CN102463723B - Laminated film - Google Patents
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- CN102463723B CN102463723B CN201010533834.0A CN201010533834A CN102463723B CN 102463723 B CN102463723 B CN 102463723B CN 201010533834 A CN201010533834 A CN 201010533834A CN 102463723 B CN102463723 B CN 102463723B
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Abstract
The present invention relates to laminated film.The invention provides a kind of solidification compound, it can obtain the excellent in te pins of durability such as fingerprint visibility, fingerprint erasing property excellence, marresistance, humidity resistance, dry heat resistance, has the cured film of high transparent simultaneously.Laminated film of the present invention has cured film at least one face of hyaline membrane base material, and described cured film uses the solidification compound containing following compositions (A) ~ (C) to be formed.(A) multifunctional (methyl) acrylate monomer; (B) Photoepolymerizationinitiater initiater; (C) that there is hydroxyl and (methyl) acryloyl group, that HLB value is in 2 ~ 15 scopes fatty acid ester system surfactant.
Description
Technical field
The present invention relates to the solidification compound containing the fatty acid ester system surfactant with (methyl) acryloyl group and cured film.In more detail, relate to as the useful solidification compound of hard coat material and cured film.
Background technology
In recent years, as plastics (Merlon, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melmac, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin etc.), metal, timber, paper, glass, roofing slates etc. are for preventing the coating material of the damage of various substrate surface (scratch) or antipollution protective finish material and antireflection film, be required that there is excellent coating, and can hardness be formed on the surface of various base material, marresistance, soil resistance, abrasion performance, surface smoothness, low crimpiness, adaptation, the transparency, the solidification compound of the equal excellent cured film of outward appearance of reagent resistance and coated surface.
In recent years, when inputting information terminal, the use of touch panel becomes many.In order to data input etc. just can be carried out by directly contacting display frame with finger or pen etc., touch panel needs marresistance, soil resistance, particularly fingerprint visibility and fingerprint and wipes property, durability, the transparency etc., but present situation is the cured film not also being met all these characteristics.
In patent document 1, disclose the HLB formed by fatty acid ester be 2 ~ 15 nonionic surface active agent add the touch panel or display hard coat film that obtain in ionizing radiation gel-type resin to.Although this film fingerprint visibility and fingerprint erasing property are well, marresistance is poor, and the transparency is also poor in addition.This is because in order to embody fingerprint visibility, fingerprint erasing property, fatty acid ester system surfactant is exuded to cured film surface, and therefore the marresistance of cured film and the transparency have dropped.
Patent Document 2 discloses a kind of hardening resin composition of hard conating; it contains: have regulation structure, have the polymer (specifically fatty acid ester system surfactant) containing polyalkylene oxide chain of polymerism unsaturated group at all ends; have the compound of more than 2 (methyl) acryloyl groups and surface to have the inorganic particles of polymerism unsaturated group, and these compositions can react to each other.This hardening resin composition is solidified and the cured film that obtains; by above-mentioned polymer containing polyalkylene oxide chain, the compound of (methyl) acryloyl group and surface is had to have the inorganic particulate of polymerizable functional group to react to each other; polymer containing polyalkylene oxide chain can not be exuded to cured film surface; and each composition can be cross-linked with each other, marresistance improves thus.The cured film of patent document 2, fingerprint visibility and fingerprint wipe property excellence, marresistance is also excellent, but also have room for improvement in the durability such as dry heat resistance and humidity resistance.
[prior art document]
[patent document]
[patent document 1] Japanese Unexamined Patent Publication 2004-114355 publication
[patent document 2] Japanese Unexamined Patent Publication 2008-165040 publication
Summary of the invention
The present invention completes in view of the above problems, its object is to provide obtained cured film to have excellent fingerprint visibility, fingerprint erasing property, marresistance, and there is the durability such as humidity resistance and dry heat resistance, have simultaneously high transparent laminated film and as the useful solidification compound of hard coat material.
In order to reach above-mentioned purpose; the present inventor etc. have carried out conscientiously studying; found that; if all hydroxyls being present in fatty acid ester system surfactant end to be become polymerism unsaturated group ((methyl) acryloyl group), then the durability such as humidity resistance, dry heat resistance can be impaired.Therefore; use has the fatty acid ester system surfactant of hydroxyl and (methyl) acryloyl group; the cured film of fingerprint visibility and fingerprint erasing property excellence, excellent scratch resistance, the simultaneously durability such as humidity resistance and dry heat resistance also excellence can be obtained, thus complete the present invention.
And then also find, by making to contain polymerism unsaturated group in fatty acid ester system surfactant, improve with the compatibility of adhesive ingredients, when namely using high concentration cooperation fatty acid ester system surfactant, also can not there is the albefaction of cured film (film), can high transparent be obtained.
That is, the invention provides following laminated film and solidification compound.
1, a laminated film, it has cured film at least one face of hyaline membrane base material, and described cured film uses the solidification compound containing following compositions (A) ~ (C) to be formed,
(A) multifunctional (methyl) acrylate monomer
(B) Photoepolymerizationinitiater initiater
(C) that there is hydroxyl and (methyl) acryloyl group, that HLB value is in 2 ~ 15 scopes fatty acid ester system surfactant.
2, the laminated film as described in above-mentioned 1, wherein, the HLB value of described composition (C) is in the scope of 2 ~ 12.
3, the laminated film as described in above-mentioned 1 or 2, wherein, the ratio of the hydroxyl that described composition (C) has and (methyl) acryloyl group is at hydroxyl: (methyl) acryloyl group=1: in the scope of 6 ~ 3: 1.
4, the laminated film according to any one of above-mentioned 1 ~ 3, wherein, the carbon number that described composition (C) has straight-chain or a branched is 1 valency or the divalent alkyl of 8 ~ 30.
5, the laminated film according to any one of above-mentioned 1 ~ 4; wherein, (methyl) acryloyl group of described composition (C) is by making the hydroxyl modification that described fatty acid ester system surfactant has with the compound with (methyl) acryloyl group and the group imported.
6, the laminated film as described in above-mentioned 5, wherein, described in there is (methyl) acryloyl group compound be the compound having NCO and (methyl) acryloyl group.
7, the laminated film according to any one of above-mentioned 1 ~ 6, wherein, containing (D) number average particle diameter is further the inorganic oxide particle of 1 ~ 200nm.
8, the laminated film as described in above-mentioned 7, wherein, the inorganic oxide particle of described composition (D) has carried out the particle of modification with particle modified dose with (methyl) acryloyl group.
9, the laminated film according to any one of above-mentioned 1 ~ 8, wherein, during using the total amount of described composition (A), (B) and (D) as 100 weight portion, described composition (C) is in the scope of 0.1 ~ 30 weight portion.
10. as the laminated film according to any one of above-mentioned 1 ~ 9, wherein, further containing the organic or inorganic particle that (E) number average particle diameter is 0.5 ~ 10 μm.
