CN1922266A

CN1922266A - Curable liquid resin composition and method for producing multilayer body using same

Info

Publication number: CN1922266A
Application number: CN 200580005350
Authority: CN
Inventors: 下村宏臣; 土居本光伸; 铃木康伸; 山村哲也; 江利山祐一; 田边隆喜; 高濑英明
Original assignee: JSR Corp
Current assignee: Arakawa Chemical Industries Ltd
Priority date: 2004-03-18
Filing date: 2005-03-16
Publication date: 2007-02-28
Anticipated expiration: 2025-03-16
Also published as: CN100513477C; CN1918229A; CN100432140C; CN1922265A

Abstract

Disclosed is a method for producing a multilayer body having a base, and a conductive layer (antistatic layer) and multilayer structure arranged on the base. The method for producing a multilayer body is characterized in that the conductive layer (antistatic layer) is formed by vapor-phase polymerization of at least one monomer selected from the group consisting of pyrrole, thiophene, furan, selenophene, 3,4-ethylenedioxythiophene and derivatives of those, then a liquid curable resin composition containing a fluorine-containing polymer (A), a thermosetting compound (B), a curing catalyst (C), metal oxide particles (D), a highly volatile solvent (E-1) and a less volatile solvent (E-2) is applied thereto for forming a coating and the solvent is evaporated from the coating, so that this single coating is formed into two or more layers. Also disclosed is a multilayer body produced by such a method.

Description

Curable liquid resin composition and used the manufacture method of its multilayer body

Technical field

The present invention relates to curable liquid resin composition and used the manufacture method of its multilayer body, particularly can be by 1 film curable liquid resin composition that forms the layer more than 2 and the manufacture method of having used its multilayer body.

Background technology

Now, be accompanied by multimedia development, in various display unit, embodied multiple progress.And, in the middle of various display unit, be the display unit that to use without at center particularly to carry usefulness, it is important that the raising of its visuognosis degree becomes gradually, even demander requires also more easily to watch in large-scale display device, and this item still becomes a technical task.

In the past, a method as the visuognosis degree that improves display unit, adopted the method that on the substrate of display unit, covers the antireflection film that constitutes by low-index material, as the method that forms antireflection film, for example known method that the film that utilizes vapour deposition method formation fluorine cpd is arranged.Yet, in recent years, be the center with the liquid crystal indicator, require with low-cost and also can form the technology of antireflection film for large-scale display unit.But,, on large-area substrate, be difficult to form uniform antireflection film, and, therefore be difficult to reduce cost owing to need vacuum unit with high-level efficiency utilizing under the situation of vapour deposition method.

Based on this kind situation, studying following method, that is, the fluorine type polymer that specific refractory power is low is dissolved in the organic solvent and modulates aqueous composition, forms antireflection film by the surface of it being coated substrate.For example, scheme (for example with reference to patent documentation 1 and patent documentation 2) at the surface coated fluorinated alkyl silane of substrate was proposed.In addition, the method (for example with reference to patent documentation 3) that coating has the fluorine type polymer of specific structure was proposed.

Patent documentation 1: the spy opens clear 61-40845 communique

Patent documentation 2: special fair 6-98703 communique

Patent documentation 3: the spy opens flat 6-115023 communique

These antireflection films in the past mostly are the multilayer body of the layer that formed different refractivity on base material, antistatic backing, hard coat etc.In the manufacture method in the past, carry out the operation of each layer of separate application on base material repeatedly.

Summary of the invention

The present invention is that background is finished with aforesaid situation, and its purpose is, the curable liquid resin composition that can make two-layer continuously arbitrarily above layer such as low-index layer and high refractive index layer effectively is provided.

Other purpose of the present invention is, provides the transparency high, big and have a cured film of good scuff resistance and dust wiping with the connecting airtight property of base material.

Other purpose of the present invention is, provides and to utilize the multilayer body that it obtains by the manufacture method of 1 that gets by the coating composition multilayer body that forms the layer more than 2 of filming.

Other purpose of the present invention is, the manufacture method of the multilayer body with good anti-reflection effect is provided and utilizes the multilayer body that it obtains.

Other purpose of the present invention is, provides with the manufacture method of the multilayer body that connecting airtight property is good, scuff resistance is high of base material and utilizes the multilayer body that it obtains.

In order to reach described purpose, the inventor etc. have carried out further investigation repeatedly, provide the curable liquid resin composition of cured film to scheme to film with two-layer above layer structure by one, and illustrate and be separated into two-layer above mechanism, discovery by will having particular configuration fluoropolymer and specific metal oxide particle and following solvent promptly, according to being divided into to the solvability of the fluoropolymer that has hydroxyl at intramolecularly and to the dispersion stabilization of metal oxide particle and by relative velocity of evaporation in 2 kinds the solvent species, the solvent of selecting respectively more than a kind and forming, then be coated with this curable liquid resin composition and one film and just be separated into multilayer, in addition, kind by selective solvent, other condition, no matter be which kind of metal oxide particle then, can both be separated into multilayer, thereby finish the present invention.

According to the present invention, provide following curable liquid resin composition etc.

1. a curable liquid resin composition is characterized in that, comprises following compositions (A)～(F):

(A) has the fluoropolymer of hydroxyl at intramolecularly

(B) number average bead diameter below the 100nm and specific refractory power the metal oxide particle more than a kind or 2 kinds more than 1.50 (below be called " (B) metal oxide particle ")

(C) (A) had the high solvent more than a kind or 2 kinds of the solvability of fluoropolymer of hydroxyl (below be called " (C) fast solvent flashing ") at intramolecularly

(D) to the dispersion stabilization of (B) metal oxide particle high and with (C) fast solvent flashing be the solvent more than a kind or 2 kinds (below be called " (D) slow-evaporating solvent ") of intermiscibility

(E) solidified nature compound

(F) hot acid propellant,

And (C) the relative velocity of evaporation of fast solvent flashing is greater than the relative velocity of evaporation of (D) slow-evaporating solvent.

2. according to the curable liquid resin composition described in 1, it is characterized in that,

(C) fast solvent flashing is the solvent a kind or 2 kind or more low to the dispersion stabilization of (B) metal oxide particle, and (D) slow-evaporating solvent is the low solvent more than a kind or 2 kinds of solvability that (A) is had the fluoropolymer of hydroxyl at intramolecularly.

3. according to the curable liquid resin composition described in 1 or 2, it is characterized in that,

Described (B) metal oxide particle is to be selected from titanium oxide, zirconium white, to contain antimony oxidation tin, stanniferous Indium sesquioxide, aluminum oxide, cerium oxide, zinc oxide, to contain aluminum zinc oxide, stannic oxide, contain antimony zinc oxide and one or more the metal oxide that contains in indium zinc oxide, the phosphorous stannic oxide is the particle of principal constituent.

4. according to the curable liquid resin composition described in 3, it is characterized in that,

(B) metal oxide particle is for being the particle of principal constituent with the titanium oxide.

5. according to any described curable liquid resin composition in 1～4, it is characterized in that,

(B) metal oxide particle is the metal oxide particle with multi-ply construction.

6. a cured film is characterized in that, is any described curable liquid resin composition in 1～5 is solidified and to get, and has the multi-ply construction more than 2 layers.

7. according to the cured film described in 6, it is characterized in that,

Each layer that constitutes described multi-ply construction is the layer that exists to high-density of (B) metal oxide particle or (B) the non-existent in fact layer of metal oxide particle, wherein the layer that exists to high-density for (B) metal oxide particle of one deck at least.

8. the manufacture method of a cured film is characterized in that, has: make any described curable liquid resin composition solidified operation in 1～5 by heating and/or shining radioactive rays.

9. the manufacture method of a multilayer body is the manufacture method with multilayer body of base material and the multi-ply construction on it, it is characterized in that,

On the described base material or be formed on the layer on the base material, any described curable liquid resin composition and forming is filmed in the coating 1～5,

By from this 1 is filmed with solvent evaporation, form the layer more than 2.

10. according to the manufacture method of the multilayer body described in 9, it is characterized in that, each layer of described layer more than 2 is layer or the non-existent in fact layer of metal oxide particle that metal oxide particle exists to high-density, at least 1 layer of layer that exists to high-density for metal oxide particle.

11. the manufacture method according to the multilayer body described in 10 is characterized in that, described layer more than 2 is 2 layers.

12. the manufacture method according to any described multilayer body in 9～11 is characterized in that, and then by heating described layer more than 2 is solidified.

13. the manufacture method according to any described multilayer body in 9～12 is characterized in that multilayer body is the optics parts.

14. the manufacture method according to any described multilayer body in 9～12 is characterized in that multilayer body is an antireflection film.

15. the manufacture method according to the multilayer body described in 11 is characterized in that,

Described multilayer body on base material from beginning near the base material side to major general's high refractive index layer and low-index layer antireflection film with this sequential cascade, 2 layers described in 11 are made of high refractive index layer and low-index layer.

