CN103842396B

CN103842396B - Active energy ray-curable resin composition, its manufacture method, coating, film and film

Info

Publication number: CN103842396B
Application number: CN201280047944.3A
Authority: CN
Inventors: 伊藤正广; 杉山将志; 渡边泰之; 谷本洋一; 渡边英树; 水口良
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2011-09-30
Filing date: 2012-09-26
Publication date: 2016-03-16
Anticipated expiration: 2032-09-26
Also published as: TWI599586B; KR20140052023A; TW201319100A; WO2013047590A1; KR101603932B1; JPWO2013047590A1; JP5472544B2; CN103842396A

Abstract

The invention provides the active energy ray-curable resin composition that excellent storage stability and then its cured coating film demonstrate very high surface hardness, the transparency, resistance to crimp tendency and alkali resistance, coating containing this resin combination, the film formed by this coating, and the film with this film layer.The feature of described active energy ray-curable resin composition is; it contains inorganic particles (A) that median size is the scope of 95 ~ 250nm and weight-average molecular weight (Mw) is 5; 000 ~ 80; the scope of 000 and the acrylic polymers (X) in molecular structure with (methyl) acryl, as neccessary composition, contain aforementioned inorganic particulate (A) with the scope of 35 ~ 60 mass parts in its nonvolatile component 100 mass parts.

Description

Active energy ray-curable resin composition, its manufacture method, coating, film and film

Technical field

The present invention relates to the active energy ray-curable resin composition that excellent storage stability and then its cured coating film demonstrate very high surface hardness, the transparency, resistance to crimp tendency and alkali resistance, coating containing this resin combination, the film formed by this coating, and the film with this film layer.

Background technology

The inorganic microparticle-dispersed type active energy ray-curable resin composition that inorganic microparticle-dispersed is obtained in resinous principle is compared with the resin combination only formed by organic-based material, as the high rigidity of cured coating film, the adjustment of specific refractory power, the contour performance-based of imparting of electroconductibility, the type material of New function can be realized, receive much concern in recent years.The purposes of this resin combination is varied; such as; performance cured coating film be this feature of high rigidity; be used as protection products formed, indicating meter surface can not scratch hard paint time; compared with using the situation of the resin combination only formed by organic-based material, the hard paint showing the resistance to marring being much better than it can be obtained.Wherein, in order to make more high rigidity and the also excellent hard paint of resistance to crimp tendency, it is effective for adding inorganic particles more, but the resin combination containing a large amount of inorganic particles easily produce inorganic particles through time precipitation, there is the shortcoming of storage stability difference.In addition, the dispersion of inorganic particles in resinous principle is insufficient, resin combination lacks storage stability, and the transparency of film also reduces.

As the hard paint formed by inorganic microparticle-dispersed type active energy ray-curable resin composition, known a kind of anti-dazzle film resin combination, it contains the acrylic polymers addition vinylformic acid of glycidyl methacrylate and the polymkeric substance, Viscoat 295, polyfunctional carbamate acrylate and the median size that obtain are the silicon dioxide microparticle (see patent documentation 1) of the scope of 297 ~ 540nm.This dispersion is compared with the hard paint only formed by organic, although the film of high rigidity can be obtained, but the silicon dioxide microparticle only containing about 17% in the nonvolatile component of resin combination, therefore do not reach the higher surface hardness of requirement, level of market demand in recent years.In addition, owing to being the resin combination of anti-dazzle film purposes, the particle diameter of therefore 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 that acryl equivalent is 214g/eq, hydroxyl value is 262mgKOH/g, weight-average molecular weight be 40,000 acrylic polymers and median size be alumina particulate, the zirconia particles (see patent documentation 2) of the scope of 55 ~ 90nm.This dispersion is compared with the hard paint only formed by organic, although the film of high rigidity can be obtained, 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 improved is sufficient hardness of film.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2008-62539 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2007-289943 publication

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 the active energy ray-curable resin composition of very high surface hardness, the transparency, resistance to crimp tendency and alkali resistance, coating containing this resin combination, the film formed by this coating, and the film with this film layer.

for the scheme of dealing with problems

The present inventor etc. conduct in-depth research to solve the problem, found that, the excellent storage stability of active energy ray-curable resin composition as described below, and the film formed by this resin combination very high surface hardness of performance and the transparency, thus complete the present invention, the feature of described active energy ray-curable resin composition is, it contains inorganic particles (A) that the median size recorded based on dynamic light scattering method is the scope of 95 ~ 250nm and weight-average molecular weight (Mw) is 5, 000 ~ 80, the scope of 000, and the acrylic polymers (X) in molecular structure with (methyl) acryl is as neccessary composition, aforementioned inorganic particulate (A) is contained with the scope of 35 ~ 60 mass parts in its nonvolatile component 100 mass parts.

Namely; the present invention relates to a kind of active energy ray-curable resin composition; it is characterized in that; it contains inorganic particles (A) that the median size recorded based on dynamic light scattering method is the scope of 95 ~ 250nm and weight-average molecular weight (Mw) is 5; 000 ~ 80; the scope of 000 and the acrylic polymers (X) in molecular structure with (methyl) acryl, as neccessary composition, contain aforementioned inorganic particulate (A) with the scope of 35 ~ 60 mass parts in its nonvolatile component 100 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 and there is the container being filled with medium in inside, turning axle, have with the turning axle of aforementioned rotating shaft coaxle and the agitating vane rotated by the rotary actuation of aforementioned turning axle, be arranged at the supplying opening of the raw material of aforesaid receptacle, be arranged at the relief outlet of the dispersion of aforesaid receptacle 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 sealing with these 2 mechanical seal unit the structure that seals by outside seal liquid, from the aforementioned supplying opening of described wet-type ball mill to aforementioned supply for receptacles inorganic particles (A) and with weight-average molecular weight (Mw) 5, 000 ~ 80, the scope of 000 and there is in molecular structure the resinous principle of acrylic polymers (X) as neccessary composition of (methyl) acryl, in aforesaid receptacle, make turning axle and agitating vane rotate, be uniformly mixed medium and raw material, carry out pulverizing and this inorganic particles (A) dispersion in aforementioned resin composition of aforementioned inorganic particulate (A) thus, then, discharge from aforementioned relief outlet.

The invention still further relates to the coating containing foregoing active energy ray curable resin composition.

The invention still further relates to the film formed by aforementioned coatings.

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, excellent storage stability and then its cured coating film can be provided to demonstrate the active energy ray-curable resin composition of very high surface hardness, the transparency, resistance to crimp tendency and alkali resistance, the manufacture method of this resin combination, coating containing this resin combination, the film formed by this coating, and the film with this film layer.

Accompanying drawing explanation

Fig. 1 is the longitudinal diagram of the operable wet-type ball mill when manufacturing resin combination of the present invention.

Fig. 2 is the longitudinal diagram of the gland seal device of the operable wet-type ball mill when manufacturing resin combination of the present invention.

Embodiment

Active energy ray-curable resin composition of the present invention contains inorganic particles (A) that the median size recorded based on dynamic light scattering method is the scope of 95 ~ 250nm and weight-average molecular weight (Mw) is 5; the scope of 000 ~ 80,000 and the acrylic polymers (X) in molecular structure with (methyl) acryl are as neccessary composition.

Active energy ray-curable resin composition of the present invention, by containing aforementioned inorganic particulate (A), can obtain the cured coating film that surface hardness is higher.The median size (dynamic light scattering method) of aforementioned inorganic particulate (A) is the scope of 95 ~ 250nm, and when median size is less than 95nm, the surface hardness of gained film reduces, and when more than 250nm, the transparency of gained film reduces.Wherein, from the viewpoint of gained film can with higher level have concurrently hardness and the transparency, preferred median size is the scope of 100 ~ 180nm.

In addition, the median size recorded based on dynamic light scattering method of the aforementioned inorganic particulate (A) in the present invention refers to and to measure according to " ISO13321 ", by the value that the Cumulant Method Using (cumulantmethod) calculates, be specially following value: diluted by active energy ray-curable resin composition MIBK, after making the MIBK solution of concentration 5%, use " ELSZ-2 " that this MIBK solution particle size determination device (Otsuka Electronics Co., Ltd. manufactures) value that records.

Aforementioned inorganic particulate (A) contained by active energy ray-curable resin composition of the present invention is dispersed in resinous principle contained by active energy ray-curable resin composition of the present invention by making the inorganic particles (a) as raw material, namely obtains in the resinous principle of neccessary composition using aforementioned acrylic polymers (X).Aforementioned inorganic particulate (a) include, for example out: the particulates such as silicon-dioxide, aluminum oxide, zirconium white, titanium dioxide, barium titanate, antimonous oxide.These can individually use, and also can combinationally use two or more.

In the middle of these inorganic particles (a), from the viewpoint of easily to obtain and easy and simple to handle, preferred silicon dioxide microparticle.Silicon dioxide microparticle include, for example out: wet silica particulate, dry silica particulate etc.Aforementioned wet silica particulate include, for example out: the silicon dioxide microparticle neutralization of water glass mineral acid obtained.When using wet silica particulate as aforementioned inorganic particulate (a), be adjusted to the aspect of aforementioned preferred value from the easy median size by the inorganic particles (A) gained resin combination, preferably use median size is the wet silica particulate of the scope of 95 ~ 250nm.Aforementioned dry silica particulate include, for example out: by burning silicon tetrachloride and the silicon dioxide microparticle obtained in oxygen or hydrogen flame.When using dry silica particulate as aforementioned inorganic particulate (a), be adjusted to the aspect of aforementioned preferred value from the easy median size by the inorganic particles (A) gained resin combination, preferably use average primary particle diameter at 3 ~ 100nm, the second particle being preferably the dry silica particles agglomerate of the scope of 5 ~ 50nm.

In the middle of aforementioned silicas particulate, from the viewpoint of obtaining the higher cured coating film of surface hardness, preferred dry silica particulate.

In the present invention, various silane coupling agent can be used to import functional group on the surface of aforementioned inorganic particulate (a).By importing functional group on the surface of this inorganic particles (a), the miscibility making to have in its and molecular structure the organic compositions such as the acrylic polymers (X) of (methyl) acryl improves, storage stability raising.

For aforementioned silane coupling agent, include, for example out: vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl group triethoxyl silane, to styryl Trimethoxy silane, 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl diethoxy silane, 3-methacryloxypropyl, 3-acryloxypropyl Trimethoxy silane, N-2-(amino-ethyl)-3-amino propyl 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-ureidopropyltriethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-mercaptopropyi methyl dimethoxysilane, 3-mercaptopropyi Trimethoxy silane, two (triethoxysilylpropyltetrasulfide) tetrasulfide, 3-isocyanate group propyl-triethoxysilicane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilanis, diethoxymethylvinylschane, trieline base silane, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, the silane coupling agent that vinyl three (2-methoxy ethoxy) silane etc. are vinyl-based,

The silane coupling agent of the epoxiess such as diethoxy (glycidoxypropyl group) methyl-monosilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl group triethoxyl silane;

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-methacryloyloxypropyl methyl dimethoxysilane, 3-acryloxypropyl Trimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl diethoxy silane, 3-methacryloxypropyl;

The silane coupling agent of N-2-(amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-APTES, 3-TSL 8330, APTES, amino such as 3-triethoxysilyl-N-(1,3-dimethyl-Ding pitches base) propyl group amine, N-phenyl-3-TSL 8330 etc.;

The silane coupling agent of the urea groups classes such as 3-ureidopropyltriethoxysilane;

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-mercaptopropyi methyl dimethoxysilane, 3-mercaptopropyi Trimethoxy silane;

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 individually use, and also can combinationally use two or more.In the middle of these; from can obtain with molecular structure have that the miscibility of the organic compositions such as the acrylic polymers (X) of (methyl) acryl is excellent, surface hardness is high and the aspect of the cured coating film that the transparency is also excellent; the preferably silane coupling agent of (methyl) acryloyl-oxy base class, more preferably 3-acryloxypropyl Trimethoxy silane, 3-methacryloxypropyl trimethoxy silane.