11, a solidification compound, it contains following compositions (A) ~ (C),
(A) multifunctional (methyl) acrylate monomer
(B) Photoepolymerizationinitiater initiater
(C) that there is hydroxyl and (methyl) acryloyl group, that HLB value is in 2 ~ 15 scopes fatty acid ester system surfactant.
12, the solidification compound as described in above-mentioned 11, it is for the formation of hard conating.
13, a cured film, it forms by making the solidification compound described in above-mentioned 11 or 12 solidify.
According to the present invention, fingerprint visibility, fingerprint erasing property can be provided excellent, there is the cured film of the durability such as marresistance, humidity resistance and dry heat resistance simultaneously.
According to the present invention, the laminated film that the transparency is excellent can also be provided.
According to the present invention, can provide and can obtain fingerprint visibility, fingerprint erasing property is excellent, marresistance is also excellent, has the durability such as humidity resistance and dry heat resistance simultaneously, and the solidification compound of the cured film of transparency excellence.
Detailed description of the invention
Below, the present invention is explained.
I. solidification compound
Solidification compound of the present invention (hereinafter referred to as composition of the present invention), can contain following compositions (A) ~ (G).In these compositions, composition (A) ~ (C) is essential component, and composition (D) ~ (G) is any composition added as required.
(A) multifunctional (methyl) acrylate monomer
(B) Photoepolymerizationinitiater initiater
(C) that there is hydroxyl and (methyl) acryloyl group, that HLB value is in 2 ~ 15 scopes fatty acid ester system surfactant
(D) number average particle diameter is the inorganic oxide particle of 1 ~ 200nm
(E) number average particle diameter is the organic or inorganic particle of 0.5 ~ 10 μm
(F) organic solvent
(G) other additive
Composition of the present invention; because mentioned component (C) has aliphatic acid ester group and the HLB value (hydrophilic lipophilic balance) of (methyl) acryloyl group to be the fatty acid ester system surfactant of 2 ~ 15; therefore composition (C) oozing out to cured film surface can be prevented; improve the marresistance of cured film, and then improve the durability such as humidity resistance, dry heat resistance.In addition, by having hydroxyl, fingerprint visibility improves.
In addition; mentioned component (C) has (methyl) acryloyl group and hydroxyl; therefore; improve with the compatibility of adhesive ingredients (A); namely use high concentration gradation composition (C) and the cured film (film) that obtains also can not albefaction, obtain the cured film with high transparent.
Below, each composition of the present composition is described.
(A) multifunctional (methyl) acrylate monomer
Composition used in the present invention (A) multifunctional (methyl) acrylate monomer has more than 2 (methyl) acryloyl group (methyl) acrylate monomers.Composition (A) is the so-called adhesive ingredients of the film forming for improving composition.By combining with aftermentioned composition (C), composition (C) can be fixed on cured film.
Should illustrate; although there is aftermentioned composition (D) to be the situation that the situation of reactive particles (Dc) and aftermentioned composition (C) also have multiple (methyl) acryloyl group; but in multifunctional (methyl) acrylate monomer (A) of the present invention, do not comprise reactive particles (Dc) and composition (C).
As the concrete example of multifunctional (methyl) acrylate monomer, trimethylolpropane tris (methyl) acrylate can be enumerated, double trimethylolpropane four (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, glycerine three (methyl) acrylate, three (2-ethoxy) isocyanuric acid ester three (methyl) acrylate etc. has multifunctional (methyl) acrylate monomer of more than 3 (methyl) acryloyl groups, ethylene glycol bisthioglycolate (methyl) acrylate, 1, 3-butanediol two (methyl) acrylate, 1, 4-butanediol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, DPG two (methyl) acrylate etc. has multifunctional (methyl) acrylate monomer of 2 (methyl) acryloyl groups, multifunctional (methyl) esters of acrylic acid containing hydroxyl such as two (2-ethoxy) isocyanuric acid ester two (methyl) acrylate, and to the oxirane of these hydroxyls or poly-(methyl) esters of acrylic acid of propylene oxide adduct, there are oligoester (methyl) esters of acrylic acid of more than 2 (methyl) acryloyl groups, oligo-ether (methyl) esters of acrylic acid and oligomeric epoxy (methyl) esters of acrylic acid etc.Multifunctional (methyl) acrylate monomer more than enumerated can be used alone or two or more kinds may be used.
Wherein, preferred dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, double trimethylolpropane four (methyl) acrylate etc.
As the commercially available product of such multifunctional (methyl) acrylate monomer (A), such as, East Asia synthesis (strain) ARONIXM-400 processed can be enumerated, M-404, M-408, M-450, M-305, M-309, M-310, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, Japan chemical drug (strain) KAYARADD-310 processed, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, common prosperity society chemistry (strain) LightAcrylatePE-4A processed, DPE-6A, DTMP-4A, Xin Zhong village chemistry (strain) NKESTERA-TMM-3LM-N processed etc.
Composition (A); using its total amount as 100 % by weight; multifunctional (methyl) acrylate monomer that preferably containing more than 50 % by weight there are more than 3 (methyl) acryloyl groups, more preferably more than 70 % by weight, more preferably 100 % by weight.
The use level of the composition (A) in the present composition, during using the total amount of composition (A), (B) and (D) as 100 weight portion, it is in the scope of 10 ~ 95 weight portions, preferably in the scope of 10 ~ 80 weight portions, more preferably in the scope of 20 ~ 70 weight portions.By by above-mentioned range fit (A) composition, the cured film of high rigidity can be obtained.
(B) Photoepolymerizationinitiater initiater
Composition (B) in the present invention is Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater (B), be irradiated by radioactive ray (light) and produce the compound (radioactive ray (light) polymerization initiator) of living radical kind, general Photoepolymerizationinitiater initiater can be enumerated.
As Photoepolymerizationinitiater initiater, decompose thus the material producing free radical and then polymerization is started as long as inject row by illumination, just have no particular limits, such as, can acetophenone be enumerated, acetophenone benzil ketals, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, xanthone, Fluorenone, benzaldehyde, fluorenes, anthraquinone, triphenylamine, carbazole, 3-methyl acetophenone, 4-chlorobenzophenone, 4,4 '-dimethoxy-benzophenone, 4,4 '-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzil dimethyl ketal, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, thioxanthones, diethyl thioxanthone, ITX, CTX, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino-propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-Isosorbide-5-Nitrae-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, oligomeric (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) acetone) etc.
As the commercially available product of Photoepolymerizationinitiater initiater, such as, can enumerate Ciba (strain) IRGACURE184 processed, 369,651,500,819,907,784,2959, CGI1700, CGI1750, CGI1850, CG24-61, DAROCUR1116,1173, BASF AG LucirinTPO, 8893, EbecrylP36, Lamberti Inc. of UCB. S.A. (BE) Bruxelles Belgium EsacureKIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75/B etc.