16. the manufacture method according to the multilayer body described in 15 is characterized in that,

The specific refractory power of low-index layer under 589nm is 1.20～1.55,

The specific refractory power of high refractive index layer under 589nm is 1.50～2.20, is higher than the specific refractory power of low-index layer.

17. the manufacture method according to the multilayer body described in 11 is characterized in that,

Described multilayer body is for index layer, high refractive index layer and low-index layer are with the antireflection film of this sequential cascade to the major general from beginning near the base material side on base material, and 2 layers described in 11 are made of high refractive index layer and low-index layer.

18. the manufacture method according to the multilayer body described in 17 is characterized in that,

The specific refractory power of low-index layer under 589nm is 1.20～1.55,

The middle specific refractory power of index layer under 589nm is 1.50～1.90, is higher than the specific refractory power of low-index layer,

The specific refractory power of high refractive index layer under 589nm is 1.51～2.20, the specific refractory power of index layer in being higher than.

19. the manufacture method according to any described multilayer body in 15～18 is characterized in that, also forms hard coat and/or antistatic backing on base material.

20. multilayer body of utilizing the manufacture method manufacturing of any described multilayer body in 9～19.

Curable liquid resin composition of the present invention obtains to have the cured film of multi-ply constructions such as high refractive index layer and low-index layer owing to can film by one, therefore the manufacturing process of cured film can be simplified.

Curable liquid resin composition of the present invention forms the layer more than 2 owing to being filmed by 1 that coating composition gets, therefore the manufacturing process with multilayer body of multi-ply construction can be simplified.

In addition, changing partially, can improve the scuff resistance of cured film or multilayer body by making metal oxide particle.

Curable liquid resin composition of the present invention can advantageously be applied in the formation of optical materials such as antireflection film, permselective membrane strainer especially, in addition, can also utilize the high situation of fluorine content, be applied to rightly on being required the base material of weathering resistance brushing with material, weather film with material, apply with in material and other materials.And the connecting airtight property of this cured film and base material is good, and the scuff resistance height can provide good anti-reflection effect.So cured film of the present invention or multilayer body are extremely useful as antireflection film,, can improve its visuognosis degree by being applied in the various display unit.

Description of drawings

Figure 1A is the figure that is used for explanation " by 1 layer more than 2 of filming and forming ".

Figure 1B is the figure that is used for explanation " by 1 layer more than 2 of filming and forming ".

Fig. 1 C is the figure that is used for explanation " by 1 layer more than 2 of filming and forming ".

Fig. 1 D is the figure that is used for explanation " by 1 layer more than 2 of filming and forming ".

Fig. 1 E is the figure that is used for explanation " by 1 layer more than 2 of filming and forming ".

Fig. 2 is the sectional view as the antireflection film of an embodiment of the invention.

Fig. 3 is as other the sectional view of antireflection film of embodiment of the present invention.

Fig. 4 is as other the sectional view of antireflection film of embodiment of the present invention.

Fig. 5 is as other the sectional view of antireflection film of embodiment of the present invention.

Fig. 6 is as other the sectional view of antireflection film of embodiment of the present invention.

Fig. 7 is as other the sectional view of antireflection film of embodiment of the present invention.

Fig. 8 is as other the sectional view of antireflection film of embodiment of the present invention.

Fig. 9 is as other the sectional view of antireflection film of embodiment of the present invention.

Figure 10 is as other the sectional view of antireflection film of embodiment of the present invention.

Figure 11 is the electron micrograph of the notion of expression two separate, each state that does not separate (localized agglomeration) and massiveness.

Embodiment

Below the present invention is divided into curable liquid resin composition, cured film and multilayer body and describes in detail.

1. curable liquid resin composition

Curable liquid resin composition of the present invention contains following compositions (A)～(F):

(A) has the fluoropolymer of hydroxyl at intramolecularly

(E) solidified nature compound

(F) hot acid propellant

Below, these compositions are described respectively.

(A) has the fluoropolymer of hydroxyl at intramolecularly

So-called fluoropolymer is the polymkeric substance that has carbon-fluorine bond at intramolecularly, and more than the preferred 30 quality % of its fluorine content, the number-average molecular weight that gets with polystyrene conversion of utilizing gel permeation chromatography to obtain in addition is preferred more than 5000.Here, fluorine content is the value of utilizing the alizarin complexon method to measure, and number-average molecular weight is the value when having used tetrahydrofuran (THF) as the expansion solvent.

As the example of fluoropolymer used among the present invention, be the fluoropolymer that has hydroxyl at intramolecularly (below be called " hydroxyl fluoropolymer ").As the preferred example of hydroxyl fluoropolymer, can enumerate the monomeric structural unit of hydroxyl formed, had polysiloxane segment in main chain the material that derives from that contains 10 moles of %～50 mole %.This hydroxyl fluoropolymer is the olefin polymer that has in main chain with the polysiloxane segment of following general formula (1) expression, and the ratio of this polysiloxane segment in the fluoropolymer is generally 0.1～20 mole of %.

[changing 1]

In the formula, R ¹And R ²Both can be the same or different expression hydrogen atom, alkyl, halogenated alkyl or aryl.

In addition, the preferred fluorine content of hydroxyl fluoropolymer is more than the 30 quality %, more preferably 40～60 quality %, in addition, utilize that gel permeation chromatography obtains with polystyrene conversion number-average molecular weight preferably more than 5000, more preferably 10000～500000.

Described hydroxyl fluoropolymer can by make (a) Fluorine containing olefine compound (below be called " (a) composition ".), (b) contain can with the monomeric compound of the hydroxyl of this (a) composition copolymerization (below be called " (b) composition ".) and (c) contain the azo-group polysiloxane compound (below be called " (c) composition ".) and (d) reactive emulsifier of using as required (below be called " (d) composition ".) and/or (e) can and obtain with monomeric compound reaction beyond (b) composition of described (a) composition copolymerization.

As the Fluorine containing olefine compound that becomes (a) composition, the unsaturated double-bond with at least 1 polymerizability, the compound of at least 1 fluorine atom be can enumerate,, (1) tetrafluoroethylene, R 1216,3 for example can be enumerated as its concrete example, 3, fluoroolefin classes such as 3-trifluoro propene; (2) perfluor (alkyl vinyl ether) class or perfluor (alkoxyalkyl vinyl ether) class; (3) perfluor (methylvinylether), perfluor (ethyl vinyl ether), perfluor (propyl vinyl ether), perfluor (butyl vinyl ether), perfluor perfluor (alkyl vinyl ether) classes such as (IVE); (4) perfluor perfluor (alkoxyalkyl vinyl ether) classes such as (propoxy-propyl vinyl ethers); Other compound.These compounds both can use separately, also can use simultaneously more than 2 kinds.In the middle of the above compound, preferred especially R 1216, perfluor (alkyl vinyl ether) or perfluor (alkoxyalkyl vinyl ether) more preferably are used in combination them.

As the hydroxyl monomeric compound that becomes (b) composition, for example can enumerate hydroxyl vinyl ethers such as (1) 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxy butyl vinyl ether, 3-hydroxy butyl vinyl ether, 5-hydroxyl amyl group vinyl ether, 6-hydroxyl hexyl vinyl ether; (2) hydroxyl allyl ether series such as 2-hydroxyethyl allyl ether, 4-hydroxyl butyl allyl ethers, allylin; (3) vinyl carbinol; (4) hydroxyethyl (methyl) acrylate; Other compound.These compounds both can use separately, also can use simultaneously more than 2 kinds.Preferred hydroxyl alkyl vinyl ethers.

Contain the azo-group polysiloxane compound as what become (c) composition, for containing with the azo-group of-easy thermo-cracking that N=N-represents and having compound, for example for utilizing the spy to open the compound that the method described in the flat 6-93100 communique is made with the polysiloxane segment of described general formula (1) expression.As the concrete example of (c) composition, can enumerate compound with following general formula (2) expression.

[changing 2]

In the formula, y=10～500, z=1～50.

Described (a) composition, (b) composition and (c) the preferred combination of composition for example be: (1) fluoroolefin/hydroxyl alkyl vinyl ether/polydimethylsiloxane unit, (2) fluoroolefin/perfluor (alkyl vinyl ether)/hydroxyl alkyl vinyl ether/polydimethylsiloxane unit, (3) fluoroolefin/perfluor (alkoxyalkyl vinyl ether)/hydroxyl alkyl vinyl ether/polydimethylsiloxane unit, (4) fluoroolefin/perfluor (alkyl vinyl ether)/hydroxyl alkyl vinyl ether/polydimethylsiloxane unit, (5) fluoroolefin/perfluor (alkoxyalkyl vinyl ether)/hydroxyl alkyl vinyl ether/polydimethylsiloxane unit.

In this hydroxyl fluoropolymer, derive from preferred 20～70 moles of % of structural unit of (a) composition, more preferably 25～65 moles of %, preferred especially 30～60 moles of %.If the ratio of structural unit that derives from (a) composition is less than 20 moles of %, then the fluorine content in the fluoropolymer of gained is very few easily, and the cured article of the curable liquid resin composition of gained is difficult to become the enough low material of specific refractory power.On the other hand, when the ratio of the structural unit that derives from (a) composition surpasses 70 moles of %, then the solvability of the fluoropolymer of gained in organic solvent reduces significantly, and the curable liquid resin composition of gained becomes, and the transparency reaches and the little material of connecting airtight property of base material.

