has the axis of rotation coaxial with aforementioned turning axle (q1) and rotates under the effect of the rotary actuation of aforementioned turning axle, supplying opening (s1) is arranged at aforementioned container (p1), relief outlet (t1) is arranged at aforementioned container (p1), gland seal device (u1) is disposed in the part that runs through container of aforementioned turning axle.Here, aforementioned axis seal apparatus (u1) has 2 mechanical seal unit, and has the structure that the sealing of these 2 mechanical seal unit is sealed by outside seal liquid, and this gland seal device (u1) for example can list the device with the structure shown in Fig. 2.
While using aforementioned wet-type ball mill to manufacture resin combination of the present invention, can list the method that aforementioned inorganic particles (a) and aforementioned acrylic polymers (X) is supplied to wet-type ball mill and carries out blending dispersion.Now, can be on the basis of aforementioned inorganic particles (a) and aforementioned acrylic polymers (X) also aforesaid compound (c), aforementioned dispersing auxiliary, aforementioned organic solvent and aforementioned various additives be supplied to wet-type ball mill together with also and carry out blending dispersion, also can, aforementioned inorganic particles (a) and aforementioned acrylic polymers (X) being supplied to after wet-type ball mill carries out blending dispersion, in gained mixture, add aforesaid compound (c), aforementioned dispersing auxiliary, aforementioned organic solvent and aforementioned various additive.Wherein, from manufacturing easy aspect, preferably aforementioned inorganic particles (a), aforementioned acrylic polymers (X), aforesaid compound (c), aforementioned dispersing auxiliary, aforementioned organic solvent and aforementioned various additive are supplied to wet-type ball mill and carry out the method for blending dispersion.In addition, for the object that prevents from producing gelation etc. in the time disperseing, Photoepolymerizationinitiater initiater preferably after add in the dispersion after dispersion.
In the wet-type ball mill shown in Fig. 1, raw material is supplied to container (p1) via the supplying opening in Fig. 1 (s1).In aforementioned container (p1), be filled with medium, the agitating vane (r1) rotating under effect by the rotary actuation at turning axle (q1) is uniformly mixed raw material and medium, carries out the pulverizing of aforementioned inorganic particles (a) and this inorganic particles (a) to the dispersion in aforementioned acrylic polymers (X), compound (c).Aforementioned turning axle (p1) is formed as its inner side and has the cavity of peristome in relief outlet (t1) side.In this cavity, be provided with the isolated body 2 as the screen cloth type of isolated body, be provided with the stream that connects relief outlet (t1) in the inner side of this isolated body 2.Dispersion in aforementioned container (p1) is delivered to the aforementioned isolated body 2 of its inner side from the peristome of aforementioned turning axle (p1) by the pushing of the supply of raw material pressure.Aforementioned isolated body 2 does not allow the larger medium of particle diameter pass through, and only allows the dispersion that contains the inorganic particles that particle diameter is less (A) pass through, and makes thus aforementioned medium stay in container (p1), only has dispersion to discharge from relief outlet (t1).
Aforementioned wet-type ball mill has gland seal device (u1) as shown in Figure 2.Aforementioned axis seal apparatus (u1) has 2 mechanical seal unit, this mechanical seal unit has the structure that the mode to be formed sealing by the set collar 4 that is fixed on swiveling ring in aforementioned axis (q1) 3 and is fixed on the housing 1 of the gland seal device in Fig. 1 arranges, and swiveling ring 3 in this unit and the arrangement mode of set collar 4 are towards equidirectional in 2 unit.Here, sealing refers to the pair of sliding face being formed by aforementioned swiveling ring 3 and set collar 4.In addition, between 2 mechanical seal unit, there is fluid-tight space 11, there is the outside seal liquid supplying opening 5 and the outside seal liquid relief outlet 6 that are communicated with this fluid-tight space 11.In aforementioned fluid-tight space 11, the outside seal liquid (R) of being supplied with by pump 8 from outside seal flow container 7 is supplied with via said external sealing liquid supplying opening 5, gets back to aforementioned tank 7 via said external sealing liquid relief outlet 6, and supply thus circulates.Thus, fill outside seal liquid (R) in aforementioned fluid-tight space 11, and the gap 9 forming between swiveling ring 3 and set collar 4 is filled up by outside seal liquid (R) in aforementioned sealing liquid-tightly.Carry out the lubrication and cooling of the slipping plane of aforementioned swiveling ring 3 and aforementioned set collar 4 by sealing liquid (R).
In addition, set the inflow pressure of sealing liquid (R) and the pressure of spring 10, make following 3 kinds of force balances: the power P1 that due to the inflow pressure of outside seal liquid (R), set collar 4 is pushed to swiveling ring 3, due to spring 10, set collar 4 is pushed to the power P2 of swiveling ring 3, and due to the inflow pressure of outside seal liquid (R), set collar 4 is pulled away to the power P3 of swiveling ring 3.Thus, in the gap 9 of the set collar 4 as slipping plane and swiveling ring 3, be filled with outside seal liquid (R) liquid-tightly, in this gap 9, do not have aforementioned acrylic polymers (X), aforesaid compound (c) enters.In the situation that aforementioned acrylic polymers (X), aforesaid compound (c) flow into this gap 9; because aforementioned swiveling ring 3 produces Mechanical free radical (mechano radical) with the slip of aforementioned set collar 4 by this acrylic polymers (X) and this compound (c); sometimes (methyl) acryl generation polymerization that they have and occur gelation, thickening; and there is the wet-type ball mill of the present invention of the such gland seal device of aforementioned axis seal apparatus (u1) by use, can avoid this risk.
For the such gland seal device of aforementioned axis seal apparatus (u1), for example, can list tandem type mechanical seal etc.In addition, for thering is the commercially available product of aforementioned tandem type mechanical seal as the wet-type ball mill of gland seal device, for example, can list " LMZ " series of Ashizawa Finetech Ltd. manufacture etc.
The reactive liquid of said external sealing liquid (R) right and wrong, for example, can list the various organic solvents cited as the organic solvent using in the time manufacturing aforementioned acrylic polymers (X) etc.In the middle of these, the same solvent of solvent phase using during preferably with the aforementioned acrylic polymers of manufacture (X), therefore, preferably ketone solvent, particularly preferably methylethylketone (MEK) or methyl iso-butyl ketone (MIBK) (MIBK).