The content of the composition (B) in the present composition, during using the total amount of composition (A), (B) and (D) as 100 weight portion, it is usually in the scope of 0.1 ~ 10 weight portion, preferably in the scope of 0.1 ~ 5 weight portion, more preferably in the scope of 0.5 ~ 5 weight portion.Should illustrate, the content of composition (B), in above-mentioned scope, the content of composition (A) can be determined as benchmark.Such as, using the content of composition (A) as 100 weight portion time, the content of composition (B) is preferably 0.5 ~ 20 weight portion, is more preferably 0.5 ~ 15 weight portion.By being located in above-mentioned scope by the content of composition (B), the film of high rigidity can be obtained.
(C) that there is hydroxyl and (methyl) acryloyl group, that HLB value is in 2 ~ 15 scopes fatty acid ester system surfactant (following, sometimes composition (C) to be called " (C) fatty acid ester system surfactant ")
Composition (C), by having (methyl) acryloyl group, can be combined thus immobilization by the adhesive ingredients in the present composition, so (C) fatty acid ester system surfactant can be prevented to be exuded to cured film surface.Therefore, the durability such as the marresistance of the cured film obtained, humidity resistance and dry heat resistance improve.And then, composition (C) because containing hydroxyl, so obtained cured film can be given with fingerprint visibility and fingerprint erasing property.Wherein so-called " fingerprint visibility ", mean when film surface attachment fingerprint with macroscopic difficulty.
In addition; because composition (C) has hydroxyl and (methyl) acryloyl group; so improve with the compatibility of other composition in composition; even if when coordinating (C) fatty acid ester system's surfactant by high concentration, the effect that albefaction does not occur gained cured film also can be obtained.
So-called HLB value (hydrophilic lipophilic balance) is the important index of the characteristic of presentation surface activating agent, represents the degree of hydrophily or oil loving size.HLB value can be obtained by following calculating formula.
HLB＝7+11.7Log(M
W/M
0)
Here M
wthe molecular weight of hydrophilic group, M
0it is the molecular weight of lipophilic group.M
w+ M
0=M (molecular weight of surfactant).The HLB value of (C) fatty acid ester system surfactant used in the present invention is necessary in the scope of 2 ~ 15, preferably in the scope of 2 ~ 12, more preferably in the scope of 2 ~ 10.By HLB value being located in above-mentioned scope, improve with the compatibility of fingerprint liquid, thus observability improves.
The carbon number that the fatty acid ester structure of composition (C) preferably comes from straight-chain or branched is the aliphatic carboxylic acid of 8 ~ 30.
In addition, aliphatic acid ester group is preferably containing polyoxyalkylenes or glyceryl group.
Composition (C) can by will having hydroxyl but not having a part of hydroxyl of the fatty acid ester system surfactant of (methyl) acryloyl group convert (methyl) acryloyl group to and obtain.Preferably, composition (C) and can have the compound of (methyl) acryloyl group to react and obtain by the hydroxyl that makes fatty acid ester system surfactant have.
There is the compound of (methyl) acryloyl group, such as, the compound of NCO and (methyl) acryloyl group can be used.By using such compound, hydroxyl and the NCO of fatty acid ester system surfactant react and form urea key, thus import (methyl) acryloyl group.
As the concrete example having NCO with the compound of (methyl) acryloyl group; 2-(methyl) acryloyloxyethyl isocyanate, 2-(methyl) acryloxypropyl isocyanates, 1,1-two [(methyl) acryloyloxymethyl] ethyl isocyanates etc. can be used.In addition, the compound containing hydroxyl and (methyl) acryloyl group and diisocyanate cpd reaction can also be made to obtain.As such diisocyanate cpd, IPDI, toluene di-isocyanate(TDI), hexamethylene diisocyanate etc. can be enumerated.
As having hydroxyl but there is no the concrete example of the fatty acid ester system surfactant of (methyl) acryloyl group; such as; polyoxyalkylene hardened castor oil, polyoxyalkylene fatty acid ester etc. can be enumerated, preferred polyoxyethylene hardened castor oil, polyoxyethylene fatty acid ester.
As the commercially available product of polyoxyethylene hardened castor oil, such as, EMALEXHC series (Japanese Emulsion Inc.), NOIGENHC series (the first industrial pharmaceutical Inc.) etc. can be enumerated.
As the commercially available product of polyoxyethylene fatty acid ester, such as, EMALEXGWIS-100EX (glyceryl isostearate, Japanese Emulsion Inc.), NOIGENGIS series (the first industrial pharmaceutical Inc.) etc. can be enumerated.
Have hydroxyl but do not have the fatty acid ester system surfactant of (methyl) acryloyl group, with the reaction of compound having NCO and (methyl) acryloyl group, can carry out as follows.
Namely, it is the reaction of isocyanate compound and hydroxy-containing compounds, usually relative to the total amount of 100 weight portion reactants, copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyl tin laurate, the triethylamine, 1 of preferred use 0.01 ~ 1 weight portion, 4-diazabicyclo (2.2.2) octane, 2, the urethanation catalyst such as 6,7-trimethyl-Isosorbide-5-Nitrae-diazabicyclo (2.2.2) octane.In addition, the reaction of these compounds also can be carried out under the condition of catalyst-free.Reaction temperature is generally 0 ~ 90 DEG C, preferably carries out at 40 ~ 80 DEG C.Reaction both can be carried out in the absence of a solvent, also can dissolve and carry out in a solvent.
Composition (C) such as can have the structure that following formula (1) represents.
In formula (1), the implication of each symbol is as follows.X represents that the carbon number that can be substituted is (the m of 3 ~ 10
1+ m
2) alkyl of valency.Multiple Y
1and Y
2represent the divalent group containing ehter bond, ester bond or urea key or singly-bound independently of one another, Y
1and Y
2in at least 1 structure had from aliphatic acid.Z indicates the group of more than 1 (methyl) acryloyl group.Multiple R
11and R
12represent that carbon number is the alkyl of the straight or branched of 1 ~ 4 independently of one another.M
1and m
2be the integer of 1 ~ 10 separately, n
1and n
2represent the integer of 0 ~ 20 independently of one another.
The compound of composition (C) can operate as follows and synthesize.
According to the ratio having among the hydroxyl of the surfactant of more than 2 hydroxyls, every 1 molecule on average remains more than 1 hydroxyl; making it to react with having the isocyanate compound of (methyl) acryloyl group or (methyl) acrylic acid, the compound of composition (C) can be obtained thus.Such as, when using there being the surfactant of 3 hydroxyls as raw material, it is made to react with the isocyanate compound of (methyl) acryloyl group or (methyl) acrylic acid with below hydroxyl 2/3 molar equivalent.