In the hydroxyl fluoropolymer, derive from preferred 10～50 moles of % of structural unit of (b) composition.Better is, lower value more preferably surpasses 20 moles of % at 13 moles more than the %, and at 21 moles more than the %, in addition, preferred higher limit is 45 moles below the %, more preferably 35 moles below the %.The fluoropolymer that contains this kind (b) composition of specified amount by use constitutes curable liquid resin composition, in its cured article, just can realize good scuff resistance and dust wiping.On the other hand, if the ratio of structural unit that derives from (b) composition is less than 10 moles of %, then the solvability of fluoropolymer in organic solvent will variation, when surpassing 50 moles of %, then the cured article that is obtained by curable liquid resin composition will become the material of the deterioration in optical properties of the transparency and antiradar reflectivity.

(c) the azo-group polysiloxane compound that contains of composition itself is hot free-radical initiator, has effect as polymerization starter in the polyreaction that is used for obtaining fluoropolymer, yet also can use other free-radical initiator simultaneously.The ratio of the structural unit of deriving from the fluoropolymer (c) composition is, preferred 0.1～20 mole of % of polysiloxane segment with general formula (1) expression, more preferably 0.1～15 mole of %, preferred especially 0.1～10 mole of %, the ratio of preferred more especially 0.1～5 mole of %.Ratio at the polysiloxane segment of representing with general formula (1) surpasses under the situation of 20 moles of %, and the fluoropolymer of gained becomes the material of transparency difference, under situation about using as the coating agent, is easy to generate depression etc. when being coated with in addition.

Except described (a)～(c) composition,, preferably reactive emulsifier is used as monomer component as (d) composition.Be somebody's turn to do (d) composition by using, under the situation that the hydroxyl fluoropolymer is used as the coating agent, just can obtain good coating and levelling property.As this reactive emulsifier, especially preferably use the nonionic reactive emulsifier.As the concrete example of nonionic reactive emulsifier, for example can enumerate compound with following general formula (3) or general formula (4) expression.

[changing 3]

In the formula, n is 1～20, and m and s represent repeating unit, m=0～4, s=3～50.

[changing 4]

In the formula, m and s are identical with general formula (3).R ³Be to can be a straight chain shape or a catenate alkyl, preferred carbon number is 1～40 alkyl.

In the hydroxyl fluoropolymer, derive from preferred 0～10 mole of % of ratio of the structural unit of (d) composition, more preferably 0.1～5 mole of %, preferred especially 0.1～1 mole of %.When this ratio surpassed 10 moles of %, then because the curable liquid resin composition of gained becomes the material that has cementability, therefore becoming was difficult to handle, and under situation about using as the coating agent, wet fastness reduces.

As (e) composition can with the monomeric compound beyond (b) composition of (a) composition copolymerization, can enumerate alkyl vinyl ether or cycloalkyl vinyl ethers such as (1) methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE, tert-butyl vinyl ether, n-amyl group vinyl ether, n-hexyl vinyl ether, n-octyl group vinyl ether, n-dodecyl vinyl, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; (2) vinyl esters of carboxylic acids classes such as vinyl acetate, propionate, vinyl butyrate, valeric acid vinyl acetate, vinyl caproate, tertiary ethylene carbonate, stearic acid vinyl ester; (3) (methyl) esters of acrylic acids such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-(n-propoxy-) ethyl ester; (4) conducts such as (methyl) vinylformic acid, Ba Dousuan, toxilic acid, fumaric acid, methylene-succinic acid contain the monomeric compound etc. of carboxyl but do not contain the compound of hydroxyl.The preferred alkyl vinyl ether.

In the hydroxyl fluoropolymer, derive from preferred 0～70 mole of % of ratio of the structural unit of (e) composition, more preferably 5～35 moles of %.When this ratio surpassed 70 moles of %, then because the curable liquid resin composition of gained becomes the material that has cementability, therefore becoming was difficult to handle, and under situation about using as the coating agent, wet fastness reduces.

(a) composition when containing (d) composition, (b) composition, (c) composition, (d) composition and (e) the preferred combination of composition is as follows.

(1) fluoroolefin/hydroxyl vinyl ether/polydimethylsiloxane unit/nonionic reactive emulsifier/alkyl vinyl ether, (2) fluoroolefin/perfluor (alkyl vinyl ether)/hydroxyl vinyl ether/polydimethylsiloxane unit/nonionic reactive emulsifier/alkyl vinyl ether, (3) fluoroolefin/perfluor (alkoxyalkyl vinyl ether)/hydroxyl vinyl ether/polydimethylsiloxane unit/nonionic reactive emulsifier/alkyl vinyl ether, (4) fluoroolefin/perfluor (alkyl vinyl ether)/hydroxyl vinyl ether/polydimethylsiloxane unit/nonionic reactive emulsifier/alkyl vinyl ether, (5) fluoroolefin/perfluor (alkoxyalkyl vinyl ether)/hydroxyl vinyl ether/polydimethylsiloxane unit/nonionic reactive emulsifier/alkyl vinyl ether.

As can with the free radical polymerization initiator of (c) composition and usefulness, for example can enumerate peroxidation two acyl classes such as (1) acetyl peroxide, benzoyl peroxide; (2) ketone peroxide class such as methyl ethyl ketone peroxide, pimelinketone superoxide; (3) hydroperoxide type such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide; (4) dialkyl classes such as peroxidation two-tertiary butyl, dicumyl peroxide, dilauroyl peroxide base; (5) peroxyesters such as t-butyl peroxy-acetate, t-butylperoxy pivarate; (6) azo based compound class such as azobis isobutyronitrile, the two isovaleronitriles of azo; (7) persulfuric acid salts such as ammonium persulphate, Sodium Persulfate, Potassium Persulphate; Other compound.

As the concrete example beyond the described free radical polymerization initiator, for example can enumerate the perfluoro ethyl iodide hydrochlorate, the perfluoro propyl iodate, the perfluoro butyl iodate, (perfluoro butyl) iodoethane hydrochlorate, the perfluoro hexyl iodate, 2-(perfluoro hexyl) iodoethane hydrochlorate, perfluor heptyl iodate, the perfluoro capryl iodate, 2-(perfluoro capryl) iodoethane hydrochlorate, perfluor iododecane hydrochlorate, 2-(perfluor decyl) iodoethane hydrochlorate, seven fluoro-2-iodopropane, perfluor-3-methyl butyl iodate, perfluor-5-methyl hexyl iodide hydrochlorate, 2-(perfluor-5-methyl hexyl) iodoethane hydrochlorate, perfluor-7-Methyl Octyl iodate, 2-(perfluor-7-Methyl Octyl) iodoethane hydrochlorate, perfluor-9-methyl iododecane hydrochlorate, 2-(perfluor-9-methyl decyl) iodoethane hydrochlorate, 2,2,3,3-tetrafluoro propyl iodide hydrochlorate, 1H, 1H, 5H-octafluoro amyl iodide hydrochlorate, 1H, 1H, 7H-ten difluoro heptyl iodates, tetrafluoro-1, the 2-ethylidene periodide, octafluoro-1,4-two butyl iodides, 12 fluoro-, 1,6-two iodohexanes etc. contain the iodine fluorochemical.Containing the iodine fluorochemical can use separately, also can and use with described organo-peroxide, azo compound or persulphate in addition.

As the polymerization methods that is used to make the hydroxyl fluoropolymer, can use for any of emulsion polymerization, suspension polymerization, mass polymerization or solution polymerization process of using free radical polymerization initiator, as converging operation, can from the operation of intermittent type, semi continuous or continous way etc., select suitable mode.

The polyreaction that is used for obtaining the hydroxyl fluoropolymer is preferably carried out at the solvent system that has used solvent.Here, as preferred organic, for example can enumerate ester classes such as (1) vinyl acetic monomer, N-BUTYL ACETATE, Iso Butyl Acetate, isobutyl acetate, oxytol acetate; (2) ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone; (3) ring-type such as tetrahydrofuran (THF), dioxane ethers; (4) N, amidess such as dinethylformamide, N,N-dimethylacetamide; (5) toluene, dimethylbenzene etc. are aromatic hydrocarbon based; Other solvent.In addition, as required, alcohols, aliphatic hydrocarbon etc. can also be mixed and use.

For the hydroxyl fluoropolymer that obtains as mentioned above, though also the reaction soln that utilizes its polyreaction to obtain directly can be used as curable liquid resin composition sometimes, also can carry out appropriate postprocessing to polymeric reaction solution.As this aftertreatment, for example can carry out with in the insoluble solvent that polymeric reaction solution is added drop-wise to this hydroxyl fluoropolymer that constitutes by alcohol etc. and to make method of purification that this hydroxyl fluoropolymer solidifies be that the general redeposition of representative is handled, then, be dissolved in the solvent by multipolymer, just can modulate the solution of hydroxyl fluoropolymer the solid shape of gained.In addition, also the solution of having removed residual monomer from polymeric reaction solution directly can be used as the solution of hydroxyl fluoropolymer.