The medium being filled in the container (p1) in Fig. 1 for example can use various microballons.The starting material of microballon for example can list: zirconium white, glass, titanium oxide, copper, silicic acid zirconium white etc.In the middle of these, due to the hardest and abrasion less and the microballon of preferential oxidation zirconium.
For aforementioned medium, separating of the slurry of the isolated body 2 of the screen cloth type from Fig. 1 and medium is good, jitter time can highly become shorter, can not cross the excessive dispersion phenomenon that does not produce by force inorganic particles (a) to the impact of aforementioned inorganic particles (a) because of the pulverizing of aforementioned inorganic particles (a), and preferably median size is counted the medium of the scope of 10～1000 μ m by median particle diameter.
Aforementioned excessive dispersion phenomenon refers to: because the destruction of inorganic particles generates new active surface, cause the phenomenon reassociating.While having produced excessive dispersion phenomenon, dispersion liquid can gelation.
From disperseing required power minimum, the aspect that can pulverize most effectively, the filling ratio of the medium in the container (p1) in Fig. 1 is preferably the scope of 75～90 long-pending volume % of container contents.
For aforementioned agitating vane (r1), impact during from the collision of medium and aforementioned inorganic particles (a) is large, dispersion efficiency improves, preferably be rotated driving, the more preferably scope of 8～20m/sec taking the circumferential speed of first end as the mode of the scope of 5～20m/sec.
While using this wet-type ball mill to manufacture resin combination of the present invention, its manufacture method can be intermittent type, can be also continous way.In addition, the in the situation that of continous way, can be the circular form of again supplying with after slurry is taken out, can be also non-circular form.In the middle of these, improve and the dispersions obtained also aspect of excellence of uniformity from production efficiency, be preferably circular form.
In addition, in the time using this wet-type ball mill to manufacture resin combination of the present invention, preferably carry out with two-stage procedure,, the larger particles that with median particle diameter is the scope of 400～1000 μ m carries out pre-dispersed operation as medium, then with median particle diameter be 15～400 μ m scope carry out main dispersion step compared with small-particle as medium.
It is the larger medium of the scope of 400～1000 μ m that aforementioned pre-dispersed operation is used median particle diameter.The surging force that this medium applies in the time colliding with inorganic particles (a) is large, and the comminuted height of the inorganic particles (a) that therefore particle diameter is large uses it inorganic particles of raw material (A) can be crushed to particle diameter to a certain degree.It is the less medium of the scope of 15～400 μ m that aforementioned main dispersion step is used median particle diameter.The surging force that this medium applies in the time colliding with inorganic particles (a) is little, but compared with the medium large with particle diameter, in same volume, the quantity of contained particle increases, and therefore increases with the collision frequency of inorganic particles (a).Therefore, it is for being further ground into fine particle by the inorganic particles (a) being crushed in pre-dispersed operation to a certain degree., when aforementioned pre-dispersed operation is long, have the worry that produces aforementioned excessive dispersion phenomenon here, therefore this pre-dispersed operation is preferably carried out in the scope in aforementioned container (p1) 1～3 cycle of internal recycle with slurry.
Active energy ray-curable resin composition of the present invention can be for coating purposes.This coating can solidify the coating use that is used as protecting substrate surface by being coated on various base materials and irradiating active energy beam.In this situation, coating of the present invention directly can be coated by the member of surface protection and used, the film that also coating on plastics film can be obtained is as protective membrane.Or, also can be by the film that is coated with coating of the present invention and formed film on plastics film as optical thin films such as antireflection film, diffusion barrier and prismatic lenses.Use the film of coating gained of the present invention to there is the feature that surface hardness is high, transparent also excellent, therefore can be coated on various plastics films to meet the thickness of purposes, use as protective membrane purposes, film like products formed.
Aforementioned plastics film for example can list: the plastics film, the plastic sheet that are formed by polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefine, epoxy resin, melamine resin, tri acetyl cellulose resin, ABS resin, AS resin, norbornene resin, cyclic olefin, polyimide resin etc.
In above-mentioned plastics film; tri acetyl cellulose film is the film that is suitable for especially the Polarizer purposes of liquid-crystal display; but general thickness is thinner; be 40～100 μ m; even if be therefore also difficult to fully improve surface hardness, and there is easily significantly curling feature in the situation that being provided with hard coat.Even if the film being formed by resin combination of the present invention is in the situation that using tri acetyl cellulose film as base material, also bring into play surface hardness high, the also effect of excellence of resistance to crimp tendency, toughness, the transparency, can be used aptly.At this use cellulose triacetate film as base material in the situation that, the glue spread while being coated with coating of the present invention preferably: scope taking dried thickness as 4～20 μ m, the mode that is preferably the scope of 6～15 μ m are coated with.Coating process now for example can list: excellent painting machine coating, the coating of Meyer rod, air knife coating, intaglio plate coating, reverse intaglio plate coating, offset printing, flexible printing, silk screen print method etc.
In above-mentioned plastics film, polyester film for example can list polyethylene terephthalate, and its thickness is generally 100～300 μ m left and right.This film is due to cheap and easily processing and for various uses such as touch-screen displays, but that it has is very soft, the feature that is also difficult to fully improve surface hardness in the situation that being provided with hard coat.Using this polyethylene film as base material in the situation that, the glue spread while being coated with coating of the present invention preferably: according to its purposes, scope taking dried thickness as 5～100 μ m, the mode that is preferably the scope of 7～80 μ m are coated with.General in the case of being coated with coating to exceed the such thickness of 30 μ m, compared with situation about being coated with the thickness with thinner, there is easily significantly curling tendency, and coating of the present invention has the feature of resistance to crimp tendency excellence, even if therefore be also not easy to produce curling in the case of the higher thickness coating that exceedes 30 μ m, can use aptly.Coating process now for example can list: excellent painting machine coating, the coating of Meyer rod, air knife coating, intaglio plate coating, reverse intaglio plate coating, offset printing, flexible printing, silk screen print method etc.