The mol ratio of the hydroxyl that composition (C) has and (methyl) acryloyl group is preferably at hydroxyl: (methyl) acryloyl group=1: in the scope of 6 ~ 3: 1.By the ratio of hydroxyl and (methyl) acryloyl group is located at above-mentioned scope, fingerprint visibility and the having concurrently of durability of cured film become possibility.
The content of the composition (C) in composition of the present invention, at composition of the present invention not containing when aftermentioned composition (D), relative to total 100 weight portion of composition (A) and (B), preferably in the scope of 0.1 ~ 30 weight portion, more preferably in the scope of 0.1 ~ 20 weight portion, preferred in the scope of 1 ~ 15 weight portion further.On the other hand, when composition of the present invention contains aftermentioned composition (D), relative to total 100 weight portion of composition (A), (B) and (D), preferably in the scope of 0.1 ~ 30 weight portion, more preferably in the scope of 0.1 ~ 20 weight portion, preferred in the scope of 1 ~ 15 weight portion further.If composition (C) containing quantity not sufficient 0.1 weight portion, then when forming cured film, likely can not get sufficient fingerprint visibility, during more than 30 weight portion, probably the hardness of cured film declines.
(D) inorganic oxide particle
Composition of the present invention can containing inorganic oxide particle as composition (D).Composition (D) is as long as using the particle of inorganic oxide as principal component, be just not particularly limited.Composition (D) be expected to be improved laminated film hardness, reduce curling effect.
Composition (D), can go out send choice for use from the viewpoint of the transparency of the cured film of the solidification compound obtained, tone.
As the preferred example of composition (D), can enumerate the inorganic oxide of at least one element that is selected from silicon, aluminium, zirconium, titanium, zinc, germanium, indium, tin, antimony and the cerium particle as principal component, specifically, the particle of silica, aluminium oxide, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide etc. can be enumerated.Wherein, from the viewpoint of high rigidity, the particle of preferred silica, aluminium oxide, zirconia and antimony oxide.These particles may be used singly or in combination of two or more.In addition, composition (D), preferably uses as powder shaped or solvent dispersion sol.When using as solvent dispersion sol, as decentralized medium, be not particularly limited with water or organic solvent etc., but from the compatibility of other composition, dispersed viewpoint, the preferred organic solvent of decentralized medium.As such organic solvent, such as, the alcohols such as methyl alcohol, ethanol, isopropyl alcohol, butanols, octanol can be enumerated; The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone; The ester classes such as ethyl acetate, butyl acetate, ethyl lactate, gamma-butyrolacton, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate; The ethers such as glycol monoethyl ether, diethylene glycol monobutyl ether; The arenes such as benzene,toluene,xylene; The amide-types such as dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE.Wherein, particular methanol, isopropyl alcohol, butanols, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl acetate, butyl acetate, toluene, dimethylbenzene.
The number average particle diameter of composition (D) is preferably in the scope of 1 ~ 200nm, more preferably in the scope of 5 ~ 150nm, preferred in the scope of 10 ~ 100nm further.Number average particle diameter is when above-mentioned scope, and transparency when making solidfied material and getting both of hardness become possibility.The number average particle diameter of inorganic oxide particle (D), refers to the mean value measuring 20 particle diameters obtained by carrying out observing with transmission electron microscope.In addition, in order to improve the dispersiveness of particle, various surfactant, amine can be added.
As silicon oxide particles (such as, silicon dioxide granule) commercial goods, such as, as colloidal silica, Nissan Chemical Industries (strain) methyl alcohol silicon dioxide gel processed, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL etc. can be enumerated.In addition as powder silica, Japanese Aerosil (strain) Aerosil130 processed, Aerosil300, Aerosil380, AerosilTT600, AerosilOX50, Asahi Glass (strain) SILDEXH31 processed, H32, H51, H52, H121, H122, Japanese SILICA industry (strain) E220A, E220, FUJISILYSIA processed (strain) SILYSIA470 processed, NHTechno (strain) SGFLAKE processed etc. can be enumerated.
In addition, as the aqueous dispersion product of aluminium oxide, Nissan Chemical Industries (strain) oxygenerating Alumina gel-100 ,-200 ,-520 can be enumerated; As the isopropyl alcohol dispersion product of aluminium oxide, Osaka, Sumitomo cement (strain) AS-150I processed can be enumerated; As the toluene dispersion product of aluminium oxide, Osaka, Sumitomo cement (strain) AS-150T processed can be enumerated; As zirconic toluene dispersion product, Osaka, Sumitomo cement (strain) HXU-110JC processed can be enumerated; As the aqueous dispersion product of zinc antimonates powder, Nissan Chemical Industries (strain) CELNAX processed can be enumerated; As powder and the solvent dispersion product of aluminium oxide, titanium oxide, tin oxide, indium oxide, zinc oxide etc., C.I. can be enumerated and change into (strain) NanoTec processed; As the aqueous dispersion colloidal sol of antimony doped tin oxide, stone can be enumerated and originate in industry (strain) SN-100D processed; As ito powder, the product that Mitsubishi Material (strain) makes can be enumerated; As cerium oxide aqueous dispersions, many wooden chemistries (strain) NEEDRAL processed etc. can be enumerated.
The shape of composition (D) is spherical, hollow form, cellular, bar-shaped, tabular, threadiness or amorphous, preferably spherical.The specific area (adopting the BET specific surface area determination method using nitrogen) of composition (D), preferably 10 ~ 1000m
2/ g, more preferably 100 ~ 500m
2/ g.
Composition (D) is preferably with there being the organic compound (Db) of polymerism unsaturated group and hydrolysable silanes base (following in molecule, be called " particle modified dose (Db) ") carry out surface-treated inorganic oxide particle (hereinafter referred to as " reactive particles (Dc) ").Relative to reactive particles (Dc), will not carry out surface-treated composition (D) with particle modified dose (Db) and be called " oxide particle (Da) ".Reactive particles (Dc) because covalent bond can be formed with adhesive ingredients, so can obtain marresistance, heat resistance and transparent in more excellent cured film.
Particle modified dose (Db)
Particle modified dose (Db) used in the present invention, as long as there is the organic compound of polymerism unsaturated group and hydrolysable silanes base, is just not particularly limited.As polymerism unsaturated group, the ethylenic unsaturated group such as vinyl, (methyl) acryloyl group can be enumerated.Should illustrate, hydrolysable silanes base refers to that energy and water react and generates the group of silanol base (Si-OH), such as, the group being combined with the alkoxyls such as more than 1 methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, aryloxy group, acetoxyl group, amino, halogen atom on silicon can be enumerated.
Particle modified dose (Db) used in the present invention, can use the commercially available products such as gamma-methyl allyl acyloxypropyl trimethoxysilane, such as, can be used in the compound recorded in International Publication publication WO97/12942 publication.