Solid formation in the curable liquid resin composition of the present invention divides the cooperation ratio of (A) hydroxyl fluoropolymer among the 100 quality % to be generally 5～70 quality %, preferred 10～50 quality %, and like this, it is good that the transparency of cured film will become.

(B) metal oxide particle

Among the present invention used (B) metal oxide particle be number average bead diameter below the 100nm and specific refractory power at the metal oxide particle of (wavelength 550nm) more than 1.50.When number average bead diameter surpasses 100nm, then have and be difficult to make metal oxide particle dispersive situation equably.In addition, the easy sedimentation of metal oxide particle, thus the situation that lacks storage stability is arranged.In addition, the situation that the transparency reduces or turbidity (Haze value) rises that also has the cured film of gained.

Number average bead diameter is 10～80nm more preferably, further preferred 20～50nm.

And, " number average bead diameter " is the number average bead diameter of measuring with electron microscope method, being primary particle size when metal oxide particle condenses, when metal oxide particle is not sphere (for example needle-like ATO etc.), is major diameter (lengthwise) and the mean value of minor axis (growing crosswise).In addition, particle shape be bar-shaped (refer to aspect ratio surpass 1 and in the shape below 10) situation under, with minor axis as particle diameter.

As metal oxide particle, can preferably use to be selected from titanium oxide, zirconium white (zirconia), to contain antimony oxidation tin, stanniferous Indium sesquioxide, aluminum oxide (alumina), cerium oxide, zinc oxide, to contain aluminum zinc oxide, stannic oxide, contain antimony zinc oxide and contain one or more metal oxide in indium zinc oxide, the phosphorous stannic oxide as the particle of principal constituent.

Here, also can use metal oxide particle with described one or more the covered metal oxide particle of metal oxide beyond this metal oxide with multi-ply construction.As the concrete example of metal oxide particle, can enumerate silicon-dioxide capping oxidation titanium particle, aluminum oxide capping oxidation titanium particle, zirconium white capping oxidation titanium particle, aluminum oxide, zirconium white capping oxidation titanium particle etc. with multi-ply construction.In the middle of this kind metal oxide particle, preferred especially is the particle of principal constituent or aluminum oxide, zirconium white capping oxidation titanium particle with the titanium oxide.

Have the metal oxide particle of multi-ply construction by use, photocatalytic activity that just can the inhibited oxidation titanium can suppress the decomposition of cured article.Consequently, can obtain specific refractory power height, cured film that photostabilization is good.

In addition, contain antimony oxidation tin particle (ATO) etc., can give static electricity resistance cured film by use.Under this situation, as described later,, therefore can realize effective static electricity resistance and the good transparency two aspects simultaneously with more a spot of particle addition because the ATO particle takes place changing partially.

As being the particle of principal constituent with the titanium oxide, can use material known, no matter its shape is that hollow-particle, porous granule, core-shell-type particle etc. can in addition.In addition, be not limited to spherical, also can be bar-shaped (refer to aspect ratio surpass 1 and in the shape below 10) or atypic particle, preferably bar-shaped.Utilize in the scope of the preferred 1～100nm of number average bead diameter that electron microscope method tries to achieve.

In addition, dispersion agent preferably water or organic solvent.As organic solvent, can enumerate alcohols such as methyl alcohol, Virahol, ethylene glycol, butanols, ethylene glycol ether; Ketone such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK); Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; Amidess such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone; Ester classes such as vinyl acetic monomer, N-BUTYL ACETATE, gamma-butyrolactone; Tetrahydrofuran (THF), 1, organic solvents such as ethers such as 4-dioxane, in the middle of them, preferred alcohols and ketone.These organic solvents can be separately use as dispersion agent, perhaps also can mix more than 2 kinds and use as dispersion agent.

As being the commercially available prod of the particle of principal constituent with the titanium oxide, for example can enumerating テイカ (strain) system or シ-アイ and change into the product of (strain) etc.

Solid formation with respect to curable liquid resin composition divides the cooperation ratio of (B) metal oxide particle of 100 quality % to be generally 10～90 quality %, preferred 20～80 quality %.

(C) fast solvent flashing

Contained (C) fast solvent flashing is the high solvent more than a kind or 2 kinds of solvability to described (A) hydroxyl fluoropolymer in the curable liquid resin composition of the present invention.Here so-called solvability height to the hydroxyl fluoropolymer is meant, (A) hydroxyl fluoropolymer is added in each solvent, makes it to reach 50 quality %, when at room temperature having stirred 8 hours, visually reaches uniform solution.In addition, (C) the relative velocity of evaporation of fast solvent flashing need be greater than the relative velocity of evaporation of (D) described later slow-evaporating solvent.Here, so-called " velocity of evaporation relatively " is meant, the required time is the relative value of the velocity of evaporation of benchmark when evaporating 90 quality % with N-BUTYL ACETATE, shown in the content of being put down in writing among details such as the TECHNIQUES OF CHEMISTRY VOL.2 ORGANIC SOLVENTS PysicalProperties and methods of purification 4th ed. (Interscience Publishers, Inc.1986 page62).In addition, (C) fast solvent flashing preferably the dispersion stabilization for described (B) metal oxide particle is low.(C) fast solvent flashing because of relative velocity of evaporation greater than (D), solvability height to (A) hydroxyl fluoropolymer, and the dispersion stabilization to (B) metal oxide particle is low, thereby curable liquid resin composition of the present invention is being coated on the base material, make solvent (C) and (D) in the evaporating course, (B) metal oxide particle is being changed partially.

As the solvent that is suitable for use as (C) fast solvent flashing among the present invention, be relative velocity of evaporation roughly at the solvent more than 1.7, specifically, can enumerate methyl ethyl ketone (MEK; Relatively velocity of evaporation is 3.8), Virahol (IPA; 1.7), methyl iso-butyl ketone (MIBK) (MIBK; Relatively velocity of evaporation is 1.6), Methyl amyl ketone (MAK; 0.3), acetone, methyl propyl ketone etc.

(D) slow-evaporating solvent

Contained (D) slow-evaporating solvent is the high solvent more than a kind or 2 kinds of dispersion stabilization to described (B) metal oxide particle in the curable liquid resin composition of the present invention.Here, so-called dispersion stabilization height for (B) metal oxide particle is meant, sheet glass be impregnated in (B) metal oxide particle dispersion liquid, (B) metal oxide particle is attached on the glass wall, under the sheet glass that this has been adhered to (B) metal oxide particle impregnated in situation in each solvent, with visual observation, (B) metal oxide particle disperses in this solvent equably.In addition, (D) slow-evaporating solvent preferably the solvability to described (A) hydroxyl fluoropolymer is low.

As the solvent that is suitable for use as (D) slow-evaporating solvent among the present invention, be relative velocity of evaporation roughly at the solvent below 1.7, specifically, can enumerate methyl alcohol (relatively velocity of evaporation be 2.1), Virahol (IPA; 1.7), n-butanols (n-BuOH; 0.5), tert-butanols, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, ethyl cellosolve, propyl cellosolve, ethylene glycol butyl ether etc.

Among the present invention used (C) fast solvent flashing and/or (D) slow-evaporating solvent can directly use used solvent in the manufacturing of described (A) hydroxyl fluoropolymer usually.

Among the present invention used (C) fast solvent flashing and (D) slow-evaporating solvent need intermiscibility.Intermiscibility is in the concrete formation of composition of the present invention, as long as (C) fast solvent flashing is arranged and (D) intermiscibility that slow-evaporating solvent can isolating degree is promptly enough.

Here, selected solvent is actually corresponding to (C) fast solvent flashing used among the present invention or (D) in the slow-evaporating solvent which, between selecteed a plurality of solvent species comparatively speaking.In addition, relatively velocity of evaporation is that 1.7 Virahol is equivalent to (C) fast solvent flashing and (D) any one of slow-evaporating solvent, yet also can and only use as (D) slow-evaporating solvent with other (C) fast solvent flashing combination.

In addition, in curable liquid resin composition of the present invention, for coating that improves composition etc. and other purpose, solvent can cooperate described (C) fast solvent flashing and (D) solvent beyond the slow-evaporating solvent.As the solvent that cooperates with this kind purpose, can enumerate ester classes such as ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, vinyl acetic monomer, N-BUTYL ACETATE.In addition, in the solution of curable liquid resin composition of the present invention, can and use the solvent that can not dissolve fluoropolymer, for example poor solvents such as water, alcohols, ethers in the scope that fluoropolymer is not separated out.Like this, the solution of this fluoropolymer just becomes the solution with good keeping quality and ideal coating sometimes.As this kind poor solvent, can enumerate ethanol, Virahol, tert-butanols, ethyl cellosolve, ethylene glycol butyl ether etc.