It is 5,000 ~ 80 that active energy ray-curable resin composition of the present invention contains weight-average molecular weight (Mw), and the scope of 000 and the acrylic polymers (X) in molecular structure with (methyl) acryl are as resinous principle.

The acrylic polymers (X) in previous molecular structure with (methyl) acryl is 5 by making its weight-average molecular weight (Mw); 000 ~ 80; the scope of 000, stably can disperse aforementioned inorganic particulate (A), and therefore the storage stability of resin combination improves.Be less than 5 in weight-average molecular weight (Mw), when 000, the dispersiveness of aforementioned inorganic particulate (A) reduces, and therefore the storage stability of resin combination, the transparency of cured coating film reduce.In addition, in weight-average molecular weight (Mw) more than 80, when 000, viscosity raises, and becomes and is difficult to process as coating applications.Wherein, become the viscosity that is suitable for applying from the viewpoint of the more excellent and active energy ray-curable resin composition of the dispersiveness of aforementioned inorganic particles (A), weight-average molecular weight (Mw) is preferably 8, the scope of 000 ~ 50,000, is more preferably 10, the scope of 000 ~ 45,000.

In addition, in the present invention, weight-average molecular weight (Mw) is the value using 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 TSKgelG5000HXL

+ TOSOH Co., Ltd manufactures TSKgelG4000HXL

+ TOSOH Co., Ltd manufactures TSKgelG3000HXL

+ TOSOH Co., Ltd manufactures TSKgelG2000HXL

Detector: RI(differential refractometer)

Data processing: TOSOH Co., Ltd manufactures SC-8010

Condition determination: column temperature 40 DEG C

Solvents tetrahydrofurane

Flow velocity 1.0ml/ minute

Standard: polystyrene

Sample: the tetrahydrofuran solution micro-strainer that will be scaled 0.4 % by weight by resin solid content filters and the solution (100 μ l) that obtains

In addition; from the viewpoint of the also excellent cured coating film of resistance to crimp tendency when can obtain having high surface hardness, solidification; (methyl) acryl equivalent in previous molecular structure with the acrylic polymers (X) of (methyl) acryl is preferably the scope of 220g/eq ~ 1650g/eq, is more preferably the scope of 240g/eq ~ 1100g/eq.And then from the viewpoint of the active energy ray-curable resin composition that can obtain ageing stability excellence, the more preferably scope of 350g/eq ~ 800g/eq, be particularly preferably the scope of 380g/eq ~ 650g/eq.

The acrylic polymers (X) in previous molecular structure with (methyl) acryl include, for example out: the acrylic polymers (Y) that the compound (y) making to have reactive functional groups and (methyl) acryl carries out being polymerized as neccessary composition and obtain with there is functional group that the reactive functional groups that can have with aforesaid compound (y) reacts react with the compound (z) of (methyl) acryl and the polymkeric substance that obtains.

More specifically, can list: the acrylic polymers (Y1) that the compound (y1) making to have epoxy group(ing) and (methyl) acryl carries out being polymerized as neccessary composition and obtain with there is the compound (z1) of carboxyl with (methyl) acryl react and the acrylic polymers (X1) that obtains; The acrylic polymers (Y2) that the compound (y2) making to have carboxyl and (methyl) acryl carries out being polymerized as neccessary composition and obtain with there is the compound (z2) of epoxy group(ing) with (methyl) acryl react and the acrylic polymers (X2) that obtains; The acrylic polymers (Y3) that the compound (y3) making to have hydroxyl and (methyl) acryl carries out being polymerized as neccessary composition and obtain with there is the compound (z3) of isocyanate group with (methyl) acryl react and the acrylic polymers (X3) etc. that obtains.

First, foregoing acrylic polymkeric substance (X1) is described.

Foregoing acrylic polymkeric substance (Y1) as the raw material of foregoing acrylic polymkeric substance (X1) can be the aforementioned homopolymer with the compound (y1) of epoxy group(ing) and (methyl) acryl, also can be the multipolymer with other polymerizable compounds (v1).

For the compound (y1) with epoxy group(ing) and (methyl) acryl of the material composition as foregoing acrylic polymkeric substance (Y1), include, for example out: (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-methylglycidyl esters, (methyl) vinylformic acid-3, 4-epoxy cyclohexyl, lactone-modified (methyl) vinylformic acid-3, 4-epoxy cyclohexyl, vinylcyclohexene oxide etc.These can individually use, and also can combinationally use two or more.In the middle of these; from the viewpoint of easily (methyl) acryl equivalent of gained acrylic polymers (X1) being adjusted to 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 manufacture foregoing acrylic polymkeric substance (Y1) time can with aforementioned other polymerizable compounds (v1) that there is epoxy group(ing) and be polymerized together with the compound (y1) of (methyl) acryl, include, for example out: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) lauryl ester, (methyl) vinylformic acid tetradecane ester, (methyl) vinylformic acid n-Hexadecane ester, (methyl) stearyl acrylate ester, (methyl) octadecyl ester, (methyl) behenyl ester etc. has (methyl) acrylate of the alkyl of carbon number 1 ~ 22,

(methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid two ring pentyl ester, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester etc. have (methyl) acrylate of ester ring type alkyl;

(methyl) vinylformic acid benzoyloxy ethyl ester, (methyl) benzyl acrylate, (methyl) phenylethyl acrylate, (methyl) acrylate, (methyl) vinylformic acid phenoxy group binaryglycol ester, (methyl) vinylformic acid-2-hydroxyl-3-phenoxy-propyl etc. have (methyl) acrylate of aromatic nucleus;

(methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) hy-droxybutyl, (methyl) glycerol acrylate; (methyl) acrylate etc. that lactone-modified (methyl) Hydroxyethyl acrylate, (methyl) polyalkylene glycol acrylate ester, (methyl) vinylformic acid polypropylene glycol ester etc. have a 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 diolefinic 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;

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 (entirely) fluoroalkyl perfluoroalkyl vinyl ether of 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, 2H-17 the carbon number of (entirely) fluoroalkyl of fluorine ester in the last of the ten Heavenly stems or (methyl) perfluoroethyl ethoxy ethyl ester and so on be 1 ~ 18 (entirely) fluoroalkyl (methyl) acrylate;

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, the N-dialkyl amido alkane esters etc. such as N-diethylamino propyl ester.These can individually use, and also can combinationally use two or more.In the middle of these; from the viewpoint of easily (methyl) acryl equivalent of gained acrylic polymers (X1) being adjusted to aforesaid preferable range and gained cured coating film is high rigidity and is rich in toughness; preferably there is (methyl) acrylate of the alkyl of carbon number 1 ~ 22 and there is (methyl) acrylate of ester ring type alkyl, 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.

Foregoing acrylic polymkeric substance (Y1) as previously mentioned; can be the aforementioned homopolymer with the compound (y1) of epoxy group(ing) and (methyl) acryl, also can be aforementionedly 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 the viewpoint of easily (methyl) acryl equivalent of gained acrylic polymers (X1) being adjusted to suitable scope, can obtain there is high surface hardness and solidification time resistance to crimp tendency also excellent cured coating film; preferably with both mass ratioes [there is the compound (y1) of epoxy group(ing) and (methyl) acryl] during copolymerization: [other polymerizable compounds (v1)] is the polymkeric substance that the ratio of the scope of 10/90 ~ 90/10 is carried out copolymerization and obtained, and is more preferably the scope of 15/85 ~ 80/20.And then from the viewpoint of the active energy ray-curable resin composition that can obtain ageing stability excellence, the more preferably scope of 20/80 ~ 50/50, be particularly preferably the scope of 25/75 ~ 45/55.

Foregoing acrylic polymkeric substance (Y1) has the epoxy group(ing) from aforesaid compound (y1); and from the viewpoint of easily the acryl equivalent of gained acrylic polymers (X1) being adjusted to the scope of 220 ~ 1650g/eq; the epoxy equivalent (weight) of this acrylic polymers (Y1) is preferably the scope of 150 ~ 1600g/eq; be more preferably the scope of 170 ~ 1100g/eq; the more preferably scope of 270 ~ 750g/eq, is particularly preferably the scope of 300 ~ 550g/eq.

Foregoing acrylic polymkeric substance (Y1) such as can by under the existence of polymerization starter, make aforesaid compound (y1) carry out separately being polymerized or combinationally using aforesaid compound (y1) the temperature provinces of 60 DEG C ~ 150 DEG C to carry out addition polymerization to manufacture with aforesaid compound (v1), can random copolymers, segmented copolymer, graft copolymer etc. be listed.The method of polymerization include, for example out: mass polymerization, solution polymerization process, suspension polymerization, emulsion polymerization etc.In the middle of these; there is the reaction of the compound (z1) of carboxyl and (methyl) acryl, preferred solution polymerization from the viewpoint of the manufacture of foregoing acrylic polymkeric substance (Y1) and foregoing acrylic polymkeric substance (Y1) subsequently can be carried out continuously with aforementioned.

If consider temperature of reaction, the solvent then used when carrying out the manufacture of foregoing acrylic polymkeric substance (Y1) with solution polymerization process to be boiling point the be solvent of more than 80 DEG C, include, for example out: 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 monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, glycol monobutyl 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 solvent such as toluene, dimethylbenzene, No. 5, Solvesso100, Solvesso150, Swazole1800, Swazole310, IsoparE, IsoparG, 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 viewpoint of the solvability excellence of gained acrylic polymers (Y1), the ketone solvents such as preferred methylethylketone, methyl iso-butyl ketone (MIBK), the glycol ether solvents such as propylene glycol monomethyl ether.

The catalyzer used in the manufacture of foregoing acrylic polymkeric substance (Y1) include, for example out: 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo is two-(2,4-methyl pentane nitrile), 2,2 '-azo is two-azo-compound such as (4-methoxyl group-2,4-methyl pentane nitrile); Benzoyl peroxide, lauroyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, the ethylhexanoate tert-butyl ester, 1, organo-peroxide and the hydrogen peroxide etc. such as 1 '-bis-(tert-butyl hydroperoxide) hexanaphthene, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, peroxidation-tertiary own ester of 2 ethyl hexanoic acid.

When using superoxide as catalyzer, superoxide can be used as redox type initiator together with reductive agent.

Raw material as foregoing acrylic polymkeric substance (X1) uses, the compound (z1) with carboxyl and (methyl) acryl include, for example out: (methyl) vinylformic acid, (acryloxy) acetic acid, vinylformic acid-2-carboxyethyl, vinylformic acid-3-carboxyl propyl ester, succsinic acid-1-[2-(acryloxy) ethyl ester], phthalic acid-1-(2-acryloyloxyethyl ester), the unsaturated monocarboxylics such as hexahydrophthalic acid hydrogen-2-(acryloxy) ethyl ester and their lactone-modified thing, the unsaturated dicarboxylic acids such as toxilic acid, make the hydroxyls such as the acid anhydrides such as succinyl oxide, maleic anhydride and pentaerythritol triacrylate multifunctional (methyl) acrylate monomer 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 the viewpoint of easily (methyl) acryl equivalent of foregoing acrylic polymkeric substance (X1) being adjusted to aforesaid preferable range; preferably (methyl) vinylformic acid, (acryloxy) acetic acid, vinylformic acid-2-carboxyethyl, vinylformic acid-3-carboxyl propyl ester, particularly preferably (methyl) vinylformic acid.