The preparation of reactive particles (Dc)
Reactive particles (Dc) is by mixing, making it hydrolysis, make both combine and obtain by particle modified dose (Db) and oxide particle (Da).Organic polymer compositions in the reactive particles (Dc) obtained and the hydrolysate of hydrolysable silanes and the ratio of condensation product, usually, weight when burning completely in atmosphere as making the dry powder of reactive particles (Dc) reduces the steady state value of %, can by such as obtaining from the thermogravimetry of room temperature to usual 800 DEG C in atmosphere.
Using reactive particles (Dc) (total of oxide particle (Da) and particle modified dose (Db)) as 100 % by weight time, particle modified dose (Db) is preferably 0.01 ~ 40 % by weight to the binding capacity of oxide particle (Da), be more preferably 0.1 ~ 30 % by weight, be particularly preferably 1 ~ 20 % by weight.By the amount of particle modified dose (Db) reacting with oxide particle (Da) is controlled in above-mentioned scope, the dispersiveness of the reactive particles (Dc) in composition can be improved, can expect to improve the transparency of gained solidfied material, the effect of marresistance.
Composition (D) in the present composition is any composition, but content when adding, no matter it is oxide particle (Da) or reactive particles (Dc), using composition (A), (B) and (D) total amount as 100 weight portion time, all be preferably 10 ~ 80 weight portions, more preferably in the scope of 20 ~ 80 weight portions.Composition (D) containing quantity not sufficient 10 weight portion time, probably can not show and coordinate the effect brought, during more than 80 weight portion, the marresistance probably as hard conating declines.
Should illustrate, the content of inorganic oxide particle (D), refers to the content of solid constituent, and when inorganic oxide particle (D) uses with the form of solvent dispersion sol, its content does not comprise the amount of solvent.
(E) number average particle diameter is the organic or inorganic particle of 0.5 ~ 10 μm
Composition (E) in the present composition is the composition carrying out as required coordinating, and the cured film that imparting obtains is with anti-glare.As composition (E), the organic or inorganic particle of number average particle diameter within the scope of 0.5 ~ 10 μm can be used.Should illustrate, the number average particle diameter of the particle of composition (E) is the value adopting dynamic light scattering determination to obtain.
The material of the inorganic particulate that can use as composition (E), can enumerate silica, aluminium oxide, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide etc., preferred silica.
The material of the organic filler that can use as composition (E), can enumerate acrylic resin, polystyrene, polyethylene, styrene-ethylene copolymers etc.
The content of composition (E) coordinated as required in the compositions of the present invention, relative to the composition (A) of 100 weight portions, the total amount of (B) and (D), preferably in the scope of 0.1 ~ 30 weight portion, more preferably in the scope of 0.5 ~ 20 weight portion.The content of composition (E) can change according to the design of antiglare film.
(F) organic solvent
Composition of the present invention, in order to regulate the thickness of film, can carry out diluting rear use with organic solvent.Such as, viscosity when using as hard coat material, normally 0.1 ~ 50000mPa second/25 DEG C, be preferably 0.5 ~ 10000mPa second/25 DEG C.
As organic solvent (F), such as, the alcohols such as methyl alcohol, ethanol, isopropyl alcohol, butanols, octanol can be enumerated; The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone; The ester classes such as ethyl acetate, butyl acetate, ethyl lactate, gamma-butyrolacton, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate; The ethers such as glycol monoethyl ether, diethylene glycol monobutyl ether; The arenes such as benzene,toluene,xylene; The amide-types etc. such as dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE.
The use level of the organic solvent (F) used as required in the compositions of the present invention, using remove the composition of solvent total amount as 100 weight portion time, preferably in the scope of 50 ~ 10000 weight portions.The use level of solvent, can consider coating film thickness, the viscosity etc. of composition suitably determines.
(G) other additive
In the present compositions, in addition to the aforementioned ingredients, the free-radical polymerised compound, antioxidant, ultra-violet absorber, levelling agent etc. beyond (A), (C) and (Dc) composition can be added as required.
Composition of the present invention, can, by adding above-mentioned (A) ~ (C) composition and optional composition from (D) ~ (G) composition as required respectively, then carry out mixing under room temperature or heating condition preparing.Specifically, the mixer such as blender, kneading machine, ball mill, three rollers can be used to be prepared.Just, when mixing in a heated condition, preferably start below the temperature of decomposing at polymerization initiator or polymerism unsaturated group and carry out.
As the present composition that aforesaid operations obtains, it can be made to solidify with radioactive ray (light).
II. cured film
Cured film of the present invention, can by be coated on described composition of the present invention on various hyaline membrane base material and to make it solidify and obtain.Specifically, can obtaining in the following way: coating composition, when containing the volatile ingredients such as (F) organic solvent preferably after 0 ~ 200 DEG C makes these compositions volatilization removing, being cured process with radioactive ray, thus obtained.
To the coating process of base material, common coating process can be enumerated, such as dip-coating, spraying, flow coat, showering, roller coat, spin coating, brushing etc.The thickness of the film in these coatings, is the thickness after drying, solidification, is preferably 0.1 ~ 400 μm, is more preferably 0.5 ~ 200 μm.
As radioactive ray, as long as can it be made at short notice to solidify after coating composition, be just not particularly limited, but be easy to the reasons such as acquisition, preferred ultraviolet, electron beam due to irradiation unit.As ultraviolet radiographic source, mercury lamp, halogen lamp, laser etc. can be used, and as the radiographic source of electron beam, the thermionic mode etc. utilizing and produced by commercially available tungsten filament can be used.When using ultraviolet or electron beam as radioactive ray, preferred ultraviolet irradiation light quantity is 0.01 ~ 10J/cm
2, be more preferably 0.1 ~ 2J/cm
2.In addition, the illuminate condition of preferred electron beam is, accelerating potential is 10 ~ 300kV, electron density is 0.02 ~ 0.30mA/cm
2, electron beam irradiation amount is 1 ~ 10Mrad.
III. hyaline membrane base material
As the hyaline membrane base material becoming coating object, be not particularly limited, such as, the plastic foil of Merlon, polymethacrylates, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin etc. can be enumerated.The thickness of plastic foil is not particularly limited, but from easy-to-handle viewpoint, preferably 40 μm ~ 5mm.The hyaline membrane base material that the present invention uses, preferably has the transmitance of more than 85% in the complete wavelength range of wavelength 400 ~ 800nm.
IV. laminated film
Laminated film of the present invention has cured film at least one face of hyaline membrane base material, and described cured film uses the solidification compound containing following compositions (A) ~ (C) to be formed.Laminated film of the present invention, cured film of the present invention, can by be coated on the composition of the invention described above on various hyaline membrane base material and to make it solidify and obtain.The transparent base be applicable to, the lamination method of cured film are the same with described in cured film one.Laminated film of the present invention, because have the high transparency and hardness, and soil resistance, particularly fingerprint erasing property and fingerprint visibility, humidity resistance, dry heat resistance are also excellent, so be applicable as the surface protection film etc. of various display unit.