With respect to the solvent in the curable liquid resin composition (comprising that (C) composition reaches (D) composition) composition total amount 100 mass parts in addition, the total amount of solvent (C) and solvent (D) is used 300～5000 mass parts usually, preferred 300～4000 mass parts, more preferably 300～3000 mass parts.The proportioning (mass ratio) of solvent (C) and solvent (D) can for arbitrary value in 1: 99～99: 1 scope.

(E) solidified nature compound

(E) the solidified nature compound is by heating etc. and the composition of solidified nature is given in polymerization to the application's composition.

As the solidified nature compound, for example can enumerate various hydroxy-containing compounds and other compounds such as various aminocompounds, tetramethylolmethane, polyphenol, ethylene glycol.

Be used as aminocompound that the solidified nature compound uses and be add up to contain more than 2 can with the amino of hydroxyl reaction in described (A) hydroxyl fluoropolymer, the for example any one party of hydroxyalkyl amino and alkoxyalkyl amino or both sides' compound, specifically, for example can enumerate melamine compounds, urea compound, benzo guanamine compounds, glycoluril compounds etc.

In general the melamine compounds is to be used as compound with the skeleton that combines nitrogen-atoms on triazine ring and known, specifically, can enumerate melamine, alkylation melamine, methylol melamine, alkoxylate methylmelamine etc., however preferred methylol and any one party of alkoxylate methyl or both sides' the compound that has more than 2 that in 1 molecule, add up to.Specifically, the methylolation melamine, alkoxylate methylmelamine or their derivative that melamine and formaldehyde are reacted under alkaline condition and get, particularly from can curable liquid resin composition, obtain good storage stability aspect and obtain good reactive aspect and consider preferred alkoxylate methylmelamine.For being used as methylolation melamine and the not special restriction of alkoxylate methylmelamine that the solidified nature compound uses, for example also can using the various arborescens things that the method put down in writing in the document " plastic material lecture [8] urea melamine resin " (daily magazine industry newspaper office) obtains.

In addition, as urea compound, except urea, can also enumerate poly-methylolation urea and as the alkoxylate methyl urea of its derivative, methylolation uronic acid lactone and alkoxylate methyl uronic acid lactone etc. with uronic acid lactone (urone) ring.In addition, for compounds such as urea derivatives, can use the various arborescens things of being put down in writing in the described document.

Solid formation in the curable liquid resin composition divides the cooperation ratio of solidified nature compound contained among the 100 quality % to be generally 3～70 quality %, preferred 3～50 quality %, the more preferably scope of 5～30 quality %.When the usage quantity of solidified nature compound is very few, then have the insufficient situation of weather resistance of the film that the curable liquid resin composition by gained forms, when breaking away from the scope of 3～70 quality %, then with the reaction of fluoropolymer in be difficult to avoid gelation, the situation that has cured article to become fragile.

(A) the hydroxyl fluoropolymer for example can add the solidified nature compound with (E) reaction of solidified nature compound in the solution of the organic solvent that has dissolved the hydroxyl fluoropolymer, carries out when utilizing the heating of reasonable time, stirring etc. to make the reaction system homogenizing.Preferred 30～150 ℃ scope of Heating temperature that is used for this reaction, more preferably 50～120 ℃ scope.If this Heating temperature is less than 30 ℃, then Fan Ying carrying out is very slow, when surpassing 150 ℃, then except required reaction, also produce the crosslinking reaction that causes by the reaction between methylol in the solidified nature compound or the alkoxylate methyl, generate gel, therefore not ideal enough.The carrying out of reaction can carry out quantitative affirmation by methylol or alkoxylate methyl being utilized quantitative methods such as infrared spectroscopic analysis, perhaps lysed polymkeric substance utilized reprecipitation method to reclaim, and carries out quantitative affirmation by measuring its increasing amount.

In addition, in the reaction of (A) hydroxyl fluoropolymer and (E) solidified nature compound, organic solvent for example preferably uses the solvent identical with organic solvent used in the manufacturing of hydroxyl fluoropolymer.Among the present invention, both the reaction soln of the hydroxyl fluoropolymer that so obtains and solidified nature compound directly can be used as the solution of curable liquid resin composition, also can after having cooperated various additives as required, use.

(F) hot acid propellant

Can be matched with hot acid propellant in the curable liquid resin composition of the present invention and be heating such as filming of this curable liquid resin composition under the solidified situation, can be heated the material of improvement of terms for more gentle condition.As the concrete example of this hot acid propellant, for example can enumerate various aromatic carboxylic acids and salt, alkyl benzene sulphonate (ABS) and ammonium salt thereof, various metal-salt, phosphoric acid or organic acid phosphoric acid ester etc. such as various aliphatic carboxylic acids such as various aliphatic sulfonics and salt thereof, citric acid, acetic acid, toxilic acid and salt thereof, phenylformic acid, phthalic acid.

Solid formation in the curable liquid resin composition divides the usage ratio of this contained among 100 quality % hot acid propellant to be generally 0.01～10 quality %, preferred 0.1～5 quality %.Because when this ratio is excessive, the storage stability variation of curable liquid resin composition then, thereby not ideal enough.

(G) additive

In curable liquid resin composition of the present invention, for the coating that improves this curable liquid resin composition and the rerum natura of the film after solidifying, or give photosensitivity etc. to filming, for example can make it to contain: have various additives such as the various polymkeric substance of hydroxyl or stabilization agents such as tinting materials such as monomer, pigment or dyestuff, antiaging agent or UV light absorber, photosensitivity acid-producing agent, tensio-active agent, polymerization retarder.Particularly, for the hardness of improving formed cured film and the purpose of weather resistance, preferably add light acid propellant, preferred especially use can not reduce the transparency after the curing of curable liquid resin composition, and is dissolved in the material in its solution equably.

(1) has the polymkeric substance of hydroxyl

As the polymkeric substance with hydroxyl that can be matched with in the curable liquid resin composition of the present invention, for example can enumerate hydroxyl co-polymerized monomer copolymerization such as hydroxyethyl (methyl) acrylate and polymkeric substance, as novolac resin or soluble phenolic resin and known resin etc. with phenol skeleton.

(2) tinting material such as pigment or dyestuff

As the tinting material that can be matched with in the curable liquid resin composition of the present invention, for example can enumerate body pigments such as (1) aluminium is white, clay, barium carbonate, barium sulfate; (2) mineral dye such as zinc white, white lead, chrome yellow, red lead, ultramarine, Prussian blue, titanium oxide, zinc chromate, red iron oxide, carbon black; (3) pigment dyestuffs such as bright fuchsin 6B, permanent red 6B, permanent red R, diarylide yellow, phthalocyanine blue, phthalocyanine green; (4) basic color such as fuchsin, rhodamine; (5) geranine, direct directly pigment such as orange; (6) matching stain such as Luo Seling, rice tower Neil Huang; Other tinting material.

(iii) stabilization agent such as antiaging agent, UV light absorber

As antiaging agent, the UV light absorber that can be matched with in the curable liquid resin composition of the present invention, can use known material.

Concrete example as protective agent, for example can enumerate two-tert.-butyl phenol, pyrogallol, benzoquinones, Resorcinol, methylenum coeruleum, tert-butyl catechol, single-benzyl ether, methyl hydroquinone, amyl group quinone, pentyloxy Resorcinol, normal-butyl phenol, phenol, Resorcinol list propyl ether, 4,4 '-[1-[4-(1-(4-hydroxy phenyl)-1-methylethyl) phenyl] ethylidene] biphenol, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane, phenylbenzene amine, phenylenediamine, thiodiphenylamine, mercaptobenzimidazole etc.

In addition, concrete example as UV light absorber, for example can utilize with the salol is the salicylic acid UV light absorber of representative, dihydroxy benaophenonel, 2-hydroxyl-benzophenone UV light absorber such as 4-methoxy benzophenone, the benzotriazole category UV light absorber, the UV light absorber that the various additives that are used as plastics such as cyanoacrylate UV light absorber use.

(4) photosensitivity acid-producing agent

The photosensitivity acid-producing agent that can be matched with in the curable liquid resin composition of the present invention is to give photosensitivity to filming of this curable liquid resin composition, for example can pass through the irradiates light isoradial, and this is filmed the material of photocuring takes place.As this photosensitivity acid-producing agent, for example can enumerate various salt such as (1) salt compounded of iodine, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt; (2) beta-ketoester, β-sulphonyl sulfone and their sulphones such as α-azo-compound; (3) sulfonic acid esterses such as alkyl sulfonic ester, haloalkyl sulphonate, aromatic yl sulphonate, imino-sulphonate; (4) the sulfone imide compound class of representing with following general formula (9); (5) the diazomethane compounds of representing with following general formula (5); Other compound.

[changing 5]

In the formula, X represents the base of divalents such as alkylidene group, arylidene, alkylene oxide group, R ⁴The base of 1 valencys such as expression alkyl, aryl, halogen substituted alkyl, halogen substituted aryl.