In above-mentioned plastics film, polymethyl methacrylate film general thickness is 100～2,000 about μ m, thicker and solid, therefore this film can be aptly for the front panel purposes of liquid-crystal display etc., particularly require the purposes of high surface hardness.In the situation that using this polymethyl methacrylate film as base material, glue spread while being coated with coating of the present invention is preferably: according to its purposes, scope taking dried thickness as 5～100 μ m, the mode that is preferably the scope of 7～80 μ m are coated with.Generally, polymethyl methacrylate film such compared with thick film on when exceeding the such thickness of 30 μ m and be coated with coating, although can form the laminate film that surface hardness is high, but the tendency that exists the transparency to reduce, and coating of the present invention has the very high transparency compared with existing coating, therefore can obtain having concurrently high surface hardness and transparent laminate film.Coating process now for example can list: excellent painting machine coating, the coating of Meyer rod, air knife coating, intaglio plate coating, reverse intaglio plate coating, offset printing, flexible printing, silk screen print method etc.
The active energy beam irradiating in the time that paint solidification of the present invention is made to film for example can list ultraviolet ray, electron rays.In the time utilizing ultraviolet ray to be cured, can use the UV irradiation equipment with xenon lamp, high voltage mercury lamp, metal halide lamp as light source, adjust as required the configuration of light quantity, light source etc.Using when high voltage mercury lamp, conventionally, preferably with respect to 1 lamp of light quantity of scope with 80～160W/cm, be cured with the scope of transfer rate 5～50m/ minute.And in the time utilizing electron rays to be cured, conventionally preferably use the electron rays booster machinery of the acceleration voltage of the scope with 10～300kV to be cured with the scope of transfer rate 5～50m/ minute.
In addition, the base material that is coated with coating of the present invention is not only plastics film, also can be used as aptly the surface coated agent of collision bumper of various plastic molded articles, such as mobile phone, household electrical appliance, automobile etc.In this situation, as the formation method of its film, for example, can list finishing, transfer printing, sheet bonding method etc.
Aforementioned finishing is following method: aforementioned coating is sprayed and is coated with or uses curtain to be coated with the printing equipments such as machine, roller coating machine, intaglio plate coating machine after finishing coat is coated on products formed, irradiate active energy beam it is solidified.
Aforementioned transfer printing can list following method: will on the base sheet with release property, be coated with aforementioned coating of the present invention and transfer materials be bonded in products formed surface after, peel off base sheet, at products formed surface transfer finishing coat, then irradiate active energy beam it is solidified; Or, after this transfer materials is bonded in to products formed surface, irradiates active energy beam it is solidified, then, peel off base sheet, thus at products formed surface transfer finishing coat.
And aforementioned bonding method is following method: by thering is the screening glass of the film being formed by aforementioned coating of the present invention or there is the film that formed by aforementioned coating and the screening glass of ornament layer is adhered to plastic molded article on base sheet on base sheet, form protective layer on products formed surface thus.
In the middle of these, coating of the present invention can be preferred for transfer printing and sheet bonding method purposes.
In aforementioned transfer printing, first make transfer materials.This transfer materials for example can by aforementioned coating separately or be coated in substrate sheets with the mixture that polyisocyanate compound is obtained by mixing, heating manufactures film semicure (B-rank).
Here, contained aforementioned acrylic polymers (X), the aforesaid compound (c) of active energy ray curable compound of the present invention is while having the compound of hydroxyl in molecular structure, in order more effectively to carry out aforementioned B-rank chemical industry order, can be used in combination polyisocyanate compound.
In order to manufacture transfer materials, first, the aforementioned coating of the present invention of application in substrate sheets.The method of the aforementioned coating of application for example can list: the coating methods such as intaglio plate coating method, rolling method, spraying coating method, lip coating method, comma coating method, the print processes such as woodburytype, silk screen print method etc.From antifriction consumption and the good aspect of chemical proofing, thickness when application preferably: the mode that reaches 0.5～30 μ m with the thickness of the film after solidifying is carried out application, more preferably carries out application in the mode that reaches 1～6 μ m.
After the aforementioned coating of preceding method application in substrate sheets, heat drying makes film semicure (B-rank).Heating 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.
Used the formation of the sealer of the products formed of aforementioned transfer materials for example to carry out as follows: by the B-rank of aforementioned transfer materials resin layer and products formed bonding after, irradiate active energy beam make resin layer solidify.Particularly, for example can list following method etc.: by the B-rank of transfer materials resin layer be bonded in products formed surface, then, peel off the base sheet of transfer materials, thus by the B-rank of transfer materials resin layer be transferred on products formed surface after, irradiate the method (transfer printing) of can actinic radiation-curable carrying out the crosslinking curing of resin layer by active energy beam; Aforementioned transfer materials is clipped in forming mould, fill up resin to mould intracavitary administration, in obtaining synthetic resin at its surface bonding transfer materials, after peeling off base sheet and being transferred on products formed, irradiate the method (moulding is transfer printing simultaneously) of can actinic radiation-curable carrying out the crosslinking curing of resin layer by active energy beam.
Then, for sheet bonding method, specifically can list following method etc.: by the protective layer made in advance form with the base sheet of sheet and products formed bonding after, make its thermofixation carry out the method (rear bonding method) of the crosslinking curing of the resin layer that B-rank form by heating; Aforementioned protective layer formation is clipped in forming mould with sheet; fill up resin to mould intracavitary administration; in obtaining synthetic resin, by after bonding with sheet to its surface and protective layer formation, make its thermofixation carry out the method for the crosslinking curing of resin layer (moulding is bonding method simultaneously) by heating.
Then; film of the present invention is on aforementioned plastics film, to be coated with coating of the present invention and to make it solidify the film forming; or be coated with coating of the present invention as the surface protectant of plastic molded article and solidify the film forming; and film of the present invention is the film that is formed with film on plastics film.
In the middle of the various uses of aforementioned film; as previously mentioned; from the aspect of hardness of film excellence, preferably by plastics film, be coated with coating of the present invention and irradiate active energy beam and film as the Polarizer protective membrane of use in liquid-crystal display, touch-screen display etc.Particularly, on the protective membrane of Polarizer using, be coated with coating of the present invention and irradiate active energy beam in liquid-crystal display, touch-screen display etc. and it is solidified and while making film, form cured coating film and have concurrently the protective membrane of high rigidity and high transparent.In the protective membrane purposes of Polarizer, also can be formed with binder layer on the surface of a side contrary to the coating layer that is coated with coating of the present invention.