Foregoing acrylic polymkeric substance (X1) makes foregoing acrylic polymkeric substance (Y1) react with the compound (z1) with carboxyl and (methyl) acryl to obtain.This reaction method include, for example out: be polymerized by acrylic polymers (Y1) with solution polymerization process; the compound (z1) with carboxyl and (methyl) acryl is added in this reaction system; in the temperature range of 60 ~ 150 DEG C, suitably use the method etc. of the catalyzer such as triphenylphosphine.(methyl) acryl equivalent of acrylic polymers (X1) is preferably the scope of 220 ~ 1650g/eq, and this can be regulated by foregoing acrylic polymkeric substance (Y1) and the aforementioned reactive ratio with the compound (z1) of carboxyl and (methyl) acryl.Usually; relative to the epoxy group(ing) 1 mole that foregoing acrylic polymkeric substance (Y1) has; the carboxyl had with aforesaid compound (z1) is that the mode of the scope of 0.8 ~ 1.1 mole is reacted, thus easily (methyl) acryl equivalent of gained acrylic polymers (X1) is adjusted to above-mentioned preferable range.

The acrylic polymers (X1) so obtained has reaction by epoxy group(ing) and carboxyl and the hydroxyl generated in its molecular structure.For the object acryl equivalent of acrylic polymers (X1) being adjusted to suitable scope, can this hydroxyl be made to carry out addition reaction with the compound (w) with isocyanate group and (methyl) acryl as required.The acrylic polymers that so obtains (X1 ') also same with foregoing acrylic polymkeric substance (X1), can acrylic polymers of the present invention (X) be used as.

The aforementioned compound (w) with isocyanate group and (methyl) acryl include, for example out the compound shown in following general formula 1, can list: the monomer etc. having the monomer of 1 isocyanate group and 1 (methyl) acryl, have the monomer of 1 isocyanate group and 2 (methyl) acryls, have the monomer of 1 isocyanate group and 3 (methyl) acryls, have the monomer of 1 isocyanate group and 4 (methyl) acryls, have 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 the integer of 1 ~ 5.

There is as these example of the specific product of the compound (w) of isocyanate group and (methyl) acryl; can list: 2-acryloyloxyethyl isocyanate (trade(brand)name: " KarenzAOI " that Showa Denko K. K manufactures etc.), 2-methacryloxyethyl isocyanic ester (trade(brand)name: " KarenzMOI " that Showa Denko K. K manufactures etc.), 1,1-two (acryloyloxymethyl) ethyl isocyanate (trade(brand)name: " KarenzBEI " that Showa Denko K. K manufactures etc.).

As other examples of aforesaid compound (w), 1 isocyanate group addition hydroxyl (methyl) acrylic compound to diisocyanate cpd can be listed and the compound obtained.The diisocyanate cpd used in the 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 diisocyanate, a tetramethyl-xylylene diisocyanate;

Hexanaphthene-1,4-vulcabond, isophorone diisocyanate, lysinediisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, 1,3-two vulcabond such as ester ring type such as (isocyanatomethyl) hexanaphthene, methylcyclohexane diisocyanate etc.;

1,5-naphthalene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 4,4 '-diphenyldimethyhnethane vulcabond, 4,4 '-dibenzyl diisocyanate, dialkyl group diphenylmethanediisocyanate, tetraalkyl diphenylmethanediisocyanate, 1,3-phenylene diisocyanate, Isosorbide-5-Nitrae-aromatic diisocyanate such as phenylene diisocyanate, tolylene diisocyanate etc.These can individually use, and also can combinationally use two or more.

In addition, for the hydroxyl used in the reaction (methyl) acrylic compound, can list: aliphatics (methyl) acrylic compound such as 2-Hydroxy ethyl acrylate, vinylformic acid-2-hydroxy ester, vinylformic acid-4-hydroxybutyl, glycerol diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate;

There is 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-propyl equimolecular structure (methyl) acrylic compound etc. of aromatic nucleus.These can individually use, and also can combinationally use two or more.

Foregoing acrylic polymkeric substance (X1) such as can wait by the following method with the reaction of the compound (w) with isocyanate group and (methyl) acryl and carry out: in the system manufactured with preceding method after acrylic polymers (X1), add the aforementioned compound (w) with isocyanate group and (methyl) acryl, be heated to 50 ~ 120 DEG C.

For foregoing acrylic polymkeric substance (X1) and (X1 '), from molecule, contain more hydroxyl, make to improve the dispersive ability of inorganic particles (A) by the interaction of this hydroxyl and inorganic particles (A), preferred foregoing acrylic polymkeric substance (X1).

Then, foregoing acrylic polymkeric substance (X2) is described.

Foregoing acrylic polymkeric substance (Y2) as the raw material of foregoing acrylic polymkeric substance (X2) can be the aforementioned homopolymer with the compound (y2) of carboxyl and (methyl) acryl, also can be the multipolymer of itself and other polymerizable compound (v2).

As the material composition of foregoing acrylic polymkeric substance (Y2), the compound (y2) with carboxyl and (methyl) acryl include, for example out: (methyl) vinylformic acid, (acryloxy) acetic acid, vinylformic acid-2-carboxyethyl, vinylformic acid-3-carboxyl propyl ester, succsinic acid-1-[2-(acryloxy) ethyl ester], phthalic acid-1-(2-acryloyloxyethyl ester), the unsaturated monocarboxylics such as hexahydrophthalic acid hydrogen-2-(acryloxy) ethyl ester and their lactone-modified thing, the unsaturated dicarboxylic acids such as toxilic acid, make the hydroxyls such as the acid anhydrides such as succinyl oxide, maleic anhydride and pentaerythritol triacrylate multifunctional (methyl) acrylate monomer carry out reacting 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 the viewpoint of easily (methyl) acryl equivalent of foregoing acrylic polymkeric substance (X1) being adjusted to aforesaid preferable range; preferably (methyl) vinylformic acid, (acryloxy) acetic acid, vinylformic acid-2-carboxyethyl, vinylformic acid-3-carboxyl propyl ester, particularly preferably (methyl) vinylformic acid.

For manufacture foregoing acrylic polymkeric substance (Y2) time can with aforementioned other polymerizable compounds (v2) that there is carboxyl and be polymerized together with the compound (y2) of (methyl) acryl, include, for example out the illustrative various compound as aforesaid compound (v1).These can individually use, and also can combinationally use two or more.Wherein, from the viewpoint of easily (methyl) acryl equivalent of gained acrylic polymers (X2) being adjusted to aforesaid preferable range and gained cured coating film is high rigidity and is rich in toughness; preferably there is (methyl) acrylate of the alkyl of carbon number 1 ~ 22 and there is (methyl) acrylate of ester ring type alkyl, 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.

Foregoing acrylic polymkeric substance (Y2) as previously mentioned; can be the aforementioned homopolymer with the compound (y2) of carboxyl and (methyl) acryl, also can be aforementionedly have carboxyl and the compound (y2) of (methyl) acryl and the multipolymer of aforementioned other polymerizable compounds (v2).In the middle of these; from the viewpoint of easily (methyl) acryl equivalent of gained acrylic polymers (X2) being adjusted to suitable scope; preferably with the mass ratio [there is the compound (y2) of carboxyl and (methyl) acryl] both during copolymerization: the polymkeric substance that the ratio copolymerization of [other polymerizable compounds (v2)] scope 10/90 ~ 90/10 obtains; be more preferably the scope of 15/85 ~ 80/20; the more preferably scope of 20/80 ~ 50/50, is particularly preferably the scope of 25/75 ~ 45/55.

Foregoing acrylic polymkeric substance (Y2) such as by making aforesaid compound (y2) carry out separately being polymerized or combinationally using aforesaid compound (y2) and aforesaid compound (v2) carries out addition polymerization to manufacture under the existence of polymerization starter, the temperature provinces of 60 DEG C ~ 150 DEG C, can be able to list: random copolymers, segmented copolymer, graft copolymer etc.For the method for polymerization, include, for example out: mass polymerization, solution polymerization process, suspension polymerization, emulsion polymerization etc.In the middle of these; there is the reaction of the compound (z2) of epoxy group(ing) and (methyl) acryl, preferred solution polymerization from the viewpoint of the manufacture of foregoing acrylic polymkeric substance (Y2) and back to back foregoing acrylic polymkeric substance (Y2) can be carried out continuously with aforementioned.

For the solvent used when carrying out the manufacture of foregoing acrylic polymkeric substance (Y2) with solution polymerization process, the solvent as using when carrying out the manufacture of foregoing acrylic polymkeric substance (Y1) with solution polymerization process can be listed and illustrative all kinds of SOLVENTS.These may be used singly or in combination of two or more.Wherein, from the viewpoint of the solvability excellence of gained acrylic polymers (Y2), the ketone solvents such as preferred methylethylketone, methyl iso-butyl ketone (MIBK).

For the catalyzer used in the manufacture of foregoing acrylic polymkeric substance (Y2), the catalyzer as using in the manufacture of foregoing acrylic polymkeric substance (Y1) can be listed and illustrative various catalyzer.

Raw material as foregoing acrylic polymkeric substance (X2) uses, the compound (z2) with epoxy group(ing) and (methyl) acryl include, for example out: (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-methylglycidyl esters, (methyl) vinylformic acid-3, 4-epoxy cyclohexyl, lactone-modified (methyl) vinylformic acid-3, 4-epoxy cyclohexyl, vinylcyclohexene oxide etc.These can individually use, and also can combinationally use two or more.In the middle of these; from the viewpoint of easily (methyl) acryl equivalent of gained acrylic polymers (X2) being adjusted to aforementioned preferable range, particularly preferably (methyl) glycidyl acrylate, α-ethyl (methyl) glycidyl acrylate and α-n-propyl (methyl) glycidyl acrylate.

Foregoing acrylic polymkeric substance (X2) makes foregoing acrylic polymkeric substance (Y2) react with the compound (z2) with epoxy group(ing) and (methyl) acryl to obtain.This reaction method include, for example out following method etc.: with solution polymerization process, acrylic polymers (Y2) is polymerized; the compound (z2) with epoxy group(ing) and (methyl) acryl is added in this reaction system; 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 be regulated by foregoing acrylic polymkeric substance (Y2) and the aforementioned reactive ratio with the compound (z2) of epoxy group(ing) and (methyl) acryl.Usually; relative to the carboxyl 1 mole that foregoing acrylic polymkeric substance (Y2) has; the epoxy group(ing) had with aforesaid compound (z2) is that the mode of the scope of 0.9 ~ 1.25 mole is reacted, thus easily (methyl) acryl equivalent of gained acrylic polymers (X2) is adjusted to above-mentioned preferable range.

The acrylic polymers (X2) so obtained has reaction by carboxyl and epoxy group(ing) and the hydroxyl generated in its molecular structure.For the object acryl equivalent of acrylic polymers (X2) being adjusted to suitable scope, can this hydroxyl and the aforementioned compound (w) with isocyanate group and (methyl) acryl be made to carry out addition reaction as required.The acrylic polymers that so obtains (X2 ') also same with foregoing acrylic polymkeric substance (X2), can acrylic polymers of the present invention (X) be used as.

Foregoing acrylic polymkeric substance (X2) such as can wait by the following method with the reaction of the compound (w) with isocyanate group and (methyl) acryl and carry out: in the system manufactured with preceding method after acrylic polymers (X2), add the aforementioned compound (w) with isocyanate group and (methyl) acryl, be heated to 50 ~ 120 DEG C.