Laminated film of the present invention, because fingerprint visibility and fingerprint are wiped the excellent in te pins of durability such as property excellence, excellent scratch resistance, dry heat resistance and humidity resistance and then are had high transparent, so be particularly suitable for the antireflection film etc. of liquid crystal display cells, touch panel, plastic optical members etc.In addition; solidification compound of the present invention; because fingerprint visibility and the fingerprint erasing property excellent in te pins of durability such as excellence, excellent scratch resistance, dry heat resistance and humidity resistance can be obtained and then there is the cured film of high transparent, thus be suitable as the record disks such as CD, DVD, MO, plastic optical members, touch panel, film-type liquid crystal elements, plastic containers, as the flooring material, wall material, synthetic marble etc. of building built-in material for preventing damage (scratch) or antipollution protective finish material.
[embodiment]
Below, specifically describe the present invention further by embodiment, but the present invention is not by any restriction of these embodiments.Should illustrate, unless otherwise specified, " % " represents % by weight, and " part " represents weight portion.
Synthesis example 1: compound (C-1)
(in formula, R
1represent the group that hydrogen atom or following formula represent independently of one another.a+b+c＝7。)
2 are added to the there-necked flask installing agitator, 6-BHT (Ji Fu FineChemical Inc., YOSHINOXBHT) 0.013g, pentaerythritol triacrylate (Xin Zhong village chemistry system, NKESTERA-TMM-3LM-N) 14.82g, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexylisocyanate (Zhu Hua BayerUrethane Inc., DesmodurI) 6.66g, and methyl iso-butyl ketone (MIBK) (Mitsubishi Chemical Ind's system) 50.00g, add tin dilaurate dioctyl tin (common drug company system wherein, KS-1200-A) after 0.044g, stirred at ambient temperature 2 hours.Then, polyoxyethylene hardened castor oil (Japanese Emulsion Inc., EMALEXHC-7 is added; HLB value is 6) 28.47g.Reactant liquor be warming up to 60 DEG C thus obtain the compound (C-1) that HLB value is 4.In addition, because acrylation almost carries out quantitatively, so come the hydroxyl of deterministic compound (C-1) and the mol ratio of (methyl) acryloyl group by addition.
Synthesis example 2 ~ 7
Use except the compound shown in table 1 except according to the ratio shown in table 1, operate in the same manner as synthesis example 1, obtain compound (C-2) ~ (C-7).
Compound (C-2)
(in formula, R
2represent the group that hydrogen atom or following formula represent independently of one another.a+b+c＝7。)
Compound (C-3), (C-4) and (C-5)
(in formula, R
3represent the group that hydrogen atom or following formula represent independently of one another.a+b+c＝7。)
Compound (C-6)
Compound (C-7)
Relatively synthesis example 1: compound (G-1)
(in formula, R
1represent the group that following formula represents.a+b+c＝7。)
Use except the compound shown in table 1 except according to the ratio shown in table 1, operate in the same manner as synthesis example 1, obtain compound (G-1).
The HLB value of compound (C-1) ~ (C-7) is shown in table 1.In addition, by the hydroxyl of compound (C-1) ~ (C-7) and compound (G-1): the mol ratio of (methyl) acryloyl group is shown in table 1.
[table 1]
The compound recorded in table 1 is as described below.
HC-7:EMALEXHC-7, has the polyoxyethylene hardened castor oil of the structure that following formula represents, Japanese Emulsion Inc..
EMALEXHC-7 (a+b+c=7), HLB value: 6
GWIS-100EX:EMALEXGWIS-100EX, glyceryl isostearate (compound that following formula represents), Japanese Emulsion Inc., molecular weight: 358.56, HLB value: 6
TDI: Mitsui Chemicals polyurethane Inc., TOLDY-100, toluene di-isocyanate(TDI) (compound that following formula represents), molecular weight: 174.16
IPDI:DesmodurI, Zhu Hua BayerUrethane Inc., IPDI (compound that following formula represents), molecular weight: 222.29
KarenzMOI: Showa electrician Inc., methylacryoyloxyethyl isocyanates (compound that following formula represents), molecular weight: 155.15
Chemical company of PETA:NKESTERA-TMM-3LM-N, Xin Zhong village system, pentaerythritol triacrylate (compound that following formula represents), molecular weight: 298.3
HEA: Osaka organic chemistry Inc., hydroxy ethyl methacrylate (compound that following formula represents), molecular weight: 116.11
H
2C＝CH-COO-CH
2CH
2-OH
BHT:YOSHINOXBHT, Ji Fu FineChemical Inc., BHT (compound that following formula represents), molecular weight: 220
KS-1200-A: common drug company system, tin dilaurate dioctyl tin
MIBK: methyl iso-butyl ketone (MIBK)
Production Example 1
The synthesis of particle modified dose (Db)
In dry air, to by mercaptopropyi trimethoxy silane 221 parts, dibutyl tin laurate 1 part of solution formed, after dripping IPDI 222 parts at 50 DEG C with 1 hour while stirring, add thermal agitation 3 hours at 70 DEG C.Dripped Xin Zhong village chemistry NKESTERA-TMM-3LM-N processed at 30 DEG C wherein with 1 hour (to be made up of pentaerythritol triacrylate 60 % by weight and tetramethylol methane tetraacrylate 40 % by weight.Wherein, relevant with reaction is only the pentaerythritol triacrylate having hydroxyl.) after 549 parts, add thermal agitation 10 hours at 60 DEG C, thus obtain particle modified dose (Db) containing polymerism unsaturated group.Analyze the amount of the residual isocyanate in product with FT-IR, result is less than 0.1%, and display reaction finishes substantially quantitatively.The infrared absorption spectroscopy of product, the characteristic absorption peak 2550cm of the sulfydryl in raw material
-1and the characteristic absorption peak 2260cm of isocyanate material compound
-1disappear, the characteristic peak 1660cm of newly observed urea key and S (C=O) NH-base
-1and the characteristic peak 1720cm of acryloyl group
-1, this indicates to have simultaneously modifies alkoxy silane generation as the acryloyl group of polymerism unsaturated group and the acryloyl group of-S (C=O) NH-, urea key.As mentioned above, particle modified dose (Db) can be obtained and add up to 773 parts and tetramethylol methane tetraacrylate 220 parts.