Embodiment
Below provide concrete Production Example, embodiment is described more specifically the present invention, but the present invention is not limited to these embodiment.In case of no particular description, part and the % in example is quality criteria.
In embodiments of the invention, weight-average molecular weight (Mw) is the value that uses gel permeation chromatography (GPC) to record according to following condition.
Determinator; TOSOH Co., Ltd manufactures HLC-8220
Chromatographic column: TOSOH Co., Ltd manufactures guard column HXL-H
+ TOSOH Co., Ltd manufactures TSKgel G5000HXL
+ TOSOH Co., Ltd manufactures TSKgel G4000HXL
+ TOSOH Co., Ltd manufactures TSKgel G3000HXL
+ TOSOH Co., Ltd manufactures TSKgel G2000HXL
Detector: RI(differential refractometer)
Data processing: TOSOH Co., Ltd manufactures SC-8010
Condition determination: 40 DEG C of column temperatures
Solvents tetrahydrofurane
Flow velocity 1.0ml/ minute
Standard: polystyrene
Sample: (100 μ l) by the solution that is scaled the tetrahydrofuran solution micro-strainer filtration of 0.4 % by weight by resin solid composition and obtain
The inorganic particles (a) using in the embodiment of the present application
Inorganic particles (a-1): Nippon Aerosil Co., " AEROSIL R7200 " median size that Ltd. manufactures is 12nm, the silicon dioxide microparticle at particle surface with (methyl) acryl
Inorganic particles (a-2): Nippon Aerosil Co., " AEROSIL R711 " median size that Ltd. manufactures is 12nm, the silicon dioxide microparticle at particle surface with (methyl) acryl
Inorganic particles (a-3): by Nippon Aerosil Co., 100 parts of " AEROSIL OX50 " (median size be 40nm silicon dioxide microparticle), 4 parts, water and 18 parts of mixed silicon dioxide microparticles of heat-treating gained at 140 DEG C that are incorporated in of 3-trimethoxysilyl-propyl methyl acid esters that Ltd. manufactures
Inorganic particles (a-4): by Nippon Aerosil Co., 100 parts of " AEROSIL90G " (median size be 20nm silicon dioxide microparticle), 4 parts, water and 18 parts of mixed silicon dioxide microparticles of heat-treating gained at 140 DEG C that are incorporated in of 3-trimethoxysilyl-propyl methyl acid esters that Ltd. manufactures
Inorganic particles (a-5): Nippon Aerosil Co., " AEROSIL50 " median size that Ltd. manufactures is 30nm, the silicon dioxide microparticle at particle surface without modification group
Inorganic particles (a-6): " MEK-ST " that Misao Kusano manufactures
Inorganic particles (a-7): " the ELCOM V-8804 " that wave the manufacture of catalyst Hua Zhi Co., Ltd. day has the silicon dioxide microparticle of (methyl) acryl at particle surface
Inorganic particles (a-8): Nippon Aerosil Co., " AEROSIL974 " median size that Ltd. manufactures is 12nm, the silicon dioxide microparticle at particle surface with methyl
Inorganic particles (a-9): the alumina particulate of " UFA-150 " median size 15nm that Showa Denko K. K manufactures
Production Example 1
The manufacture of acrylic polymers (X-1)
Drop into propylene glycol monomethyl ether 480 mass parts to possessing in the reaction unit of whipping appts, cooling tube, dropping funnel and nitrogen ingress pipe, make while stirring temperature in system be warming up to 110 DEG C, then, the mixed solution that utilizes dropping funnel cost to drip for 3 hours to comprise glycidyl methacrylate 91 mass parts, methyl methacrylate 318 mass parts, cyclohexyl methacrylate 45 mass parts and peroxide-2-ethyl hexanoic acid tert-butyl (" PERBUTYL O " that Japanese emulsifying agent Co., Ltd. manufactures) 15 mass parts then keeps 15 hours at 110 DEG C.Then, be cooled to after 90 DEG C, after dropping into first quinone 0.1 mass parts and vinylformic acid 46 mass parts, add triphenylphosphine 5 mass parts, then be further warming up to 100 DEG C and keep 8 hours, obtain propylene glycol monomethyl ether solution 1000 mass parts (nonvolatile component 50.0 quality %) of acrylic polymers (X-1).Each character value of this acrylic polymers (X-1) is as follows.Weight-average molecular weight (Mw): 24,000, the theoretical acryl equivalent that solids component converts: 747g/eq, hydroxyl value 75mgKOH/g.
Production Example 2
The manufacture of acrylic polymers (X-2)
Drop into methyl iso-butyl ketone (MIBK) 480 mass parts to possessing in the reaction unit of whipping appts, cooling tube, dropping funnel and nitrogen ingress pipe, make while stirring temperature in system be warming up to 110 DEG C, then, the mixed solution that utilizes dropping funnel cost to drip for 3 hours to comprise glycidyl methacrylate 130 mass parts, methyl methacrylate 304 mass parts and peroxide-2-ethyl hexanoic acid tert-butyl (" PERBUTYL O " that Japanese emulsifying agent Co., Ltd. manufactures) 15 mass parts then keeps 15 hours at 110 DEG C.Then, be cooled to after 90 DEG C, after dropping into first quinone 0.1 mass parts and vinylformic acid 66 mass parts, add triphenylphosphine 5 mass parts, then be further warming up to 100 DEG C and keep 8 hours, obtain methyl isobutyl ketone solution 1000 mass parts (nonvolatile component 50.0 quality %) of acrylic polymers (X-2).Each character value of this acrylic polymers (X-2) is as follows.Weight-average molecular weight (Mw): 26,000, the theoretical acryl equivalent that solids component converts: 522g/eq, hydroxyl value 108mgKOH/g.