For foregoing acrylic polymkeric substance (X2) and (X2 '), from molecule, contain more hydroxyl, make to improve the dispersive ability of inorganic particles (A) by the interaction of this hydroxyl and inorganic particles (A), preferred foregoing acrylic polymkeric substance (X2).

Then, foregoing acrylic polymkeric substance (X3) is described.

Foregoing acrylic polymkeric substance (Y3) as the raw material of foregoing acrylic polymkeric substance (X3) can be the aforementioned homopolymer with the compound (y3) of hydroxyl and (methyl) acryl, also can be the multipolymer of itself and other polymerizable compound (v3).

As foregoing acrylic polymkeric substance (Y3) material composition, the compound (y3) with hydroxyl and (methyl) acryl include, for example out: 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, vinylformic acid-4-hydroxybutyl, vinylformic acid-2; 3-dihydroxyl propyl ester, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, methacrylic acid-4-hydroxybutyl, 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 the viewpoint of easily (methyl) acryl equivalent of foregoing acrylic polymkeric substance (X3) being adjusted to aforesaid preferable range and hydroxyl value is high, can obtain the foregoing acrylic polymkeric substance (X3) of the excellent dispersion of aforementioned inorganic particulate (A), preferred 2-Hydroxy ethyl acrylate and 2-hydroxypropyl acrylate.

For manufacture foregoing acrylic polymkeric substance (Y3) time can with aforementioned other polymerizable compounds (v3) that there is hydroxyl and be polymerized together with the compound (y3) of (methyl) acryl, include, for example out the illustrative various compound as aforesaid compound (v1).These can individually use, and also can combinationally use two or more.Wherein, from the viewpoint of easily (methyl) acryl equivalent of gained acrylic polymers (X3) being adjusted to aforesaid preferable range and gained cured coating film is high rigidity and is rich in toughness; preferably there is (methyl) acrylate of the alkyl of carbon number 1 ~ 22 and there is (methyl) acrylate of ester ring type alkyl, 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.

Foregoing acrylic polymkeric substance (Y3) as previously mentioned, can be the homopolymer of the compound (y3) with hydroxyl and (methyl) acryl, also can be the multipolymer of itself and other polymerizable compound (v3).In the middle of these; in order to (methyl) acryl equivalent of gained acrylic polymers (X3) is adjusted to suitable scope; preferably with the mass ratio [there is the compound (y3) of hydroxyl and (methyl) acryl] both during copolymerization: the ratio of [other polymerizable compounds (v3)] scope 10/90 ~ 90/10 carries out the polymkeric substance that copolymerization obtains; be more preferably the scope of 15/85 ~ 80/20; the more preferably scope of 20/80 ~ 50/50, is particularly preferably the scope of 25/75 ~ 45/55.

Foregoing acrylic polymkeric substance (Y3) such as by making aforesaid compound (y3) carry out separately being polymerized or combinationally using aforesaid compound (y3) and aforesaid compound (v3) carries out addition polymerization to manufacture under the existence of polymerization starter, the temperature provinces 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; there is the reaction of the compound (z3) of isocyanate group and (methyl) acryl, preferred solution polymerization from the viewpoint of the manufacture of foregoing acrylic polymkeric substance (Y3) and foregoing acrylic polymkeric substance (Y3) subsequently can be carried out continuously with aforementioned.

For the solvent used when carrying out the manufacture of foregoing acrylic polymkeric substance (Y3) with solution polymerization process, the solvent as using when carrying out the manufacture of foregoing acrylic polymkeric substance (Y1) with solution polymerization process can be listed and illustrative all kinds of SOLVENTS.These may be used singly or in combination of two or more.Wherein, from the viewpoint of the solvability excellence of gained acrylic polymers (Y3), the ketone solvents such as preferred methylethylketone, methyl iso-butyl ketone (MIBK).

For the catalyzer used in the manufacture of foregoing acrylic polymkeric substance (Y3), the catalyzer as using in the manufacture of foregoing acrylic polymkeric substance (Y1) can be listed and illustrative various catalyzer.

Compound (z3) that use for the raw material as foregoing acrylic polymkeric substance (X3), that have isocyanate group and (methyl) acryl, include, for example out the compound (w) and illustrative various compound that have isocyanate group and (methyl) acryl as aforementioned.These can individually use, and also can combinationally use two or more.In the middle of these; become from the viewpoint of gained acrylic polymers (X3) there is more multi-functional compound, the film that can obtain more high rigidity; preferably there is in 1 molecule the compound of (methyl) acryl of more than 2; specifically; preferably 1,1-two (acryloyloxymethyl) ethyl isocyanate.

Foregoing acrylic polymkeric substance (X3) makes foregoing acrylic polymkeric substance (Y3) react with the compound (z3) with isocyanate group and (methyl) acryl to obtain.This reaction such as can wait by the following method to be carried out: be polymerized by acrylic polymers (Y3) with solution polymerization process; the compound (z3) with isocyanate group and (methyl) acryl is added in this reaction system; 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 be regulated by foregoing acrylic polymkeric substance (Y3) and the aforementioned reactive ratio with the compound (z3) of isocyanate group and (methyl) acryl.Usually; relative to the hydroxyl 1 mole that foregoing acrylic polymkeric substance (Y3) has; the isocyanate group had with aforesaid compound (z3) is that the mode of the scope of 0.7 ~ 0.9 mole is reacted, thus easily (methyl) acryl equivalent of gained acrylic polymers (X3) is adjusted to above-mentioned preferable range.

In the middle of foregoing acrylic polymkeric substance (X), from the viewpoint of the superior storage stability good, dispersions obtained with the affinity of aforementioned inorganic particulate (A), preferred foregoing acrylic polymkeric substance (X1) and (X2).Herein, more excellent from the viewpoint of the dispersiveness of aforementioned inorganic particles (A), the hydroxyl value of foregoing acrylic polymkeric substance (X1) and (X2) is preferably the scope of 35 ~ 250mgKOH/g, be more preferably the scope of 50 ~ 230mgKOH/g, the more preferably scope of 65 ~ 160mgKOH/g, is particularly preferably the scope of 80 ~ 150mgKOH/g.And then, easier from the viewpoint of synthesis, preferred foregoing acrylic polymkeric substance (X1), more preferably uses the acrylic polymers that (methyl) glycidyl acrylate obtains 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 foregoing acrylic polymkeric substance (X) as neccessary composition, contains aforementioned inorganic particulate (A) with the scope of 35 ~ 60 mass parts in their summation 100 mass parts.When the content of aforementioned inorganic particulate (A) is less than 35 mass parts, resistance to crimp tendency during solidification reduces.In addition, when the content of aforementioned inorganic particulate (A) is more than 60 mass parts, the storage stability of active energy ray-curable resin composition reduces.In the middle of, can obtain having concurrently the cured coating film of high surface hardness and the transparency, resistance to crimp tendency from the viewpoint of the excellent storage stability of resin combination, 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 previous molecular structure, can also contain beyond acrylic polymers (X), to have (methyl) acryl in molecular structure compound (c).In the present invention, from the viewpoint of forming viscosity active energy ray-curable resin composition that is lower, that easily use as coating applications, preferably this compound (c) is used.Now, from the viewpoint of obtaining resistance to crimp tendency and the more excellent cured coating film of toughness, in summation 100 mass parts of aforementioned inorganic particulate (A), foregoing acrylic polymkeric substance (X) and aforesaid compound (c), the content of foregoing acrylic polymkeric substance (X) is preferably the scope of 35 ~ 60 mass parts, is more preferably the scope of 40 ~ 50 mass parts.In addition, from the viewpoint of the higher and scuff resistance of surface hardness also excellent cured coating film can be obtained, the scope of 5 ~ 35 mass parts is preferably, the more preferably scope of 10 ~ 25 mass parts.

The compound (c) in previous molecular structure with (methyl) acryl include, for example out: various (methyl) acrylate monomer, carbamate (methyl) acrylate.

Aforementioned (methyl) acrylate monomer include, for example out: (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxybutyl, (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-methoxybutyl, (methyl) acrylic acid ethyl carbitol ester, phosphoric acid (methyl) acrylate, ethylene-oxide-modified phosphoric acid (methyl) acrylate, phenoxy group (methyl) acrylate, ethylene-oxide-modified phenoxy group (methyl) acrylate, epoxy pronane modification phenoxy group (methyl) acrylate, nonylphenol (methyl) acrylate, ethylene-oxide-modified 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) acryloyl-oxyethyl-2-hydroxypropyl phthalate, (methyl) vinylformic acid-2-hydroxyl-3-phenoxy-propyl, 2-(methyl) acrylyl oxy-ethyl hydrogen phthalic ester, 2-(methyl) acryloxypropyl hydrogen phthalic ester, 2-(methyl) acryloxypropyl hexahydrophthalic acid ester, 2-(methyl) acryloxypropyl tetrahydrophthalic acid ester, (methyl) acrylate, (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 above (methyl) acrylate,

And the part alkyl of above-mentioned various multifunctional (methyl) acrylate, 6-caprolactone are replaced and (methyl) acrylate etc. of obtaining.

Aforementioned carbamate (methyl) acrylate include, for example out: make carbamate (methyl) acrylate that polyisocyanate compound and hydroxyl (methyl) acrylic compound react and obtain.

Aforementioned polyisocyanates compound for the raw material of aforementioned carbamate (methyl) acrylate can list: the urea acid esters type polyisocyanate compound etc. in various diisocyanate monomer, molecule with isocyanuric acid ester ring structure.

Aforementioned diisocyanates monomer include, for example out: butane-1,4-vulcabond, hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2, the aliphatic diisocyanates such as 4,4-trimethyl hexamethylene diisocyanate, xylylene diisocyanate, a tetramethyl-xylylene diisocyanate;

1,5-naphthalene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 4,4 '-diphenyldimethyhnethane vulcabond, 4,4 '-dibenzyl diisocyanate, dialkyl group diphenylmethanediisocyanate, tetraalkyl diphenylmethanediisocyanate, 1,3-phenylene diisocyanate, Isosorbide-5-Nitrae-aromatic diisocyanate such as phenylene diisocyanate, tolylene diisocyanate etc.

The urea acid esters type polyisocyanate compound in previous molecular with isocyanuric acid ester ring structure include, for example out: make diisocyanate monomer and monohydroxy-alcohol and/or diol reaction and the compound obtained.As the diisocyanate monomer used in the reaction, aforesaid various diisocyanate monomer can be listed, can individually use, also can combinationally use two or more.In addition, the monohydroxy-alcohol used in the 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 individually use, and also can combinationally use two or more.

In the middle of these polyisocyanate compounds, from the viewpoint of the cured coating film that can obtain tenacity excellent, preferred aforementioned diisocyanates 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, include, for example out: aliphatics (methyl) acrylic compound such as 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, vinylformic acid-4-hydroxybutyl, glycerol diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate;

There is 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-propyl equimolecular structure (methyl) acrylic compound etc. of aromatic nucleus.These can individually use, and also can combinationally use two or more.

In the middle of these hydroxyls (methyl) acrylic compound; from the viewpoint of tenacity excellent can being obtained and there is the cured coating film of high surface hardness, there is in preferably glycerine diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate equimolecular structure aliphatics (methyl) acrylic compound of more than 2 (methyl) acryls.And then; from the viewpoint of the cured coating film that can obtain demonstrating more high surface hardness, more preferably there is in pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate equimolecular structure aliphatics (methyl) acrylic compound of more than 3 (methyl) acryls.