[changing 6]

In the formula, R ⁵And R ⁶Both can be the same mutually, also can be different, the base of 1 valencys such as expression alkyl, aryl, halogen substituted alkyl, halogen substituted aryl.

The photosensitivity acid-producing agent both can use separately, and also two or more kinds may be used in addition, can also and use with described hot acid propellant.Solid formation in the curable liquid resin composition divides the usage ratio of the photosensitivity acid-producing agent in 100 mass parts preferred 0～20 mass parts, more preferably 0.1～10 mass parts.Because when this ratio is excessive, then solidify the film strength variation, the transparency also reduces, and is therefore not ideal enough.

(5) tensio-active agent

In curable liquid resin composition of the present invention, for the purpose of the coating that improves this curable liquid resin composition, can also the matching surface promoting agent.As this tensio-active agent, can use known material, specifically, for example can use various anionic species tensio-active agents, cationic tensio-active agent, nonionic class tensio-active agent, especially preferably use the cationic tensio-active agent, because it makes cured film have good intensity, and has the good optical characteristic.In addition, preferred quaternary ammonium salt, wherein when using the polyethers quaternary ammonium salt, owing to the dust wiping is further improved, thereby preferred especially.As the cationic tensio-active agent that belongs to the polyethers quaternary ammonium salt, can enumerate the system アデカコ of Asahi Electro-Chemical Co. Ltd-Le CC-15, CC-36, CC-42 etc.The usage ratio of tensio-active agent is, with respect to curable liquid resin composition 100 quality %, below the preferred 5 quality %.

(6) polymerization retarder

As the thermal polymerization inhibitor that can be matched with in the curable liquid resin composition of the present invention, for example can enumerate pyrogallol, benzoquinones, Resorcinol, methylenum coeruleum, tert-butyl catechol, single-benzyl ether, methyl hydroquinone, amyl group quinone, pentyloxy Resorcinol, normal-butyl phenol, phenol, Resorcinol list propyl ether, 4,4 '-[1-[4-(1-(4-hydroxy phenyl)-1-methylethyl) phenyl] ethylidene] biphenol, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane etc.This thermal polymerization inhibitor preferably uses below the 5 quality % with respect to curable liquid resin composition 100 quality %.

(7) (C) and (D) solvent beyond the composition

In curable liquid resin composition of the present invention, can add (C) and reach (D) composition solvent in addition.This kind solvent types and use level can freely be selected in the scope of not damaging effect of the present invention.

2. cured film

Being characterized as of cured film of the present invention is described curable liquid resin composition of the present invention is solidified and to get, and has the multilayered structure more than 2 layers.Particularly, preferably have the two-layer above layer structure that the non-existent in fact layer below 1 of layer, described (B) metal oxide particle more than 1 of being existed to high-density by described (B) metal oxide particle constitutes.

And because multilayer body described later contains cured film, so the explanation of cured film goes for the explanation of multilayer body, and the explanation of multilayer body goes for the explanation of cured film.

When forming cured film, preferably base material (suitable member) is applied by curable liquid resin composition of the present invention.As this kind coating method, can use dip coating, spraying method, rod to be coated with methods such as method, rolling method, spin coating method, curtain-type curtain coating, woodburytype, silk screen print method or ink jet method.

In addition, curable liquid resin composition solidified method is not particularly limited, however for example preferably heating.Under this situation, preferably heated 1～180 minute down at 30～200 ℃.By heating like this, just can not damage base material or formed cured film, more effectively obtain the good cured film of antireflection.Preferably heated 1～120 minute down, more preferably heated 1～60 minute down at 80～150 ℃ at 50～180 ℃.

In addition, by adding described light acid propellant, and, also can be cured by the irradiation radioactive rays.Under this situation, for example can use UV irradiation equipment (metal halide lamp, high pressure mercury vapour lamp etc.), at 0.001～10J/cm ²The rayed condition under carry out, yet illuminate condition is not limited thereto.More preferably 0.01～5J/cm ², further preferred 0.1～3J/cm ²

And, state of cure for cured film, for example when having used melamine compound as the solidified nature compound, can be by the methylol of melamine compound or the amount of alkoxylate methyl be carried out infrared spectroscopic analysis, or confirm quantitatively by using cable-styled extractor to measure the gelation rate.

After being coated with curable liquid resin composition, in solvent in the composition (C) and solvent (D) evaporating course, (B) metal oxide particle in the coated base bottom side (near the boundary of adjacent layers) or its opposite lateral deviation changing.Thus, exist with high-density, do not exist in fact, therefore just form the resin layer of low-refraction at the opposing party's of cured film near interface (B) metal oxide particle at a side's of cured film near interface (B) metal oxide particle.So,, just can be had the cured film of two-layer above multi-ply construction in fact by making a curing of coating that constitutes by curable liquid resin composition.These separation and each layer of forming for example can be confirmed by the section of the film that gets with electron microscope observation post.Though the layer that so-called (B) metal oxide particle exists to high-density is meant the notion of the part of metal oxide particle set, is to be in fact the layer that principal constituent constitutes with the metal oxide particle, yet the situation at the inner coexistence of layer (A) composition is arranged also.On the other hand, the non-existent in fact layer of so-called metal oxide is meant the notion of the non-existent part of metal oxide particle, yet also can be comprised on a small quantity in the scope of not damaging effect of the present invention.This layer is in fact by (A) composition and (E) layer that constitutes of the composition beyond the metal oxide particles such as cured article of composition.Cured film of the present invention has and has formed two layers of structure that layer that metal oxide particle exists to high-density and the non-existent in fact layer of metal oxide particle are distinguished the successive layer under many circumstances.When in base material, having used polyethylene terephthalate (PET) resin (comprising PET resin) etc. with easy adhesive linkage, as a rule, layer, the non-existent in fact layer of metal oxide particle that exists to high-density as layer, the metal oxide particle of base material is adjacent to this form in proper order.To be described in detail in the back for the layer structure more than two layers.

The cured film of gained is on its film thickness direction, and preferably specific refractory power changes with 0.05～0.8, more preferably changes with 0.1～0.6.In addition, described variations in refractive index has main variation near being preferably in the boundary of two layers of structure of described essence.

The degree of change of refractive can utilize content, kind, (A) fluoropolymer of metal oxide particle content, form and (E) content, the kind of solidified nature compound wait and adjust.

In addition, the specific refractory power of the low-refraction of cured film part for example is 1.3～1.5, and the specific refractory power of high refractive index part is 1.6～2.2.

3. multilayer body

In the manufacture method of multilayer body of the present invention, by from base material or be formed at 1 of getting of the described curable liquid resin composition of coating films on the layer on the base material, make solvent evaporation (followingly also will " make solvent evaporation " sometimes and be called drying.), form the layer more than 2.And, also can not be the state of solvent completely dissolve after the drying, also can be in can obtaining as the scope of the characteristic of cured film remaining solvent.In addition, among the present invention, can will implement more than 2 times by 1 process that forms the layer more than 2 of filming.

Specific curable liquid resin composition is coated with usual method, when making it drying thereafter, promptly is separated into the layer more than 2.Here, the situation of the existing layer more than 2 that will " layer that metal oxide particle exists to high-density " and " the non-existent in fact layer of metal oxide particle " comprises jointly of so-called layer more than 2, only also have in addition by " metal oxide particle exist to high-density layer " formation more than 2 layer situation.

Below, will use accompanying drawing that the situation of " layer or the non-existent in fact layer of metal oxide particle that each layer of the layer more than 2 exists to high-density as metal oxide particle, at least 1 layer of layer that exists to high-density for metal oxide particle " is described.Figure 1A represents that the layer more than 2 is 2 layers a situation of " layer 1 that metal oxide particle exists to high-density " and " the non-existent in fact layer 3 of metal oxide particle ".Figure 1B represents that the layer more than 2 is 2 layers the situation of " layer 1 that metal oxide particle exists to high-density, 1a ".Fig. 1 C represents that the layer more than 2 is 3 layers a situation of " layer 1 that metal oxide particle exists to high-density, 1a " and " the non-existent in fact layer 3 of metal oxide particle ".Fig. 1 D represents that the layer more than 2 is 3 layers a situation of " layer 1 that metal oxide particle exists to high-density, 1a " and " the non-existent in fact layer 3 of metal oxide particle ".Fig. 1 E represents that the layer more than 2 is 2 layers a situation of " the layer 1b that metal oxide particle exists to high-density " and " the non-existent in fact layer 3 of metal oxide particle ".

When curable liquid resin composition contains metal oxide particle more than 2 kinds, shown in Figure 1B, 1C, 1D, can form on " layer that metal oxide particle exists to high-density " more than 2 kinds.