Production Example 3
The manufacture of acrylic polymers (X-3)
Drop into propylene glycol monomethyl ether 455 mass parts to possessing in the reaction unit of whipping appts, cooling tube, dropping funnel and nitrogen ingress pipe, make while stirring temperature in system be warming up to 110 DEG C, then, utilize dropping funnel cost to drip for 3 hours to comprise glycidyl methacrylate 166 mass parts, methyl methacrylate 208 mass parts, isobornyl methacrylate 42 mass parts and peroxide-2-ethyl hexanoic acid tert-butyl (" PERBUTYL O " that the Japanese emulsifying agent Co., Ltd. manufactures) mixed solution that 40 mass parts form, then at 110 DEG C, keep 15 hours.Then, be cooled to after 90 DEG C, after dropping into first quinone 0.1 mass parts and vinylformic acid 84 mass parts, add triphenylphosphine 5 mass parts, then be further warming up to 100 DEG C and keep 8 hours, obtain propylene glycol monomethyl ether solution 1000 mass parts (nonvolatile component 50.0 quality %) of acrylic polymers (X-3).Each character value of this acrylic polymers (X-3) is as follows.Weight-average molecular weight (Mw): 11,000, the theoretical acryl equivalent that solids component converts: 409g/eq, hydroxyl value 137mgKOH/g.
Production Example 4
The manufacture of acrylic polymers (X-4)
Drop into methyl iso-butyl ketone (MIBK) 485 mass parts to possessing in the reaction unit of whipping appts, cooling tube, dropping funnel and nitrogen ingress pipe, make while stirring temperature in system be warming up to 110 DEG C, then, the mixed solution that utilizes dropping funnel cost to drip for 3 hours to comprise glycidyl methacrylate 230 mass parts, methyl methacrylate 115 mass parts, cyclohexyl methacrylate 38 mass parts and peroxide-2-ethyl hexanoic acid tert-butyl (" PERBUTYL O " that Japanese emulsifying agent Co., Ltd. manufactures) 10 mass parts then keeps 15 hours at 110 DEG C.Then, be cooled to after 90 DEG C, after dropping into first quinone 0.1 mass parts and vinylformic acid 117 mass parts, add triphenylphosphine 5 mass parts, then be further warming up to 100 DEG C and keep 8 hours, obtain methyl isobutyl ketone solution 1000 mass parts (nonvolatile component 50.0 quality %) of acrylic polymers (X-4).Each character value of this acrylic polymers (X-4) is as follows.Weight-average molecular weight (Mw): 42,000, the theoretical acryl equivalent that solids component converts: 297g/eq, hydroxyl value 189mgKOH/g.
Production Example 5
The manufacture of acrylic polymers (X-5)
Drop into methyl iso-butyl ketone (MIBK) 470 mass parts to possessing in the reaction unit of whipping appts, cooling tube, dropping funnel and nitrogen ingress pipe, make while stirring temperature in system be warming up to 110 DEG C, then, utilize dropping funnel cost to drip for 3 hours to comprise glycidyl methacrylate 321 mass parts, methyl methacrylate 17 mass parts and peroxide-2-ethyl hexanoic acid tert-butyl (" PERBUTYL O " that the Japanese emulsifying agent Co., Ltd. manufactures) mixed solution that 25 mass parts form, then at 110 DEG C, keep 15 hours.Then, be cooled to after 90 DEG C, after dropping into first quinone 0.1 mass parts and vinylformic acid 163 mass parts, add triphenylphosphine 5 mass parts, then be further warming up to 100 DEG C and keep 8 hours, obtain methyl isobutyl ketone solution 1000 mass parts (nonvolatile component 50.0 quality %) of acrylic polymers (X-5).Each character value of this acrylic polymers (X-5) is as follows.Weight-average molecular weight (Mw): 22,000, the theoretical acryl equivalent that solids component converts: 221g/eq, hydroxyl value 253mgKOH/g.
In the molecular structure using in the embodiment of the present application, there is the compound (c) of (methyl) acryl:
Compound (c-1): dipentaerythritol acrylate
Compound (c-2): Viscoat 295
Production Example 6
The manufacture of compound (c-3)
Add dicyclohexyl methyl hydride-4,4 '-vulcabond, 166 mass parts, dibutyl tin laurate 0.2 mass parts and first quinone 0.2 mass parts, warming while stirring to 60 DEG C to possessing in the reaction unit of whipping appts.Then, divide input 10 times by pentaerythritol triacrylate (" ARONIXM-305 " that Toagosei Co., Ltd manufactures) 630 mass parts, dropped into once every 10 minutes.Further reaction 10 hours finishes reaction after the absorption disappearance of isocyanate group that confirms 22500cm-1 by infrared spectrum, obtains urethane acrylate (c-3).Each character value of this urethane acrylate (c-3) is as follows.Weight-average molecular weight (Mw): Isosorbide-5-Nitrae 00, theoretical acryl equivalent: 120g/eq.
Embodiment 1
Methyl isobutyl ketone solution 20 mass parts (acrylic polymers in 20 mass parts (X-2) is 10.0 mass parts) of the acrylic polymers (X-2) obtaining in the aforementioned Production Example 2 of compounding, dipentaerythritol acrylate (c-1) 45 mass parts, inorganic particles (a-1) 45 mass parts, methyl iso-butyl ketone (MIBK) (following brief note is " MIBK ") 80 mass parts and propylene glycol monomethyl ether (following brief note is " PGM ") 10 mass parts, make the slurry of nonvolatile component 50 quality %, use wet-type ball mill (" Star mill LMZ015 " that AshizawaLtd. manufactures) to carry out blending dispersion to it, obtain dispersion.
Each condition of utilizing aforementioned wet-type ball mill to disperse is as follows.
Medium: the zirconium white microballon of median particle diameter 100 μ m
Resin combination is with respect to the filling ratio of internal volume of mill: 70 volume %
The circumferential speed of the first end of agitating vane: 11m/sec
The flow velocity of resin combination: 200ml/min
Jitter time: 60 minutes
In dispersions obtained, add light trigger (" IRGACURE#184 " that Ciba Specialty Chemicals Inc. manufactures) 2 mass parts, further add MIBK and PGM to be prepared into nonvolatile component rate 40 quality %, obtain active energy ray-curable resin composition.For this active energy ray-curable resin composition, by following its performance of various test evaluations, the results are shown in table 1.