The method manufacturing aforementioned carbamate (methyl) acrylate include, for example out following method etc.: the mol ratio [(NCO)/(OH)] of the hydroxyl that the isocyanate group had with aforementioned polyisocyanate compound and aforementioned hydroxyl (methyl) acrylic compound have is that the ratio of the scope of 1/0.95 ~ 1/1.05 uses aforementioned polyisocyanates compound and aforementioned hydroxyl (methyl) acrylic compound, in the temperature range of 20 ~ 120 DEG C, the method using known usual urethanation catalyst to carry out as required.

During by (methyl) acrylic compound in aforementioned polyisocyanates compound and previous molecular structure with 1 hydroxyl to manufacture aforementioned carbamate (methyl) acrylate, its reaction can be carried out with the system containing acrylic compound such as tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate.For the carbamate in this way obtained (methyl) acrylate, specifically can list: make the raw material reaction containing aforementioned polyisocyanates compound, tetramethylolmethane three (methyl) acrylate and tetramethylolmethane four (methyl) acrylate and carbamate (methyl) acrylate obtained; Make the raw material reaction containing aforementioned polyisocyanates compound, Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate and the urethane acrylate etc. obtained.

From the viewpoint of the excellent compatibility with foregoing acrylic polymkeric substance (X), the weight-average molecular weight (Mw) of carbamate (methyl) acrylate so obtained is preferably the scope of 800 ~ 20,000, is more preferably 900 ~ 1, the scope of 000.

These compounds (c) can individually use, and also can combinationally use two or more.Wherein, from the viewpoint of the film that can obtain more high rigidity, preferably 3 officials can above (methyl) acrylate monomer or 3 officials can above carbamate (methyl) acrylate.Can above (methyl) acrylate monomer as aforementioned 3 officials, preferred tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate.In addition, can above carbamate (methyl) acrylate as aforementioned 3 officials, preferably make diisocyanate cpd and glycerol diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, there is in Dipentaerythritol Pentaacrylate equimolecular structure hydroxyl (methyl) the acrylic compound reaction of more than 2 (methyl) acryls and carbamate (methyl) acrylate that obtains, more preferably diisocyanate cpd is made to react with hydroxyl (methyl) acrylic compound with more than 3 (methyl) acryls and carbamate (methyl) acrylate that obtains.

Active energy ray-curable resin composition of the present invention is at aforementioned inorganic particulate (A), time on the basis in previous molecular structure with the acrylic polymers (X) of (methyl) acryl also containing aforesaid compound (c), from the excellent storage stability of resin combination, and the aspect of the cured coating film having high surface hardness and the transparency concurrently can be obtained, at aforementioned inorganic particulate (A), in summation 100 mass parts of foregoing acrylic polymkeric substance (X) and aforesaid compound (c), preferably with the scope of 35 ~ 60 mass parts, more preferably inorganic particles (A) is contained with the scope of 40 ~ 55 mass parts.

Resin combination of the present invention can contain dispersing auxiliary as required.For this dispersing auxiliary, include, for example out: the phosphate compounds etc. such as isopropyl acid phosphoric acid ester, triisodecyl phosphite ester, ethylene-oxide-modified di(2-ethylhexyl)phosphate methacrylic ester.These can individually use, and also can combinationally use two or more.In the middle of these, from the viewpoint of dispersion ilities excellence, optimization ethylene oxide modified phosphate dimethacrylate.

For the commercially available product of aforementioned dispersing auxiliary, include, for example out: " KAYAMERPM-21 ", " KAYAMERPM-2 " that Nippon Kayaku K. K manufactures, " LightEsterP-2M " that Kyoeisha Chemical Co., Ltd. manufactures etc.

When using aforementioned dispersing auxiliary, from the viewpoint of forming storage stability higher resin combination, 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, such as when manufacturing foregoing acrylic polymkeric substance (X) with solution polymerization process, directly containing solvent used at that time, also can supplement and add other solvent further.Or, also first the organic solvent used during the manufacture of foregoing acrylic polymkeric substance (X) can be removed and re-use other solvent.The object lesson of the solvent used 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 monopropyl ether.These can individually use, and also can combinationally use two or more.In the middle of these, from the viewpoint of the resin combination of coating excellence when forming excellent storage stability and be used as coating, preferred ketone solvent, more preferably methyl iso-butyl ketone (MIBK).In addition, also glycol ether solvent can be combinationally used for the deliquescent object improving foregoing ion liquid (B) on the basis of aforementioned ketone solvent.

Resin combination of the present invention can also contain the additives such as UV light absorber, antioxidant, silicon system additive, organic microbead, fluorine class additive, rheology control agent, deaerating agent, releasing agent, static inhibitor, antifogging agent, tinting material, organic solvent, mineral filler.

Aforementioned UV light absorber include, for example out: and 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 benzophenones, the adjacent nitro benzyloxy of 2--4-dodecyloxy benzophenones etc.

Aforementioned antioxidant include, for example out: hindered phenol anti-oxidants, hindered amines antioxidant, organosulfur class antioxidant, phosphate-based antioxidants etc.These can individually use, and also can combinationally use two or more.

Aforementioned silicon system additive include, for example out: dimethyl polysiloxane, methyl phenyl silicone, cyclic dimethyl polysiloxane, methylhydrogenpolysi,oxane, polyether-modified dimethyl polysiloxane multipolymer, polyester modification dimethyl polysiloxane multipolymer, fluorine richness 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 etc. of polyester modification acryl.These can individually use, and also can combinationally use two or more.

Aforementioned organic microbead include, for example out: polymethylmethacrylate microballon, polycarbonate microballon, polystyrene microbeads, polyacrylic acid vinylbenzene microballon, polysiloxane microballon, glass microballon, vinylformic acid microballon, benzoguanamine resinoid microballon, melamine class resin microbeads, 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 microbead is the scope of 1 ~ 10 μm.These can individually use, and also can combinationally use two or more.

Aforementioned fluorine class additive include, for example out " Megafac " series etc. of Dainippon Ink Chemicals.These can individually use, and also can combinationally use two or more.

Aforementioned releasing agent include, for example out: " Tegorad2200N ", " Tegorad2300 ", " Tegorad2100 " that EvonikDegussaCorporation manufactures, " UV3500 " that Byk-ChemieCorporation manufactures, DowCorningTorayCo., Ltd. " Paintad8526 ", " SH-29PA " etc. that manufacture.These can individually use, and also can combinationally use two or more.

Foregoing antistatic agents include, for example out: two (trifyl) imide or two (fluorosulfonyl) imido pyridine, imidazoles, Phosphonium, ammonium or lithium salts.These can individually use, and also can combinationally use two or more.

The consumption of aforementioned various additive preferably gives full play to its effect and does not damage the scope of ultraviolet curing, specifically, 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 is also containing Photoepolymerizationinitiater initiater.This Photoepolymerizationinitiater initiater include, for example out: benzophenone, 3,3 '-dimethyl-4-methoxy benzophenone, 4,4 '-bis-dimethylamino benzopheone, 4,4 '-bis-diethylin benzophenone, 4,4 '-dichloro benzophenone, michaelis ketone, 3, the various benzophenone such as 3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone;

Xanthone, the thioxanthene ketones such as xanthone, thioxanthone, 2-methyl thioxanthone, CTX, 2,4-diethyl thioxanthones; 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-morphlinophenyl)-butane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2,4,6-trimethylbenzoyl 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 (the trichloromethyl)-6-of 2,4-[two-(ethoxy carbonyl methyl) is amino] phenyl s-triazine, two (the trichloromethyl)-6-(4-oxyethyl group 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 individually use, and also can combinationally use two or more.

In the middle of foregoing photo-polymerization initiator, 1-hydroxycyclohexylphenylketone is selected from by using, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, thioxanthone and thioxanthone derivates, 2, 2 '-dimethoxy-1, 2-diphenylethane-1-ketone, 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, two (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone group in one kind or two or more mixed system, activity can be shown for the light display of the more wavelength of wide region, the coating that solidified nature is high can be obtained, so preferably.

The commercially available product of foregoing photo-polymerization initiator include, for example out: " IRGACURE-184 " that CibaSpecialtyChemicalsInc. 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 ", BASFCo., Ltd. manufacture " LucirinTPO ", " KAYACURE-DETX ", " KAYACURE-MBP ", " KAYACURE-DMBI " that Nippon Kayaku K. K manufactures, " KAYACURE-EPA ", " KAYACURE-OA ", " Vicure-10 ", " Vicure-55 " that StaufferChemicalCompany manufactures, " TrigonalP1 " that Akzo company manufactures, SANDOZCo., Ltd. manufacture " SANDORAY1000 ", " DEAP " that APJOHN company manufactures, WARDBLENKINSOPCo., " QUANTACURE-PDO ", " QUANTACURE-ITX ", " QUANTACURE-EPD " etc. of Ltd. manufacture.

The consumption of foregoing photo-polymerization initiator preferably can give full play to the amount of the function as Photoepolymerizationinitiater initiater, and crystal is separated out, the scope of Physical properties of coating film deterioration in order not produce, specifically, relative to resin combination 100 mass parts, preferably use with the scope of 0.05 ~ 20 mass parts, centrally particularly preferably to use with the scope of 0.1 ~ 10 mass parts.

Resin combination of the present invention can also use various photosensitizer together with foregoing photo-polymerization initiator.Photosensitizer include, for example out: amine, ureas, sulfocompound, P contained compound, chlorine-containing compound or nitrile or other nitrogenous compounds etc.

The method manufacturing active energy ray-curable resin composition of the present invention include, for example out following method: use there is the agitating vane such as decollator, turbine blade the dispersion machine such as dispersion machine, paint shaker, roller mill, ball mill, masher, sand mill, ball mill by aforementioned inorganic particulate (a) blending dispersion to the method in foregoing acrylic polymkeric substance (X), or, by aforementioned inorganic particulate (a) blending dispersion to the method in the resinous principle formed by foregoing acrylic polymkeric substance (X) and aforesaid compound (c).When aforementioned inorganic particulate (a) is for wet silica particulate, all can obtain even and stable dispersion when using above-mentioned any dispersion machine.And aforementioned inorganic particulate (a) for dry silica particulate time, in order to obtain even and stable dispersion, preferably use ball mill or ball mill.

The ball mill that can preferably use when manufacturing active energy ray-curable resin composition of the present invention include, for example out has 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 rotates under the effect of the rotary actuation of aforementioned turning axle, described supplying opening is arranged at aforesaid receptacle, described relief outlet is arranged at aforesaid receptacle, described gland seal device is disposed in the part running through container of aforementioned turning axle, aforementioned axis seal apparatus has 2 mechanical seal unit, and the sealing with these 2 mechanical seal unit the structure that seals by outside seal liquid.

Namely, for the method manufacturing active energy ray-curable resin composition of the present invention, include, for example out 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 rotates under the effect of the rotary actuation of aforementioned turning axle, described supplying opening is arranged at aforesaid receptacle, described relief outlet is arranged at aforesaid receptacle, described gland seal device is disposed in the part running through container of aforementioned turning axle, aforementioned axis seal apparatus has 2 mechanical seal unit, and the sealing with these 2 mechanical seal unit the structure that seals by outside seal liquid, from the aforementioned supplying opening of described wet-type ball mill to aforementioned supply for receptacles aforementioned inorganic particulate (a) with using aforementioned acrylic polymers (X) as the resinous principle of neccessary composition, in aforesaid receptacle, make turning axle and agitating vane rotate, be uniformly mixed medium and raw material, carry out the pulverizing of aforementioned inorganic particulate (a) and this inorganic particles (a) thus to the dispersion in aforementioned resinous principle, then, discharge from aforementioned relief outlet.

By showing the accompanying drawing of an example of the concrete structure of aforementioned wet-type ball mill, further this manufacture method is described in detail.