Production Example 2
As the manufacture of the silicon dioxide granule (I) of reactive particles (Dc)
By composition 2.98 parts (containing particle modified dose (Db) 2.32 parts), silicon dioxide granule dispersion liquid (Da) (solid constituent: 35 % by weight that Production Example 1 li manufactures, MEK-ST-L, number average particle diameter 0.08 μm, Nissan Chemical Industries (strain) is made) 89.90 parts, after the mixed liquor of ion exchange water 0.12 part and p-hydroxybenzene monomethyl ether 0.01 part stirs 4 hours at 60 DEG C, add original acid A ester 1.36 parts, and then add thermal agitation at the same temperature 1 hour, thus obtain reactive particles dispersion liquid.Be placed in after in aluminium dish by this dispersion liquid weighing 2g, drying 1 hour on the heating plate of 175 DEG C, carry out weighing and obtain solid component content, result is 36.5 % by weight.In addition, after dispersion liquid weighing 2g is placed in magnetic crucible, on the heating plate of 80 DEG C predrying 30 minutes, in the Muffle furnace of 750 DEG C, calcination was after 1 hour, is obtained the inorganic content in solid constituent by inorganic residues, and result is 95 % by weight.Solid component content is concentrated into 70 % by weight, obtained silicon dioxide granule (I) dispersion liquid.It is 80nm that silicon dioxide granule (I) the transmission electron microscope method obtained measures the number average particle diameter obtained.
Production Example 3
As the manufacture of the silicon dioxide granule (S) of reactive particles (Dc)
By gamma-methyl allyl acyloxypropyl trimethoxysilane (eastern beautiful DOW CORNING organosilicon Inc. SZ6030) 3.14 parts, silicon dioxide granule dispersion liquid (Da) (solid constituent: 35 % by weight, MEK-ST-L, number average particle diameter 0.08 μm, Nissan Chemical Industries (strain) are made) 89.90 parts, after the mixed liquor of ion exchange water 0.12 part and p-hydroxybenzene monomethyl ether 0.01 part stirs 4 hours at 60 DEG C, add original acid A ester 1.36 parts, and then add thermal agitation at the same temperature 1 hour, thus obtain reactive particles dispersion liquid.Be placed in after in aluminium dish by this dispersion liquid weighing 2g, drying 1 hour on the heating plate of 175 DEG C, carry out weighing and obtain solid component content, result is 36.5 % by weight.In addition, after dispersion liquid weighing 2g is placed in magnetic crucible, on the heating plate of 80 DEG C predrying 30 minutes, in the Muffle furnace of 750 DEG C, calcination was after 1 hour, is obtained the inorganic content in solid constituent by inorganic residues, and result is 93 % by weight.It is 50nm that silicon dioxide granule (S) the transmission electron microscope method obtained measures the number average particle diameter obtained.
Embodiment 1
Add dipentaerythritol acrylate (Nippon Kayaku K. K's system: KAYARADDPHA) 94.0 weight portions, Photoepolymerizationinitiater initiater (make: compound (C-2) 6.5 weight portion IRGACURE184) manufactured in 6.0 weight portions and synthesis example 1 by Ciba (strain), methyl iso-butyl ketone (MIBK) is added in the mode that solid component concentration is 50 % by weight, stir, obtain solidification compound 1.
Embodiment 2
Use except each composition by the use level shown in table 2 except as solid constituent, and embodiment 1 similarly operates, manufacture solidification compound 2.
Embodiment 3
Add manufacture in Production Example 2 silicon dioxide granule (I) (be 78.1 weight portions as solid constituent amount), dipentaerythritol acrylate (Nippon Kayaku K. K's system: KAYARADDPHA) 20.1 weight portions, Photoepolymerizationinitiater initiater (make: IRGACURE184) compound (C-2) 4.2 weight portion that manufactures of 1.8 weight portions and synthesis example 2 li by Ciba (strain), methyl iso-butyl ketone (MIBK) is added in the mode that solid component concentration is 50 % by weight, stir, obtain solidification compound.
Embodiment 4 ~ 11 and comparative example 1 ~ 7
Use except each composition except by the use level shown in table 2, and embodiment 3 similarly operates, manufacture each solidification compound.
The manufacture > of < cured film
Using wire bar applicator (12mil) each solidification compound obtained in above-described embodiment and comparative example to be applied to thickness is on the TAC film of 80 μm.80 DEG C of dryings after 2 minutes, use high-pressure sodium lamp with exposure 1.0J/cm under air
2intensity illumination ultraviolet carry out photocuring thus make each cured film.
The evaluation of physical property > of < cured film
Evaluate the following characteristic of the cured film made by aforesaid operations, the obtained results are shown in table 2.
(1) mensuration of mist degree (%)
Use colored haze meter (COLORHAZEMETER, Suga testing machine (strain) system), measure the mist degree (%) of cured film according to JISK7105.
(2) total light penetration (Tt; Mensuration %)
Use colored haze meter (Suga testing machine (strain) system), measure total light penetration (%) of cured film according to JISK7105.
(3) fingerprint visibility
By the back side blacking of film, fingerprint is made to be attached to film surface.Afterwards, from the vertical direction visualization on film surface, evaluate according to following metewand.
Zero: be difficult to see fingerprint
×: be clear that fingerprint
(4) fingerprint erasing property test
By the back side blacking of film, fingerprint is made to be attached to film surface.Afterwards, wipe fingerprint with paper handkerchief, evaluate according to following metewand.
Zero: erasable.
△: difficult erasing.
×: can not wipe.
(5) solvent resistance
Have the cloth wipe surfaces of liquid ガ ラ ス Network Le one (trade name: Johnson Co., Ltd. system) with infiltration after, carry out above-mentioned (4) fingerprint erasing test, evaluate according to following metewand.
Zero: erasable.
△: difficult erasing.
×: can not wipe.
(6) marresistance (woolliness of resistance to steel wire)
Steel wool (BonstarNo.0000, Japanese steel wool (strain) are made) is installed on Gakushin-TypeRubbingTester (AB-301, TESTER industry (strain) system), with load 500g repeatedly 10 cured film of nuzzling up surface or with the surface of load 900g 10 cured film of nuzzling up repeatedly, whether produce scar with visual confirmation on the surface of this cured film, evaluate according to following metewand.
A: do not produce scar in cured film.
B: produce trickle scar in cured film.
C: produce several scar in cured film.
D: produce a large amount of scar in cured film.
E: produce scar in whole of cured film.
(7) mensuration of contact angle (°)
Use the contact angle meter DropMaster500 of consonance surface chemistry Co., Ltd., measure the contact angle of cured film to water and hexadecane according to JIS6768.
(8) humidity resistance
Cured film is put into the constant temperature and humidity cabinet of 60 DEG C × 90%RH, leave standstill after 500 hours, carry out evaluation of physical property, evaluate according to following metewand.
Zero: with preliminary phase than not change.
×: change with preliminary phase ratio.
(9) dry heat resistance
Cured film is put into 80 DEG C of thermostats, leave standstill after 500 hours, carry out evaluation of physical property, evaluate according to following metewand.
Zero: with preliminary phase than not change.
×: change with preliminary phase ratio.
[table 2]
The compound recorded in table 2 is as described below.