The mensuration of the median size of inorganic particles (A)
For the median size recording based on dynamic light scattering method of the inorganic particles in active energy ray-curable resin composition (A), dilute with MIBK dispersions obtained, after being adjusted into the MIBK solution of concentration 5%, " ELSZ-2 " that uses this MIBK solution, manufactures with particle size determination device (Otsuka Electronics Co., Ltd.: according to " ISO13321 ".Calculate by the Cumulant Method Using) measure.
The storage stability test of active energy ray-curable resin composition
Aforementioned active energy ray-curable resin composition is left standstill to 1 month under the temperature condition of 40 DEG C, and evaluating each process time point has sediment-free.
Zero: do not observe throw out
△: observed throw out after 3 weeks
×: after 1 week, observe throw out
The pencil hardness test of film
1. the making method of test film
By aforementioned active energy ray-curable resin composition with excellent painting machine so that the thickness after solidifying is the mode of prescribed value is separately coated on following plastics film, at 70 DEG C, be dried 1 minute, under nitrogen, use high voltage mercury lamp by film, it to be solidified with the irradiation dose of 250mJ/cm2, obtain thus having the test film of cured coating film.
(thickness 80 μ are m) upper, 10 μ m for cellulose triacetate film (following brief note is " TAC ")
(thickness 188 μ are m) upper, 10,20,50 μ m for pet film (following brief note is " PET ")
(thickness 300 μ are m) upper, 10,20,50 μ m for polymethyl methacrylate film (following brief note is " PMMA ")
2. pencil hardness test method
For the curing overlay film of above-mentioned test film, according to JIS K5400, test film taking cellulose triacetate film as base material is carried out to the pencil test of load 500g, test film taking pet film as base material is carried out to the pencil test of load 750g, test film taking polymethyl methacrylate film as base material is carried out to the pencil test of load 1000g, evaluate thus.Carry out 5 tests, will cause above for 1 time the hardness of low one-level of the hardness of cut as the pencil hardness of this film.
The transparency test of film
1. the making method of cured coating film
Method same when with above-mentioned pencil hardness test is made test film.In addition, about the transparency of film, only to the thickness of test film entirety the thinnest, cellulose triacetate film (thickness 80 μ are the test film of made under the condition of upper, thickness 10 μ m m), and the thickness of test film entirety the thickest, polymethyl methacrylate film (thickness 188 μ m) under the condition of upper, thickness 50 μ m the test film of made test.
2. transparent test method
Use Suga Test Instruments Co., " the Haze Computer HZ-2 " that Ltd. manufactures measures the haze value of film.Haze value is lower, and the transparency of film is higher.
The woolliness of the resistance to steel wire test of film
1. the making method of cured coating film
Method same when with above-mentioned pencil hardness test is made film.In addition, because the woolliness of resistance to steel wire of film does not exist the difference producing because of the kind of base material film substantially, therefore test only for cellulose triacetate film (thickness 80 μ m) under the condition of upper, thickness 10 μ m the test film of made carry out.
2. the woolliness of resistance to steel wire test
With steel wool, (Nippon Steel Wool Co., " Bonstar#0000 " 0.5g that Ltd. manufactures encases the discoid pressure head of 2.4 centimetres of diameters, this pressure head is applied to the load that 1000g is heavy and evaluating with coming and going 100 times in the film aspect of film.Use Suga Test Instruments Co., the haze value of the film before and after " HazeComputer HZ-2 " determination test that Ltd. manufactures, by their difference of δ H evaluation.δ H value is less, and the scuff resistance of cured coating film is more excellent.
The resistance to crimp tendency test of film
1. the making method of cured coating film
Method same when with above-mentioned pencil hardness test is made film.In addition, about the resistance to crimp tendency of film, only curling to especially easily producing, cellulose triacetate film (thickness 80 μ m) under the condition of upper, thickness 10 μ m the test film of made and pet film (thickness 188 μ m) under the condition of upper, thickness 50 μ m the test film of made test.
2. resistance to crimp tendency test
Test film is cut into 10cm square, measures 4 angles from the floating of level, evaluate with its mean value.Be worth less film curling less, the resistance to crimp tendency of film is more excellent.
The bending test of film
1. the making method of cured coating film
Method same when with above-mentioned pencil hardness test is made film.In addition, about the bending of film, only to most requirement have this performance, cellulose triacetate film (thickness 80 μ m) under the condition of upper, thickness 10 μ m the test film of made test.
2. bending property test
Use mandrel trier (" flexing machine " that TP Ji Yan Co., Ltd. manufactures), test film is twisted on proof stick, carry out the test whether cracking with the cured coating film layer of Visual Confirmation film, using the minimum diameter of the proof stick not cracking as evaluation result.Minimum diameter is less, and the bending of film is more excellent.
The alkaline resistance test of film
1. the making method of cured coating film
Method same when with above-mentioned pencil hardness test is made film.In addition, because the alkali resistance of film does not exist the difference producing because of the thickness of the kind of base material film, cured coating film layer substantially, therefore test only to cellulose triacetate film (thickness 80 μ m) under the condition of upper, thickness 10 μ m the test film of made carry out.
2. alkaline resistance test
To make film closely sealed with the absorbent cotton (3cm × 3cm) that has flooded 5% aqueous sodium hydroxide solution, to cover glass cover in order preventing dry, at 25 DEG C, place 24 hours, evaluate the condition of surface of film.
Zero: do not observe variation
△: observe foaming
×: film generation gonorrhoea
Make to consist of the formula shown in table 1 and 2, in addition obtain similarly to Example 1 active energy ray-curable resin composition.They are carried out to test similarly to Example 1.The results are shown in table 1 and 2.
[table 1]
[table 2]
Comparative example 1
The formulation homogenous disperse device that methyl isobutyl ketone solution 40 mass parts of the acrylic polymers (X-2) obtaining in aforementioned compounding Production Example 2 (acrylic polymers in 40 mass parts (X-1) is 20.0 mass parts), dipentaerythritol acrylate (c-1) 35 mass parts, inorganic particles (a-6) 150 mass parts are obtained carries out blending dispersion, obtains dispersion.For this dispersion, prepare similarly to Example 1 active energy ray-curable resin composition, carry out test similarly to Example 1.The results are shown in table 3.