In addition, " metal oxide particle " in " layer that metal oxide particle exists to high-density " is meant at least a kind, i.e. " metal oxide particle " more than a kind or 2 kinds.When curable liquid resin composition comprised more than 2 kinds metal oxide particle, " layer that metal oxide particle exists to high-density " can be made of (for example Fig. 1 E) metal oxide particle more than 2 kinds.Among Fig. 1 E, " the layer 1b that metal oxide particle exists to high-density " is made of particle X and particle Y.Particle Y is owing to the thickness greater than " the layer 1b that metal oxide particle exists to high-density ", therefore outstanding to " the non-existent in fact layer 3 of metal oxide particle ", and this protuberance also is contained in " the layer 1b that metal oxide particle exists to high-density ".

And, among Figure 1A～Fig. 1 E, though in " the non-existent in fact layer 3 of metal oxide particle ", there is not metal oxide particle usually, also can in the scope of not damaging effect of the present invention, contain on a small quantity.In addition, " layer 1 that metal oxide particle exists to high-density, 1a, 1b " similarly also can comprise other the material beyond the metal oxide particle.

As the coating method of curable liquid resin composition, can use known coating process, can use the whole bag of tricks such as dip coating, coating machine method, print process especially.

Dry normally implemented about 1～60 minute with the heating from about room temperature to 100 ℃.

Preferably these layers more than 2 are solidified by heating.Concrete condition of cure is narrated in the back.

Among the present invention, curable liquid resin composition is coated on the various base materials with the solution shape, made the dried coating film/curing of gained and can obtain multilayer body.For example, be under the situation of transparent substrate at base material, by being set at outermost layer, low-index layer can form good antireflection film.

The concrete structure of antireflection film normally with base material and low refractive index film or base material, high refractive index film and low refractive index film with this sequential cascade structure.In addition, also can be between base material, high refractive index film and low refractive index film, folder for example can be provided with the combination layer of hard coat, antistatic backing, middle index layer, low-index layer, high refractive index layer etc. every other layer.

Fig. 2 is illustrated on the base material 10 high refractive index layer 40 and low-index layer 50 antireflection film with this sequential cascade.

In this antireflection film, high refractive index layer 40 is equivalent to the layer that metal oxide particle exists to high-density, and low-index layer 50 is equivalent to the non-existent in fact layer of metal oxide particle.

According to the present invention, can film by 1 and form high refractive index layer 40 and low-index layer 50.

Fig. 3 is illustrated on the base material 10 hard coat 20, antistatic backing 30, high refractive index layer 40 and low-index layer 50 antireflection film with this sequential cascade.

Fig. 4 is illustrated on the base material 10 antistatic backing 30, hard coat 20, high refractive index layer 40 and low-index layer 50 antireflection film with this sequential cascade.

Fig. 5 is illustrated on the base material 10 hard coat 20, antistatic backing 30, middle index layer 60, high refractive index layer 40 and low-index layer 50 antireflection film with this sequential cascade.

In this antireflection film, high refractive index layer 40 is equivalent to the layer that metal oxide particle exists to high-density, and low-index layer 50 is equivalent to the non-existent in fact layer of metal oxide particle.Perhaps, middle index layer 60 and high refractive index layer 40 all are equivalent to the layer that metal oxide particle exists to high-density, or middle index layer 60 is equivalent to the layer that metal oxide particle exists to high-density, and high refractive index layer 40 is equivalent to the non-existent in fact layer of metal oxide particle.

According to the present invention, can by 1 film form in index layer 60 and high refractive index layer 40, perhaps form high refractive index layer 40 and low-index layer 50.Preferably film and form high refractive index layer 40 and low-index layer 50 by 1.

Fig. 6 is illustrated on the base material 10 antistatic backing 30, hard coat 20, middle index layer 60, high refractive index layer 40 and low-index layer 50 antireflection film with this sequential cascade.

Fig. 7 is illustrated in hard coat 20 on the base material 10, high refractive index layer 40 and low-index layer 50 with the stacked antireflection film of this order.

Fig. 8 is illustrated in hard coat 20 on the base material 10, middle index layer 60, high refractive index layer 40 and low-index layer 50 with the stacked antireflection film of this order.

Fig. 9 is illustrated in antistatic backing 30 on the base material 10, high refractive index layer 40 and low-index layer 50 with the stacked antireflection film of this order.

Figure 10 is illustrated in antistatic backing 30 on the base material 10, middle index layer 60, high refractive index layer 40 and low-index layer 50 with the stacked antireflection film of this order.

And, in the described antireflection film, as metal oxide contained in the employed curable liquid resin composition, if add electroconductive particles such as containing antimony oxidation tin (ATO) particle, then the layer that contains metal oxide to high-density of gained just becomes the film with static electricity resistance.So if for example high refractive index layer or middle index layer are had the layer that contains metal oxide to high-density of static electricity resistance as this kind and form, then high refractive index layer or middle index layer just can be made as the film that has static electricity resistance concurrently.Under this situation, the formation of preventing charged membrane can be omitted.

The thickness of cured film of the present invention for example is 0.05 μ m～50 μ m in the antireflection film, yet is not limited thereto.

Below, each layer of described antireflection film described.

(1) base material

The kind of used base material is not particularly limited in the antireflection film of the present invention, yet concrete example as base material, for example can enumerate cellulosetri-acetate, pet resin (East レ (strain) ester Le ミラ-etc.), various transite plates, films etc. such as glass, polycarbonate resin, acrylic resin, styrene resin, aromatic polyester-based resin, norbornene resin (JSR (strain) makes ア-ト Application, Japanese ZEON (strain) system ゼオネ Star Network ス etc.), methyl methacrylate/styrene copolymerized resin, polyolefin resin.Can preferably enumerate cellulosetri-acetate, pet resin (East レ (strain) ester Le ミラ-etc.), norbornene resin (JSR (strain) system ア-ト Application etc.).

(2) low-index layer

So-called low-index layer represents that the specific refractory power under the wavelength 589nm is 1.20～1.55 layer.

As material used in the low-index layer, as long as can obtain required characteristic, just be not particularly limited, yet for example can enumerate the solidification compound, acryloyl monomer (acryl monomer), the fluorine-containing acryloyl monomer that contain fluoropolymer, contain epoxy compounds, the fluorine-containing cured article that contains epoxy compounds etc.In addition, in order to improve the intensity of low-index layer, can also cooperate silicon dioxide microparticle etc.

(3) high refractive index layer

So-called high refractive index layer represents that the specific refractory power under the wavelength 589nm is 1.50～2.20, has the layer of the specific refractory power that is higher than low-index layer.

In order to form high refractive index layer, can cooperate the inorganic particulate of high refractive index, for example metal oxide particle.

As the concrete example of metal oxide particle, can enumerate contain antimony oxidation tin (ATO) particle, stanniferous Indium sesquioxide (ITO) particle, zinc oxide (ZnO) particle, contain antimony zinc oxide, contain the aluminum zinc oxide particle, zirconium white (ZrO ₂) particle, titanium oxide (TiO ₂) particle, silicon-dioxide cover TiO ₂Particle, Al ₂O ₃/ ZrO ₂Cover TiO ₂Particle, cerium oxide (CeO ₂) particle, phosphorous stannic oxide (ATO) particle etc.Preferably contain antimony oxidation tin (ATO) particle, stanniferous Indium sesquioxide (ITO) particle, phosphorous stannic oxide particle, contain aluminum zinc oxide particle, Al ₂O ₃/ ZrO ₂Cover TiO ₂Particle.These metal oxide particles can be used alone, and also can make up two or more uses.

In addition, also can make high refractive index layer have the function of hard coat or antistatic backing.

(4) index layer in

Under the situation of the layer that has made up the specific refractory power that has more than 3 kinds, with the specific refractory power wavelength 589nm under be 1.50～1.90 and have be higher than low-index layer be lower than high refractive index layer specific refractory power layer be expressed as middle index layer.In the specific refractory power of index layer preferred 1.50～1.80, more preferably 1.50～1.75.

For index layer in forming, can cooperate the inorganic particulate of high refractive index, for example metal oxide particle.

As the concrete example of metal oxide particle, can enumerate contain antimony oxidation tin (ATO) particle, stanniferous Indium sesquioxide (ITO) particle, zinc oxide (ZnO) particle, contain antimony zinc oxide, contain the aluminum zinc oxide particle, zirconium white (ZrO ₂) particle, titanium oxide (TiO ₂) particle, silicon-dioxide capping oxidation titanium particle, Al ₂O ₃/ ZrO ₂Cover TiO ₂Particle, cerium oxide (CeO ₂) particle etc.Preferably contain antimony oxidation tin (ATO) particle, stanniferous Indium sesquioxide (ITO) particle, contain aluminum zinc oxide particle, zirconium white (ZrO ₂) particle, phosphorous stannic oxide (PTO) particle.These metal oxide particles can be used alone, and also can make up two or more uses.

In addition, also can make middle index layer have the function of hard coat or antistatic backing.

By with the combination of low-index layer and high refractive index layer, can reduce reflectivity, in addition,, reflectivity can be reduced, and form and aspect (tone) twinkling, that turn blue and so on can be reduced by with low-index layer, high refractive index layer, the combination of middle index layer.