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 aforesaid receptacle (p1), relief outlet (t1) is arranged at aforesaid receptacle (p1), gland seal device (u1) is disposed in the part running through container of aforementioned turning axle.Here, aforementioned axis seal apparatus (u1) has 2 mechanical seal unit, and the sealing with these 2 mechanical seal unit the structure that seals by outside seal liquid, this gland seal device (u1) include, for example out the device with the structure shown in Fig. 2.

When using aforementioned wet-type ball mill to manufacture resin combination of the present invention, can list and aforementioned inorganic particulate (a) and foregoing acrylic polymkeric substance (X) are supplied to the method that wet-type ball mill carries out blending dispersion.Now, can aforementioned inorganic particulate (a) on the basis of foregoing acrylic polymkeric substance (X) also by aforesaid compound (c), aforementioned dispersing auxiliary, aforementioned organic solvents and aforementioned various additive also together be supplied to wet-type ball mill and carry out blending dispersion, also after aforementioned inorganic particulate (a) and foregoing acrylic polymkeric substance (X) being supplied to wet-type ball mill and carrying out blending dispersion, aforesaid compound (c), aforementioned dispersing auxiliary, aforementioned organic solvents and aforementioned various additive can be added in gained mixture.Wherein, easy from the viewpoint of manufacture, preferably aforementioned inorganic particulate (a), foregoing acrylic polymkeric substance (X), aforesaid compound (c), aforementioned dispersing auxiliary, aforementioned organic solvents and aforementioned various additive are supplied to the method that wet-type ball mill carries out blending dispersion.In addition, for preventing the object producing gelation etc. when disperseing, in the dispersion of Photoepolymerizationinitiater initiater preferably after adding dispersion to afterwards.

In the wet-type ball mill shown in Fig. 1, raw material is supplied to container (p1) via the supplying opening (s1) in Fig. 1.Medium is filled with in aforesaid receptacle (p1), be uniformly mixed raw material and medium by the agitating vane (r1) rotated under the effect of the rotary actuation of turning axle (q1), carry out the pulverizing of aforementioned inorganic particulate (a) and this inorganic particles (a) to the dispersion in aforementioned acrylic polymers (X), compound (c).Aforementioned turning axle (p1) is formed as the cavity in relief outlet (t1) side inside it with opening portion.In this cavity, be provided with the isolated body 2 of the screen cloth type as isolated body, be provided with the stream connecting relief outlet (t1) in the inner side of this isolated body 2.Dispersion in aforesaid receptacle (p1) is delivered to the aforementioned isolated body 2 inside it by the pushing of the supply of raw material pressure from the opening portion of aforementioned turning axle (p1).Aforementioned isolated body 2 does not allow the larger medium of particle diameter pass through, and only allows the dispersion containing the less inorganic particles (A) of particle diameter pass through, makes aforementioned medium stay in container (p1) thus, only have 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 arranged in the mode forming sealing by the swiveling ring 3 be fixed in aforementioned axis (q1) and the set collar 4 of housing 1 that is fixed on the gland seal device in Fig. 1, and the arrangement mode of swiveling ring 3 in this unit and set collar 4 is towards equidirectional in 2 unit.Here, sealing refers to the pair of sliding face 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 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) supplied by pump 8 from outside seal flow container 7 supplies via said external sealing liquid supplying opening 5, gets back to aforementioned tank 7 via said external sealing liquid relief outlet 6, and circulate supply thus.Thus, fill outside seal liquid (R) in liquid-tight manner in aforementioned fluid-tight space 11, and the gap 9 formed between swiveling ring 3 and set collar 4 in aforementioned seal portion is filled up by outside seal liquid (R).The lubrication and cooling of the slipping plane of aforementioned swiveling ring 3 and aforementioned set collar 4 is carried out by sealing liquid (R).

In addition, the inflow pressure of setting sealing liquid (R) and the pressure of spring 10, make following 3 kinds of force balances: the power P1 due to the inflow pressure of outside seal liquid (R), set collar 4 being pushed to swiveling ring 3, due to spring 10, set collar 4 is pushed to the power P2 of swiveling ring 3, and set collar 4 is pulled away from the power P3 of swiveling ring 3 due to the inflow pressure of outside seal liquid (R).Thus, in as the set collar 4 of slipping plane and the gap 9 of swiveling ring 3, be filled with outside seal liquid (R) in liquid-tight manner, in this gap 9, do not have foregoing acrylic polymkeric substance (X), aforesaid compound (c) enters.When foregoing acrylic polymkeric substance (X), aforesaid compound (c) flow into this gap 9; Mechanical free radical (mechanoradical) is produced by this acrylic polymers (X) and this compound (c) due to aforementioned swiveling ring 3 and the slip of aforementioned set collar 4; there is polymerization and occur gelation, thickening in (methyl) acryl that they have sometimes; and be there is by use the wet-type ball mill of the present invention of the such gland seal device of aforementioned axis seal apparatus (u1), this risk can be avoided.

For the gland seal device that aforementioned axis seal apparatus (u1) is such, include, for example out tandem type mechanical seal etc.In addition, for having the commercially available product of aforementioned tandem type mechanical seal as the wet-type ball mill of gland seal device, include, for example out " LMZ " series etc. that AshizawaFinetechLtd. manufactures.

The reactive liquid of said external sealing liquid (R) right and wrong, include, for example out as the various organic solvents etc. cited by the organic solvent used when manufacturing foregoing acrylic polymkeric substance (X).In the middle of these, preferably same with the solvent phase used when manufacturing foregoing acrylic polymkeric substance (X) solvent, therefore, preferred ketone solvent, particularly preferably methylethylketone (MEK) or methyl iso-butyl ketone (MIBK) (MIBK).

The medium of filling in container (p1) in FIG such as can use various microballon.The starting material of microballon include, for example out: zirconium white, glass, titanium oxide, copper, silicic acid zirconium white etc.In the middle of these, due to the hardest and abrasion microballon of preferential oxidation zirconium less.

For aforementioned medium,, jitter time good with being separated of medium from the slurry of the isolated body 2 of the screen cloth type in Fig. 1 because of the pulverizing of aforementioned inorganic particulate (a) can be high and become shorter, the excessive dispersion phenomenon by force and not producing inorganic particles (a) can not be crossed the impact of aforementioned inorganic particulate (a), preferred median size counts the medium of the scope of 10 ~ 1000 μm by median particle diameter.

Aforementioned excessive dispersion phenomenon refers to: generate new active surface because of the destruction of inorganic particles, causes the phenomenon reassociated.When creating excessive dispersion phenomenon, dispersion liquid can gelation.

From the viewpoint of the power needed for dispersion minimum, can carry out most effectively pulverizing, the filling ratio of the medium in the container (p1) in Fig. 1 is preferably the scope of 75 ~ 90 volume % that container contents is amassed.

For aforementioned agitating vane (r1), impact when colliding from medium and aforementioned inorganic particulate (a) is large, dispersion efficiency improves, be preferably that the mode of the scope of 5 ~ 20m/sec carries out rotary actuation with the circumferential speed of first end, be more preferably the scope of 8 ~ 20m/sec.

When using this wet-type ball mill to manufacture resin combination of the present invention, its manufacture method can be intermittent type, also can be continous way.In addition, when continous way, can be the circular form again supplied after being taken out by slurry, also can be non-circulation type.In the middle of these, to improve and dispersions obtained uniformity is also excellent from the viewpoint of production efficiency, be preferably circular form.

In addition, when using this wet-type ball mill to manufacture resin combination of the present invention, preferably carry out with two-stage procedure, namely, use median particle diameter be the larger particles of the scope of 400 ~ 1000 μm as medium to carry out pre-dispersed operation, then use median particle diameter be the comparatively small-particle of the scope of 15 ~ 400 μm as medium to carry out main dispersion step.

Aforementioned pre-dispersed operation use median particle diameter is the larger medium of the scope of 400 ~ 1000 μm.The surging force that this medium applies when colliding with inorganic particles (a) is large, 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.Aforementioned main dispersion step use median particle diameter is the less medium of the scope of 15 ~ 400 μm.The surging force that this medium applies when colliding with inorganic particles (a) is little, but compared with the medium large with particle diameter, the increasing number of particle contained in same volume, therefore increases with the collision frequency of inorganic particles (a).Therefore, it is for being ground into fine particle further by the inorganic particles (a) be crushed in pre-dispersed operation to a certain degree.Here, when aforementioned pre-dispersed operation is long, there is the worry producing aforementioned excessive dispersion phenomenon, therefore this pre-dispersed operation is preferably carried out with the scope of slurry in 1 ~ 3 cycle of aforesaid receptacle (p1) internal recycle.

Active energy ray-curable resin composition of the present invention may be used for coating applications.This coating can by be coated on various base material and to irradiate active energy beam and solidify the coating being used as protecting substrate surface and use.In this situation, coating of the present invention directly can be coated and be used by the component of surface protection, the film that also can obtain being coated with on a plastic film is used as protective membrane.Or, also will can be coated with coating of the present invention on a plastic film and the film defining film is used as the optical thin film such as antireflection film, diffusion barrier and prismatic lens.Use the film of coating gained of the present invention to have the feature that surface hardness is high, the transparency is also excellent, therefore can be coated on various plastics film with the thickness meeting purposes, use as protective membrane purposes, film like products formed.

Foregoing plastics film include, for example out: 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; triacetyl cellulose film is the film of the Polarizer purposes being suitable for liquid-crystal display especially; but general thickness is thinner; it is 40 ~ 100 μm; even if be therefore also difficult to when being provided with hard coat fully improve surface hardness, and there is easily significantly curling feature.Even if the film formed by resin combination of the present invention is when using triacetyl cellulose film as base material, also play surface hardness high, resistance to crimp tendency, toughness, the effect that the transparency is also excellent, can use aptly.When this use cellulose triacetate film is as base material, glue spread when being coated with coating of the present invention preferably: with dried thickness be the scope of 4 ~ 20 μm, the mode of scope that is preferably 6 ~ 15 μm is coated with.Coating process now include, for example out: bar coater coating, the coating of Meyer rod, air knife coating, rotogravure application, oppositely rotogravure application, offset printing, flexible printing, silk screen print method etc.

In above-mentioned plastics film, polyester film include, for example out polyethylene terephthalate, and its thickness is generally about 100 ~ 300 μm.This film is due to cheap and easily processing and for various uses such as touch-screen displays, but it has feature very soft, be also difficult to fully improve surface hardness when being provided with hard coat.When using this polyethylene film as base material, glue spread when being coated with coating of the present invention preferably: according to its purposes, with dried thickness be the scope of 5 ~ 100 μm, the mode of scope that is preferably 7 ~ 80 μm is coated with.General when being coated with coating with the thickness such more than 30 μm, compared with situation about being coated with thinner thickness, there is easily significantly curling tendency, and coating of the present invention has the feature of resistance to crimp tendency excellence, even if be therefore also not easy generation when the higher thickness more than 30 μm is coated with curling, can use aptly.Coating process now include, for example out: bar coater coating, the coating of Meyer rod, air knife coating, rotogravure application, oppositely rotogravure application, offset printing, flexible printing, silk screen print method etc.