Each condition of the dispersion based on aforementioned homogenous disperse device is as follows.
Rotating speed: 2400r/min
Jitter time: 15 minutes
Comparative example 2
Make to consist of the formula shown in table 3, in addition similarly prepare active energy ray-curable resin composition with comparative example 1, carry out test similarly to Example 1.The results are shown in table 3.
Comparative example 3 and 4
Make to consist of the formula shown in table 3, in addition prepare similarly to Example 1 active energy ray-curable resin composition, they are carried out to test similarly to Example 1.The results are shown in table 3.
Comparative example 5
The formulation homogenous disperse device that methyl isobutyl ketone solution 24 mass parts of the acrylic polymers (X-5) obtaining in aforementioned compounding Production Example 5 (acrylic polymers in 24 mass parts (X-5) is 12.0 mass parts), Viscoat 295 (c-2) 48 mass parts, urethane acrylate (c-3) 25 mass parts, inorganic particles (a-8) 15 mass parts and methyl iso-butyl ketone (MIBK) 10 mass parts are obtained carries out blending dispersion, obtains dispersion.For this dispersion, prepare similarly to Example 1 active energy ray-curable resin composition, carry out test similarly to Example 1.The results are shown in table 3.
Each condition of the dispersion based on homogenous disperse device in comparative example 5 is as follows.
Rotating speed: 2400r/min
Jitter time: 150 minutes
Comparative example 6
The paint shaker that the formulation that methyl isobutyl ketone solution 100 mass parts of the acrylic polymers (X-5) obtaining in aforementioned compounding Production Example 5 (acrylic polymers in 100 mass parts (X-5) is 50.0 mass parts), inorganic particles (a-9) 50 mass parts and methyl iso-butyl ketone (MIBK) 100 mass parts are obtained is medium in order to the zirconium white microballon of median size 0.3mm carries out 2 hours blending dispersion, obtains dispersion.For this dispersion, prepare similarly to Example 1 active energy ray-curable resin composition, carry out test similarly to Example 1.The results are shown in table 3.
[table 3]
Claims (18)
1. an active energy ray-curable resin composition; it is characterized in that; its inorganic particles (A) and weight-average molecular weight (Mw) that contains the scope that the median size that records based on dynamic light scattering method is 95～250nm is 5; 000～80; in 000 scope and molecular structure, there is the acrylic polymers (X) of (methyl) acryl as neccessary composition, in its nonvolatile component 100 mass parts, contain described inorganic particles (A) with the scope of 35～60 mass parts.
2. active energy ray-curable resin composition according to claim 1, wherein, described inorganic particles (A) is for selecting a kind of above inorganic particles in the prescription of free silicon-dioxide, aluminum oxide, zirconium white, titanium dioxide, barium titanate, antimonous oxide composition.
3. active energy ray-curable resin composition according to claim 2, wherein, described inorganic particles (A) is dry method silicon-dioxide.
4. active energy ray-curable resin composition according to claim 3, wherein, described inorganic particles (A) is for having the dry method silicon-dioxide containing the modification group of (methyl) acryl structure at its particle surface.
5. active energy ray-curable resin composition according to claim 1; wherein; described acrylic polymers (X) is for making acrylic polymers (Y) react with compound (z) polymkeric substance obtaining; the compound (y) that described acrylic polymers (Y) has reactive functional groups and (methyl) acryl carries out polymerization as neccessary composition and obtains, and described compound (z) has functional group and (methyl) acryl that the reactive functional groups that can have with described compound (y) react.
6. active energy ray-curable resin composition according to claim 5, wherein, described acrylic polymers (Y) for make described compound (y) and other acrylic monomers (v) the ratio of the scope taking their mass ratio (y)/(v) as 10/90～90/10 to carry out the polymerization that polymerization obtains resistance to.
7. active energy ray-curable resin composition according to claim 5; wherein; described compound (y) is for having the compound (y1) of epoxy group(ing) and (methyl) acryl, and described compound (z) is for having the compound (z1) of carboxyl and (methyl) acryl.
8. active energy ray-curable resin composition according to claim 1, wherein, the scope that (methyl) acryl equivalent of described acrylic polymers (X) is 220～1650eq/g.
9. active energy ray-curable resin composition according to claim 1, wherein, described acrylic polymers (X) has hydroxyl in molecular structure, the scope that its hydroxyl equivalent is 35～250mgKOH/g.
10. active energy ray-curable resin composition according to claim 1; wherein, on the basis of described inorganic particles (A) and described acrylic polymers (X), also contain compound (c) except described acrylic polymers (X), that there is (methyl) acryl in molecular structure.
11. active energy ray-curable resin compositions according to claim 1, it is manufactured by the following method: use and have container, turning axle, agitating vane, supplying opening, the wet-type ball mill of relief outlet and gland seal device, wherein, the inside of described container is filled with medium, described agitating vane has with the axis of rotation of aforementioned rotating shaft coaxle and under the effect of the rotary actuation of aforementioned turning axle and rotates, described supplying opening is arranged at described container, described relief outlet is arranged at described container, described gland seal device is disposed in the part that runs through container of described turning axle, described gland seal device has 2 mechanical seal unit, and the structure that the sealing with these 2 mechanical seal unit is sealed by outside seal liquid, from the described supplying opening of described wet-type ball mill to inorganic particles (A) described in described supply for receptacles and the resinous principle using described acrylic polymers (X) as neccessary composition, in described container, make described turning axle and the rotation of described agitating vane, be uniformly mixed medium and raw material, carry out thus the pulverizing of described inorganic particles (A) and this inorganic particles (A) to the dispersion in described resinous principle, then, discharge from described relief outlet.