Silicon dioxide granule (I): the reactive particles (Dc) of synthesis in Production Example 2
Silicon dioxide granule (S): the reactive particles (Dc) of synthesis in Production Example 3
Dipentaerythritol acrylate: Nippon Kayaku K. K's system, KAYARADDPHA
Pentaerythritol triacrylate: KCC of Xin Zhong village system, NKESTERA-TMM-3LM-N
Irg.184: Ciba (strain) system, Photoepolymerizationinitiater initiater
Each compound of composition (C) is synthesized by synthesis example 1 ~ 7
EMALEXHC-10, HC-5: there is the polyoxyethylene hardened castor oil of the structure that following formula represents, Japanese Emulsion Inc..
EMALEXHC-5 (a+b+c=5), HLB value: 5
EMALEXHC-10 (a+b+c=10), HLB value: 10
EMALEXPEIS-3EX:EMALEXPEIS-3EX, polyethyleneglycol isostearate, Japanese Emu1sion Inc., HLB value: 7
C
17H
35COOCH
2CH
2(OCH
2CH
2)
n-1OH
EMALEXGWIS-100EX: after being recorded in table 1
Compound (G-1): the compound comparing synthesis in synthesis example 1
SilaplaneFM0711:CHISSO Inc., methacryl-modified polysiloxanes (compound that following formula represents)
As can be known from the results of Table 2, the transparency of the cured film of embodiment, fingerprint visibility, fingerprint erasing property, solvent resistance, marresistance, humidity resistance, dry heat resistance are all excellent.
On the other hand, all hydroxyls have all been carried out the comparative example 7 of (methyl) acrylated fatty acid ester system surfactant by known use, and marresistance, humidity resistance and dry heat resistance are poor.
Embodiment 12
Solidification compound 100 weight portion (solid constituent 50 weight portion) manufactured in embodiment 3 adds acrylic resin particle (Soken Chemical Company system, " MX-180 ", average grain diameter 1.9 μm) 1 weight portion, the mode being 25% with solid component concentration adds methyl iso-butyl ketone (MIBK) 103 weight portion, stir, obtain solidification compound 12.Using wire bar applicator (3mil) solidification compound 12 to be coated on thickness is on the TAC film of 80 μm.80 DEG C of dryings after 2 minutes, use high-pressure sodium lamp with exposure 1.0J/cm under air
2intensity illumination ultraviolet carry out photocuring thus make cured film.By the back side blacking of the film with gained cured film, make fluorescent lamp reflect the shape that but can not confirm fluorescent lamp, thus confirm that there is anti-glare.In addition, make fingerprint be attached to this film, but with visual very difficult confirmation fingerprint, can easily be wiped by paper handkerchief.
Utilizability in industry
Composition of the present invention can provide the excellent in te pins of durability such as fingerprint visibility, fingerprint erasing property excellence, marresistance, humidity resistance and dry heat resistance, have the cured film of high transparent simultaneously.
Composition of the present invention is useful as the solidification compound for the formation of hard conating.
Make the cured film that composition of the present invention solidifies, because fingerprint visibility and fingerprint erasing property excellence, marresistance, dry heat resistance, humidity resistance is excellent, and then there is high transparent, so as CD, DVD, the record disks such as MO, plastic optical members, touch panel, film-type liquid crystal elements, plastic containers, as the flooring material of building built-in material, wall material, synthetic marbles etc. damage (scratch) or antipollution protective finish material for preventing, or as film-type liquid crystal elements, touch panel, the antireflection films of plastic optical members etc. etc. are useful especially.
Claims (15)
1. a laminated film, it has cured film at least one face of hyaline membrane base material, and described cured film uses the solidification compound containing following compositions A ~ C to be formed,
A: multifunctional (methyl) acrylate monomer
B: Photoepolymerizationinitiater initiater
C: that there is hydroxyl and (methyl) acryloyl group, that HLB value is in 2 ~ 15 scopes fatty acid ester system surfactant,
HLB value is obtained by following calculating formula,
HLB＝7+11.71g(M
W/M
0)
Wherein M
wthe molecular weight of hydrophilic group, M
0it is the molecular weight of lipophilic group.
2. laminated film as claimed in claim 1, wherein, the HLB value of described composition C is in the scope of 2 ~ 12.
3. laminated film as claimed in claim 1 or 2, wherein, the mol ratio of the hydroxyl that described composition C has and (methyl) acryloyl group is at hydroxyl: (methyl) acryloyl group=1: in the scope of 6 ~ 3: 1.
4. laminated film as claimed in claim 1 or 2, wherein, the carbon number that described composition C has straight-chain or a branched is 1 valency or the divalent alkyl of 8 ~ 30.
5. laminated film as claimed in claim 1 or 2; wherein, described composition C is by making hydroxyl but not having the hydroxyl that the fatty acid ester system surfactant of (methyl) acryloyl group has and the compound having the compound of (methyl) acryloyl group to react and obtain.
6. laminated film as claimed in claim 5, wherein, according to claim 5 have the compound of (methyl) acryloyl group to be the compound having NCO and (methyl) acryloyl group.
7. laminated film as claimed in claim 1 or 2, wherein, further containing components D: number average particle diameter is the inorganic oxide particle of 1 ~ 200nm.
8. laminated film as claimed in claim 7, wherein, described components D has carried out surface-treated inorganic oxide particle with the organic compound containing polymerism unsaturated group and hydrolysable silanes base in molecule.
9. laminated film as claimed in claim 1 or 2, wherein, described cured film is not containing components D: number average particle diameter is the film of the inorganic oxide particle of 1 ~ 200nm, and during using the total amount of described composition A and B as 100 weight portion, described composition C is in the scope of 0.1 ~ 30 weight portion.
10. laminated film as claimed in claim 7, wherein, during using the total amount of described composition A, B and D as 100 weight portion, described composition C is in the scope of 0.1 ~ 30 weight portion.
11. laminated films as claimed in claim 8, wherein, during using the total amount of described composition A, B and D as 100 weight portion, described composition C is in the scope of 0.1 ~ 30 weight portion.
12. laminated films as claimed in claim 1 or 2, wherein, further containing composition E: number average particle diameter is the organic or inorganic particle of 0.5 ~ 10 μm.
13. 1 kinds of solidification compounds, it contains following compositions A ~ C,
A: multifunctional (methyl) acrylate monomer
B: Photoepolymerizationinitiater initiater
C: that there is hydroxyl and (methyl) acryloyl group, that HLB value is in 2 ~ 15 scopes fatty acid ester system surfactant,
HLB value is obtained by following calculating formula,
HLB＝7+11.71g(M
W/M
0)
Wherein M
wthe molecular weight of hydrophilic group, M
0it is the molecular weight of lipophilic group.
14. solidification compounds as claimed in claim 13, it is for the formation of hard conating.
15. 1 kinds of cured film, it forms by making the solidification compound described in claim 13 or 14 solidify.
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