In above-mentioned plastics film, polymethyl methacrylate film general thickness is about 100 ~ 2,000 μm, thicker and solid, and therefore this film can be suitably used for the front panel purposes etc. of liquid-crystal display, particularly requires the purposes of high surface hardness.When using this polymethyl methacrylate film as base material, glue spread when being coated with coating of the present invention is preferably: according to its purposes, with dried thickness be the scope of 5 ~ 100 μm, the mode of scope that is preferably 7 ~ 80 μm is coated with.Generally, polymethyl methacrylate film such compared with when thick film is coated with coating with the thickness such more than 30 μm, although the laminate film that surface hardness is high can be formed, but there is the tendency that the transparency reduces, and coating of the present invention has the very high transparency compared with existing coating, the laminate film having high surface hardness and the transparency concurrently therefore can be obtained.Coating process now include, for example out: bar coater coating, the coating of Meyer rod, air knife coating, rotogravure application, oppositely rotogravure application, offset printing, flexible printing, silk screen print method etc.

The active energy beam irradiated when paint solidification of the present invention is made film include, for example out ultraviolet, electron rays.When utilizing ultraviolet to be cured, the UV irradiation equipment with xenon lamp, high voltage mercury lamp, metal halide lamp can be used as light source, adjusting the configuration etc. of light quantity, light source as required.When using high voltage mercury lamp, preferred 1 lamp of light quantity of scope relative to having 80 ~ 160W/cm, is cured with the scope of transfer rate 5 ~ 50m/ minute usually.And when utilizing electron rays to be cured, the electron rays booster machinery of acceleration voltage of the preferred scope with having 10 ~ 300kV is cured with the scope of transfer rate 5 ~ 50m/ minute usually.

In addition, the base material being coated with coating of the present invention is not only plastics film, also can be used as the surface coated agent of the collision bumper of various plastic molded article, such as mobile phone, household electrical appliance, automobile etc. aptly.In this situation, as the formation method of its film, include, for example out finishing, transfer printing, sheet bonding method etc.

Aforementioned finishing is following method: aforementioned coatings is carried out spraying coating or use curtain to be coated with the printing equipment such as machine, roller coating machine, gravure coater as after finishing coat is coated on products formed, irradiate active energy beam and make it solidify.

Preceding transfer method can list following method: after the transfer materials obtained being coated with aforementioned coating of the present invention on the base sheet with release property is bonded in products formed surface, stripping group body piece, at products formed surface transfer finishing coat, then irradiate active energy beam and make it solidify; Or after this transfer materials is bonded in products formed surface, irradiate active energy beam and make it solidify, then, stripping group body piece, thus at products formed surface transfer finishing coat.

And aforementioned bonding method is following method: the screening glass on base sheet with the film formed by aforementioned coating of the present invention or the screening glass on base sheet with film and the ornament layer formed by aforementioned coatings are adhered to plastic molded article, 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 preceding transfer method, first make transfer materials.This transfer materials such as can by aforementioned coatings separately or be coated in substrate sheets with the mixture that polyisocyanate compound is obtained by mixing, heat film semicure (B-rank) is manufactured.

Here, foregoing acrylic polymkeric substance (X) contained by active energy ray-curable compound of the present invention, aforesaid compound (c) are for having the compound of hydroxyl in molecular structure time, in order to more effectively carry out aforementioned B-rank chemical industry sequence, polyisocyanate compound can be combinationally used.

In order to manufacture transfer materials, first, the aforementioned coating of the present invention of application in substrate sheets.The method of application aforementioned coatings include, for example out: the coating method such as gravure coating process, rolling method, spraying coating method, lip coating method, comma coating method, the print process such as woodburytype, silk screen print method etc.From the viewpoint of resistance to abrasion and chemical proofing good, thickness during application preferably: the mode reaching 0.5 ~ 30 μm with the thickness of the film after solidifying carries out application, more preferably carries out application in the mode reaching 1 ~ 6 μm.

With preceding method in substrate sheets after application aforementioned coatings, heat drying makes film semicure (B-rank).Heating is generally 55 ~ 160 DEG C, is preferably 100 ~ 140 DEG C.Be generally 30 seconds ~ 30 minutes heat-up time, be preferably 1 ~ 10 minute, be more preferably 1 ~ 5 minute.

The formation employing the sealer of the products formed of preceding transfer material is such as carried out as follows: after the resin layer by the B-rank of preceding transfer material is bonding with products formed, irradiates active energy beam and resin layer is solidified.Specifically, include, for example out following method etc.: the resin layer by the B-rank of transfer materials is bonded in products formed surface, then, peel off the base sheet of transfer materials, resin layer thus by the B-rank of transfer materials be transferred to products formed on the surface after, irradiate can carry out the method (transfer printing) of the crosslinking curing of resin layer by actinic radiation-curable by active energy beam; By preceding transfer material clip in forming mould, resin is filled up to mould intracavitary administration, at its surface bonding transfer materials while obtaining synthetic resin, stripping group body piece after being transferred on products formed, is irradiated can be carried out the method (while of shaping transfer printing) of the crosslinking curing of resin layer by actinic radiation-curable by active energy beam.

Then, for sheet bonding method, specifically can list following method etc.: after bonding with products formed for the base sheet of the protective layer formation sheet made in advance, make its thermofixation carry out the method (rear bonding method) of the crosslinking curing of the resin layer on B-rank by heating; Aforementioned protective layer formation sheet is clipped in forming mould; resin is filled up to mould intracavitary administration; after it is surperficial bonding with protective layer formation sheet while obtaining synthetic resin, its thermofixation is made to carry out the method (while of shaping bonding method) of the crosslinking curing of resin layer by heating.

Then; film of the present invention on foregoing plastics film, is coated with coating of the present invention and makes it solidify formed film; or as plastic molded article surface protectant and be coated with coating of the present invention and also solidify the film formed; further, film of the present invention is the film being formed with film on a plastic film.

In the middle of the various uses of aforementioned film; as previously mentioned; from the aspect of hardness of film excellence, preferably coating of the present invention will be coated with on a plastic film and the film irradiating active energy beam and obtain is used as the Polarizer protective membrane that uses in liquid-crystal display, touch-screen display etc.Specifically, the protective membrane of the Polarizer used in liquid-crystal display, the touch-screen display etc. be coated with coating of the present invention and irradiate active energy beam when making it solidify and make film, forming the protective membrane that cured coating film has high rigidity and high transparent concurrently.In the protective membrane purposes of Polarizer, also can be formed with binder layer on the surface with the coating layer opposite side being coated with coating of the present invention.

Embodiment

Below provide concrete Production Example, embodiment to further illustrate the present invention, but the present invention is not limited to these embodiments.In case of no particular description, the part in example and % are quality criteria.

In embodiments of the invention, weight-average molecular weight (Mw) is the value using 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 TSKgelG5000HXL

+ TOSOH Co., Ltd manufactures TSKgelG4000HXL

+ TOSOH Co., Ltd manufactures TSKgelG3000HXL

+ TOSOH Co., Ltd manufactures TSKgelG2000HXL

Detector: RI(differential refractometer)

Data processing: TOSOH Co., Ltd manufactures SC-8010

Condition determination: column temperature 40 DEG C

Solvents tetrahydrofurane

Flow velocity 1.0ml/ minute

Standard: polystyrene

The inorganic particles (a) used in the embodiment of the present application

Inorganic particles (a-1): " AEROSILR7200 " median size that NipponAerosilCo., Ltd. manufacture is 12nm, the silicon dioxide microparticle at particle surface with (methyl) acryl

Inorganic particles (a-2): " AEROSILR711 " median size that NipponAerosilCo., Ltd. manufacture is 12nm, the silicon dioxide microparticle at particle surface with (methyl) acryl

Inorganic particles (a-3): " AEROSILOX50 " (median size is the silicon dioxide microparticle of 40nm) 100 parts NipponAerosilCo., Ltd. manufactured, 4 parts, water and 3-trimethoxysilyl-propyl methacrylic ester 18 parts are mixed is incorporated in the silicon dioxide microparticle of heat-treating gained at 140 DEG C

Inorganic particles (a-4): " AEROSIL90G " (median size is the silicon dioxide microparticle of 20nm) 100 parts NipponAerosilCo., Ltd. manufactured, 4 parts, water and 3-trimethoxysilyl-propyl methacrylic ester 18 parts are mixed is incorporated in the silicon dioxide microparticle of heat-treating gained at 140 DEG C

Inorganic particles (a-5): " AEROSIL50 " median size that NipponAerosilCo., Ltd. manufacture 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): " ELCOMV-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): " AEROSIL974 " median size that NipponAerosilCo., Ltd. manufacture 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)

Propylene glycol monomethyl ether 480 mass parts is dropped in the reaction unit possessing whipping appts, cooling tube, dropping funnel and nitrogen ingress pipe, make temperature to 110 DEG C in system while stirring, then, utilize dropping funnel to spend and within 3 hours, drip the mixed solution comprising glycidyl methacrylate 91 mass parts, methyl methacrylate 318 mass parts, cyclohexyl methacrylate 45 mass parts and peroxide-2-ethyl hexanoic acid tert-butyl (" PERBUTYLO " that Japanese emulsifying agent Co., Ltd. manufactures) 15 mass parts, then keep 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 warming up to 100 DEG C further to 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)

Methyl iso-butyl ketone (MIBK) 480 mass parts is dropped in the reaction unit possessing whipping appts, cooling tube, dropping funnel and nitrogen ingress pipe, make temperature to 110 DEG C in system while stirring, then, utilize dropping funnel to spend and within 3 hours, drip the mixed solution comprising glycidyl methacrylate 130 mass parts, methyl methacrylate 304 mass parts and peroxide-2-ethyl hexanoic acid tert-butyl (" PERBUTYLO " that Japanese emulsifying agent Co., Ltd. manufactures) 15 mass parts, then keep 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 warming up to 100 DEG C further to 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)

Propylene glycol monomethyl ether 455 mass parts is dropped in the reaction unit possessing whipping appts, cooling tube, dropping funnel and nitrogen ingress pipe, make temperature to 110 DEG C in system while stirring, then, utilize dropping funnel to spend and within 3 hours, drip the mixed solution comprising glycidyl methacrylate 166 mass parts, methyl methacrylate 208 mass parts, isobornyl methacrylate 42 mass parts and peroxide-2-ethyl hexanoic acid tert-butyl (" PERBUTYLO " that Japanese emulsifying agent Co., Ltd. manufactures) 40 mass parts and formed, then keep 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 84 mass parts, add triphenylphosphine 5 mass parts, then be warming up to 100 DEG C further to 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)

Methyl iso-butyl ketone (MIBK) 485 mass parts is dropped in the reaction unit possessing whipping appts, cooling tube, dropping funnel and nitrogen ingress pipe, make temperature to 110 DEG C in system while stirring, then, utilize dropping funnel to spend and within 3 hours, drip the mixed solution comprising glycidyl methacrylate 230 mass parts, methyl methacrylate 115 mass parts, cyclohexyl methacrylate 38 mass parts and peroxide-2-ethyl hexanoic acid tert-butyl (" PERBUTYLO " that Japanese emulsifying agent Co., Ltd. manufactures) 10 mass parts, then keep 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 warming up to 100 DEG C further to 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)

Methyl iso-butyl ketone (MIBK) 470 mass parts is dropped in the reaction unit possessing whipping appts, cooling tube, dropping funnel and nitrogen ingress pipe, make temperature to 110 DEG C in system while stirring, then, utilize dropping funnel to spend and within 3 hours, drip the mixed solution comprising glycidyl methacrylate 321 mass parts, methyl methacrylate 17 mass parts and peroxide-2-ethyl hexanoic acid tert-butyl (" PERBUTYLO " that Japanese emulsifying agent Co., Ltd. manufactures) 25 mass parts and formed, then keep 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 163 mass parts, add triphenylphosphine 5 mass parts, then be warming up to 100 DEG C further to 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.