The manufacture method of 12. 1 kinds of active energy ray-curable resin compositions, it is characterized in that, use has container, turning axle, agitating vane, supplying opening, the wet-type ball mill of relief outlet and gland seal device, wherein, the inside of described container is filled with medium, described agitating vane has with the axis of rotation of aforementioned rotating shaft coaxle and under the effect of the rotary actuation of aforementioned turning axle and rotates, described supplying opening is arranged at described container, described relief outlet is arranged at described container, described gland seal device is disposed in the part that runs through container of described turning axle, described gland seal device has 2 mechanical seal unit, and the structure that the sealing with these 2 mechanical seal unit is sealed by outside seal liquid, from the described supplying opening of described wet-type ball mill to described supply for receptacles inorganic particles (A) with weight-average molecular weight (Mw) 5, 000～80, in 000 scope and molecular structure, there is the acrylic polymers (X) of (methyl) acryl as the resinous principle of neccessary composition, in described container, make described turning axle and the rotation of described agitating vane, be uniformly mixed medium and raw material, carry out thus the pulverizing of described inorganic particles (A) and this inorganic particles (A) to the dispersion in described resinous principle, then, discharge from described relief outlet.
13. 1 kinds of coating, it contains the active energy ray-curable resin composition described in any one in claim 1～11.
14. 1 kinds of coating, it contains the active energy ray-curable resin composition of manufacturing by the manufacture method described in claim 12.
15. 1 kinds of films, it makes the paint solidification described in claim 13 or 14 and obtains.
16. 1 kinds of laminate films, its single or double at plastics film has the film described in claim 15.
17. laminate films according to claim 16, wherein, described plastics film is any in cellulose triacetate film, pet film, polymethyl methacrylate film.
18. laminate films according to claim 16, wherein, the thickness of described film is the scope of 5～100 μ m.
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| PCT/JP2012/074720 WO2013047590A1 (en) | 2011-09-30 | 2012-09-26 | Active energy beam-curable resin composition, method for producing thereof, coating, coating film, and film |
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| CN104411496A (en) * | 2012-06-21 | 2015-03-11 | Dic株式会社 | Active energy ray-curable resin composition, manufacturing method for active energy ray-curable resin composition, coating material, coating film, and film |
| CN112534009A (en) * | 2018-08-08 | 2021-03-19 | 三菱瓦斯化学株式会社 | Hard coating composition, laminate film and cured film |
| CN114350192A (en) * | 2021-02-01 | 2022-04-15 | 中南林业科技大学 | Coating with hydrophilic self-cleaning capability and preparation method thereof |
| CN115160846A (en) * | 2022-08-11 | 2022-10-11 | 广东希贵光固化材料有限公司 | Dual-curing repair putty |
| CN115873411A (en) * | 2022-10-26 | 2023-03-31 | 凤阳加松新型材料科技有限公司 | Preparation method of antiviral silica gel pad |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150177433A1 (en) * | 2012-07-13 | 2015-06-25 | Konica Minolta, Inc. | Infrared shielding film |
| JP6062810B2 (en) * | 2013-06-14 | 2017-01-18 | アピックヤマダ株式会社 | Resin mold and resin mold apparatus |
| KR101751372B1 (en) | 2013-09-25 | 2017-07-03 | 하리마 카세이 가부시키가이샤 | Photocurable resin composition and cured film thereof |
| JP6582993B2 (en) * | 2013-12-24 | 2019-10-02 | 横浜ゴム株式会社 | Hard coat layer forming composition |
| JP6421972B2 (en) * | 2014-06-24 | 2018-11-14 | Dic株式会社 | Active energy ray-curable composition, cured film thereof, and article having the cured film |
| JP6032382B2 (en) | 2014-10-24 | 2016-11-30 | Dic株式会社 | Active energy ray-curable resin composition, method for producing the same, paint, coating film, and laminated film |
| KR102406434B1 (en) * | 2014-12-24 | 2022-06-08 | 디아이씨 가부시끼가이샤 | Active energy ray-curable resin composition, coating material, coating film, and film |
| WO2017056196A1 (en) * | 2015-09-29 | 2017-04-06 | 帝国インキ製造株式会社 | Coating resin composition |
| WO2022202699A1 (en) * | 2021-03-22 | 2022-09-29 | 日本製紙株式会社 | Ionizing radiation-curable composition, hardcoat film, and method for producing hardcoat film |
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| CN101928436A (en) * | 2009-06-23 | 2010-12-29 | Dic株式会社 | Process for producing silica dispersion, energy-ray curable resin compositions, and films |
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| JP2008062539A (en) * | 2006-09-08 | 2008-03-21 | Nakajima Kogyo Kk | Glare shielding film |
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| JP2011157435A (en) * | 2010-01-29 | 2011-08-18 | Dic Corp | Method for producing inorganic particle dispersion |
| JP5610191B2 (en) * | 2010-03-24 | 2014-10-22 | Dic株式会社 | Inorganic particle dispersion, energy beam curable resin composition, and film |
| JP5035652B2 (en) * | 2010-12-22 | 2012-09-26 | Ｄｉｃ株式会社 | Method for producing dispersion, dispersion, paint, coating film, and film |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104411496A (en) * | 2012-06-21 | 2015-03-11 | Dic株式会社 | Active energy ray-curable resin composition, manufacturing method for active energy ray-curable resin composition, coating material, coating film, and film |
| CN112534009A (en) * | 2018-08-08 | 2021-03-19 | 三菱瓦斯化学株式会社 | Hard coating composition, laminate film and cured film |
| CN114350192A (en) * | 2021-02-01 | 2022-04-15 | 中南林业科技大学 | Coating with hydrophilic self-cleaning capability and preparation method thereof |
| CN114350192B (en) * | 2021-02-01 | 2023-01-06 | 中南林业科技大学 | Coating with hydrophilic self-cleaning capability and preparation method thereof |
| CN115160846A (en) * | 2022-08-11 | 2022-10-11 | 广东希贵光固化材料有限公司 | Dual-curing repair putty |
| CN115160846B (en) * | 2022-08-11 | 2023-10-20 | 广东希贵光固化材料有限公司 | Dual-curing repair putty |
| CN115873411A (en) * | 2022-10-26 | 2023-03-31 | 凤阳加松新型材料科技有限公司 | Preparation method of antiviral silica gel pad |
| CN115873411B (en) * | 2022-10-26 | 2023-10-13 | 凤阳加松新型材料科技有限公司 | Preparation method of antiviral silica gel pad |
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| KR101603932B1 (en) | 2016-03-25 |
| KR20140052023A (en) | 2014-05-02 |
| JP5472544B2 (en) | 2014-04-16 |
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| TW201319100A (en) | 2013-05-16 |
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