There is in the molecular structure used in the embodiment of the present application 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)

Dicyclohexyl methyl hydride-4,4 '-vulcabond 166 mass parts, dibutyl tin laurate 0.2 mass parts and first quinone 0.2 mass parts is added, warming while stirring to 60 DEG C in the reaction unit possessing whipping appts.Then, divide 10 inputs by pentaerythritol triacrylate (" ARONIXM-305 " that Toagosei Co., Ltd manufactures) 630 mass parts, dropped into once every 10 minutes.Further reaction 10 hours, terminates reaction, obtains urethane acrylate (c-3) after the absorption of the isocyanate group being confirmed 22500cm-1 by infrared spectrum is disappeared.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 (in 20 mass parts, acrylic polymers (X-2) is 10.0 mass parts) of the acrylic polymers (X-2) obtained in compounding aforementioned Production Example 2, dipentaerythritol acrylate (c-1) 45 mass parts, inorganic particles (a-1) 45 mass parts, methyl iso-butyl ketone (MIBK) (hereinafter referred to as " MIBK ") 80 mass parts and propylene glycol monomethyl ether (hereinafter referred to as " PGM ") 10 mass parts, make the slurry of nonvolatile component 50 quality %, wet-type ball mill (" StarmillLMZ015 " that AshizawaLtd. manufactures) is used to carry out blending dispersion to it, obtain dispersion.

The each condition utilizing aforementioned wet-type ball mill to carry out disperseing is as follows.

Medium: the zirconium white microballon of median particle diameter 100 μm

Resin combination is relative to the filling ratio of the 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

Light trigger (" IRGACURE#184 " that CibaSpecialtyChemicalsInc. manufactures) 2 mass parts are added in dispersions obtained, add MIBK and PGM further and 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 evaluation, result is shown in table 1.

The mensuration of the median size of inorganic particles (A)

For the median size recorded based on dynamic light scattering method of the inorganic particles (A) in active energy ray-curable resin composition, dispersions obtained MIBK is diluted, after being adjusted to the MIBK solution of concentration 5%, " ELSZ-2 " that use this MIBK solution, manufacture with particle size determination device (Otsuka Electronics Co., Ltd.: according to " ISO13321 ".Calculated by the Cumulant Method Using) measure.

The storage stability test of active energy ray-curable resin composition

Foregoing active energy ray curable resin composition is left standstill 1 month under the temperature condition of 40 DEG C, and evaluating respectively has sediment-free through time point.

Zero: do not observe throw out

△: observe throw out after 3 weeks

×: after 1 week, observe throw out

The pencil hardness test of film

1. the making method of test film

Be that the mode of respective prescribed value is coated on following plastics film by foregoing active energy ray curable resin composition bar coater to make the thickness after solidification, drying 1 minute at 70 DEG C, use high voltage mercury lamp to make it solidify with the irradiation dose of 250mJ/cm2 by film under a nitrogen, obtain the test film with cured coating film thus.

On cellulose triacetate film (hereinafter referred to as " TAC ") (thickness 80 μm), 10 μm

On pet film (hereinafter referred to as " PET ") (thickness 188 μm), 10,20,50 μm

On polymethyl methacrylate film (hereinafter referred to as " PMMA ") (thickness 300 μm), 10,20,50 μm

2. pencil hardness test method

For the curing overlay film of above-mentioned test film, according to JISK5400, the test film taking cellulose triacetate film as base material is carried out to the pencil test of load 500g, the test film taking pet film as base material is carried out to the pencil test of load 750g, the 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, more than 1 time is caused the pencil hardness of hardness as this film of the low one-level of the hardness of cut.

The transparency test of film

1. the making method of cured coating film

Test film is made by the method same with during above-mentioned pencil hardness test.In addition, about the transparency of film, only, test film of the condition of at cellulose triacetate film (thickness 80 μm) upper, thickness 10 μm under made the thinnest to the thickness of test film entirety, and the thickness of test film entirety the thickest, under the condition of, thickness 50 μm upper at polymethyl methacrylate film (thickness 188 μm), made test film is tested.

2. transparent test method

" HazeComputerHZ-2 " that use SugaTestInstrumentsCo., Ltd. to manufacture measures the haze value of film.Haze value is lower, then 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

Film is made by the method same with during above-mentioned pencil hardness test.In addition, because the woolliness of resistance to steel wire of film does not exist the difference produced because of the kind of base material film substantially, therefore test and only carry out for made test film under the condition of, thickness 10 μm upper at cellulose triacetate film (thickness 80 μm).

2. the woolliness of resistance to steel wire test

With steel wool, (" Bonstar#0000 " 0.5g that NipponSteelWoolCo., Ltd. manufacture encases the discoid pressure head of diameter 2.4 centimetres, applies the heavy load of 1000g come and go 100 times in the film aspect of evaluation film this pressure head.The haze value of the film before and after " HazeComputerHZ-2 " determination test using SugaTestInstrumentsCo., Ltd. to manufacture, evaluates their difference with δ H.δ H value is less, then 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

Film is made by the method same with during above-mentioned pencil hardness test.In addition, about the resistance to crimp tendency of film, only made test film under the condition of made test film under the condition especially easily producing curling, upper at cellulose triacetate film (thickness 80 μm), thickness 10 μm and, thickness 50 μm upper at pet film (thickness 188 μm) is tested.

2. resistance to crimp tendency test

Test film is cut into 10cm square, measures 4 angle floating from level, evaluate with its mean value.Be worth less then 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

Film is made by the method same with during above-mentioned pencil hardness test.In addition, about the bending of film, only to mostly require to have this performance, under the condition of, thickness 10 μm upper at cellulose triacetate film (thickness 80 μm), made test film is tested.

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 cracked with the cured coating film layer of visual confirmation film, using the minimum diameter of proof stick that do not crack 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

Film is made by the method same with during above-mentioned pencil hardness test.In addition, alkali resistance due to film does not exist substantially because of the kind of base material film, the thickness of cured coating film layer and the difference that produces, therefore tests and only carries out made test film under the condition of, thickness 10 μm upper at cellulose triacetate film (thickness 80 μm).

2. alkaline resistance test

Make film closely sealed with the absorbent cotton (3cm × 3cm) that impregnated of 5% aqueous sodium hydroxide solution, in order to prevent drying from covering glass cover, placing 24 hours at 25 DEG C, evaluating the condition of surface of film.

Zero: do not observe change

△: observe foaming

×: film generation gonorrhoea

Embodiment 2 ~ 17

Make the formula consisted of shown in table 1 and 2, in addition obtain active energy ray-curable resin composition similarly to Example 1.To the test that they carry out similarly to Example 1.Result is 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 (in 40 mass parts, acrylic polymers (X-1) is 20.0 mass parts) of the acrylic polymers (X-2) obtained in compounding aforementioned Production Example 2, dipentaerythritol acrylate (c-1) 35 mass parts, inorganic particles (a-6) 150 mass parts obtain is carried out blending dispersion, obtains dispersion.For this dispersion, prepare active energy ray-curable resin composition similarly to Example 1, carry out test similarly to Example 1.Result is shown in table 3.

Each condition based on the dispersion of aforementioned homogenous disperse device is as follows.

Rotating speed: 2400r/min

Jitter time: 15 minutes

Comparative example 2

Make the formula consisted of shown in table 3, in addition prepare active energy ray-curable resin composition in the same manner as comparative example 1, carry out test similarly to Example 1.Result is shown in table 3.

Comparative example 3 and 4

Make the formula consisted of shown in table 3, in addition prepare active energy ray-curable resin composition similarly to Example 1, to the test that they carry out similarly to Example 1.Result is shown in table 3.

Comparative example 5

The formulation homogenous disperse device that methyl isobutyl ketone solution 24 mass parts (in 24 mass parts, acrylic polymers (X-5) is 12.0 mass parts) of the acrylic polymers (X-5) obtained in compounding aforementioned Production Example 5, 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 obtain is carried out blending dispersion, obtains dispersion.For this dispersion, prepare active energy ray-curable resin composition similarly to Example 1, carry out test similarly to Example 1.Result is shown in table 3.

Each condition based on the dispersion of 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 formulation methyl isobutyl ketone solution 100 mass parts (in 100 mass parts, acrylic polymers (X-5) is 50.0 mass parts) of the acrylic polymers (X-5) obtained in compounding aforementioned Production Example 5, inorganic particles (a-9) 50 mass parts and methyl iso-butyl ketone (MIBK) 100 mass parts 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 active energy ray-curable resin composition similarly to Example 1, carry out test similarly to Example 1.Result is shown in table 3.

[table 3]

Claims

1. an active energy ray-curable resin composition; it is characterized in that; it contains scope that the median size recorded based on dynamic light scattering method is 95 ~ 250nm and the inorganic particles (A) be made up of dry silica and weight-average molecular weight are 5; 000 ~ 80; the scope of 000 and the acrylic polymers (X) in molecular structure with (methyl) acryl, as neccessary composition, contain described inorganic particles (A) with the scope of 35 ~ 60 mass parts in its nonvolatile component 100 mass parts.

2. active energy ray-curable resin composition according to claim 1; wherein; described acrylic polymers (X) is for making acrylic polymers (Y) and compound (z) react and the polymkeric substance that obtains; the compound (y) that described acrylic polymers (Y) has reactive functional groups and (methyl) acryl carries out being polymerized obtaining as neccessary composition, the functional group that the reactive functional groups that described compound (z) having can have with described compound (y) reacts and (methyl) acryl.

3. active energy ray-curable resin composition according to claim 2, wherein, described acrylic polymers (Y) is that the ratio of the scope of 10/90 ~ 90/10 carries out being polymerized and the polymkeric substance obtained with their mass ratio (y)/(v) for making described compound (y) and other acrylics monomer (v).

4. active energy ray-curable resin composition according to claim 2; 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.

5. active energy ray-curable resin composition according to claim 1, wherein, (methyl) acryl equivalent of described acrylic polymers (X) is the scope of 220 ~ 1650g/eq.

6. active energy ray-curable resin composition according to claim 1, wherein, described acrylic polymers (X) has hydroxyl in the molecular structure, and its hydroxyl equivalent is the scope of 35 ~ 250mgKOH/g.

7. 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 containing except described acrylic polymers (X), the compound (c) in molecular structure with (methyl) acryl.

8. active energy ray-curable resin composition according to claim 1, it manufactures 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 rotates under the effect of the rotary actuation of aforementioned turning axle, 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 running through container of described turning axle, described gland seal device has 2 mechanical seal unit, and the sealing with these 2 mechanical seal unit the structure that seals by outside seal liquid, the inorganic particles (a) that the second particle being the dry silica particles agglomerate of the scope of 3 ~ 100nm by average primary particle diameter from the described supplying opening of described wet-type ball mill to described supply for receptacles is formed and using described acrylic polymers (X) as the resinous principle of neccessary composition, in described container, make described turning axle and described agitating vane rotate, be uniformly mixed medium and raw material, carry out the pulverizing of described inorganic particles (a) and this inorganic particles (a) thus to the dispersion in described resinous principle, then, discharge from described relief outlet.

9. active energy ray-curable resin composition according to claim 1, wherein, described inorganic particles (A) is the dry silica at its particle surface with (methyl) acryl structure.

10. a coating, it contains the active energy ray-curable resin composition according to any one of claim 1 ~ 9.

11. 1 kinds of films, it makes paint solidification according to claim 10 and obtains.

12. 1 kinds of laminate films, it has film according to claim 11 at the single or double of plastics film.

13. laminate films according to claim 12, wherein, described plastics film is any one in cellulose triacetate film, pet film, polymethyl methacrylate film.

14. laminate films according to claim 12, wherein, the thickness of described film is the scope of 5 ~ 100 μm.