(5) hard coat

As the concrete example of hard coat, preferably by SiO ₂, redix, materials such as acrylic resin, melamine resinoid constitute.In addition, also can in these resins, cooperate silicon dioxide granule.

The hard coat has the effect of the physical strength that improves multilayer body.

(6) antistatic backing

As the concrete example of antistatic backing, can enumerate to have added and contain antimony oxidation tin (ATO) particle, stanniferous Indium sesquioxide (ITO) particle, contain the solidified nature film that aluminum zinc oxide particle, phosphorous stannic oxide particle etc. have the conductive compound of the metal oxide particle of electroconductibility or organic or inorganic; The metal oxide film that gets by evaporation or the described metal oxide of sputter; The film that constitutes by the electroconductibility organic polymer.As the electroconductibility organic polymer, can polyacetylene class electroconductive polymer, polyaniline compound electroconductive polymer, polythiophene class electroconductive polymer, polypyrrole class electroconductive polymer, polyphenylene vinylene class electroconductive polymer etc. be shown example.And, as mentioned above, as metal oxide contained in the employed curable liquid resin composition among the present invention, if add ATO particle, ITO particle, contain antimony zinc oxide particle, contain electroconductive particle, phosphorous stannic oxide particle such as aluminum zinc oxide particle, then the layer that contains metal oxide to high-density of gained just becomes the film with static electricity resistance.Under this situation, can omit the anti-charged membrane of other formation.

Antistatic backing prevents adhering to by charged dust that causes etc. by multilayer body being given electroconductibility.

These layers both can only form one deck, also different layers can be formed in addition two-layer more than.

In addition, the thickness of basic, normal, high index layer is generally 60～150nm respectively, and the thickness of antistatic backing is generally 0.05～3 μ m, and the thickness of hard coat is generally 1～20 μ m.

Among the present invention, though can form the layer of successive arbitrarily more than 2 of multilayer body with manufacture method of the present invention, yet not according to manufacture method of the present invention the layer manufacture method, can utilize methods such as known coating and curing, evaporation, sputter to make.

In addition, the layer that is made of curable liquid resin composition of the present invention is especially preferably given the thermal process of utilizing heating in order to be solidified to form the cured film with good optical characteristics and weather resistance.Certainly, even at normal temperatures under the situation of Fang Zhiing, As time goes on curing reaction also can carry out, and forms required cured film, yet in fact, heating and to make it the solidified way be effective shortening aspect the required time.In addition, by adding the hot acid propellant in advance, can further promote curing reaction as curing catalysts.As this curing catalysts, be not particularly limited, can utilize various acids or its esters that are used for general urea resin, melamine resin etc. as the solidifying agent use, can preferably use ammonium salt especially.The heating condition that is used for curing reaction can suitably be selected, yet Heating temperature need be below the heat-resistant limit temperature of base material as the object of coating.

According to the present invention, forms layer more than 2 so the manufacturing process that can simplify multilayer body owing to can film by 1.

In addition, changing partially, can improve the scuff resistance of multilayer body by making metal oxide particle.

Multilayer body of the present invention for example can also be used for optics parts such as lens, permselective membrane strainer except antireflection film.

[embodiment]

In the following description, " part " or " % " short of special narration, just expression " mass parts " or " quality % ".

Production Example 1

(1) has organic compound synthetic of polymerizability unsaturated group

In the mixing solutions that 221 parts of mercaptopropyltrimethoxy silanes in the container that has stirrer and dibutyl tin laurate are 1 part, in dry air, with 50 ℃ with behind 222 parts of the isophorone diisocyanates of dripping in 1 hour, under 70 ℃, stirred 3 hours again.

Next, in this reaction soln, (constitute with 1 hour Xin Zhong village chemistry system NK ester A-TMM-3LM-N that dripped by pentaerythritol triacrylate 60 quality % and tetramethylol methane tetraacrylate 40 quality % with 30 ℃.Wherein, the participation reaction only is the pentaerythritol triacrylate with hydroxyl.) after 549 parts, stirred 10 hours down at 60 ℃ again, obtained reaction solution.

To the resultant in this reaction solution, after the remaining amount of isocyanate that promptly has an organic compound of polymerizability unsaturated group is measured with FT-IR, be below the 0.1 quality %, confirm that each reaction is carried out basically quantitatively.Utilize above operation, obtained having the thioxanthamide key, 773 parts of the compounds of urethane bonds, alkoxysilyl, polymerizability unsaturated group and have neither part nor lot in the composition (A-1) of 220 parts of the tetramethylol methane tetraacrylates of reaction.

Production Example 2

(2) the urethanum acrylate is synthetic

In the container that has stirrer by in 18.8 parts of isophorone diisocyanates, 0.2 part of solution that constitutes of dibutyl tin laurate, under 10 ℃, 1 hour condition, dripped Xin Zhong village chemistry system NK ester A-TMM-3LM-N (participate in reaction only for having the pentaerythritol triacrylate of hydroxyl.) after 93 parts, under 60 ℃, 6 hours condition, stir, formed reaction solution.

To the resultant in this reaction solution, that is, measure remaining amount of isocyanate with FT-IR in the same manner with Production Example 1 after, be below the 0.1 quality %, confirm that reaction is carried out basically quantitatively.In addition, at intramolecularly, urethane bonds and acryl (polymerizability unsaturated group) have been confirmed to contain.

Utilize above operation, except obtaining 75 parts of urethanum six acrylic compound, also obtained mixing the composition (A-2) that has 37 parts of tetramethylol methane tetraacrylates that have neither part nor lot in reaction.

Production Example 3

[containing of the modulation of the hard coat of silicon dioxide granule] with composition

With 2.32 parts of the compositions that contains the polymerizability unsaturated group (A-1) of manufacturing in the Production Example 1, silicon dioxide granule colloidal sol (methyl ethyl ketone silicon dioxide gel, daily output chemical industry (strain) system MEK-ST, number average bead diameter 0.022 μ m, silica concentration 30%) 91.3 parts (is 27 parts as silicon dioxide granule), the mixed solution that 0.12 part of ion exchanged water and p-hydroxybenzene monomethyl ether are 0.01 part, after stirring 4 hours under 60 ℃, add 1.36 parts of original acid A esters, and then under same temperature heated and stirred 1 hour, obtained reactive particles (dispersion liquid (A-3)).In aluminum dish weighing behind this dispersion liquid of 2g (A-3), on 175 ℃ hot-plate dry 1 hour, and weighing has been tried to achieve solid formation and has been divided content, is 30.7%.In addition, in the magnetic crucible weighing behind the 2g dispersion liquid (A-3), preparation is dry 30 minutes on 80 ℃ hot-plate, according to the inorganic residues that has burnt till in 750 ℃ the retort furnace after 1 hour, has tried to achieve the inorganic content of solid formation in dividing, and is 90%.

With this dispersion liquid (A-3) 98.6g, composition (A-2) 3.4g, 1-hydroxycyclohexylphenylketone 2.1g, IRGACURE907 (2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino propane-1-ketone, the CIBASPECIALCHEMICALS system) 1.2g, dipentaerythritol acrylate (DPHA) 33.2g, pimelinketone 7g mix stirring, have obtained containing hard coat composition (Gu forming branch concentration 50%) 145g of silicon dioxide granule.

Production Example 4

[containing the modulation of the composition of Zirconia particles]

(10～30nm) 300 parts of primary particle sizes add in 700 parts of the methyl ethyl ketones (MEK), carry out disperseing in 168 hours with granulated glass sphere, remove granulated glass sphere and have obtained zirconium white and disperse 950 parts of colloidal sols with the UEP-100 of first rare element chemistry industry (strain) system.In aluminum dish weighing after the 2g zirconium white disperses colloidal sol, on 120 ℃ hot-plate dry 1 hour, and weighing has been tried to achieve solid formation and has been divided content, is 30%.Disperse among the colloidal sol 100g at this zirconium white, add the mixed solution of synthetic composition (A-1) 0.86g, dipentaerythritol acrylate (DPHA) 13.4g, p-methoxyphenol 0.016g, ion exchanged water 0.033g in the Production Example 1, after stirring 3 hours under 60 ℃, add original acid A ester 0.332g, and then under same temperature heated and stirred 1 hour, obtained the dispersion liquid 116g of surface modification Zirconia particles.With this dispersion liquid 116g, composition (A-2) 1.34g, 1-hydroxycyclohexylphenylketone 1.26g, IRGACURE907 (2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino propane-1-ketone, the CIBASPECIALCHEMICALS system) 0.76g, MEK2846g mix stirring, have obtained the composition (Gu forming branch concentration 4%) that 2964g contains Zirconia particles.

Production Example 5

[containing the modulation of the composition of stanniferous Indium sesquioxide (ITO) particle]

KCC of Fuji system ITO colloidal sol (10wt%IPA colloidal sol) 700g, DPHA29.5g, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino propane-1-ketone 1g, Virahol (IPA) 1769.5g are mixed, obtained the composition that contains the ITO particle of solid formation branch concentration 4%.

Production Example 6

[containing the modulation of the composition of antimony oxidation tin (ATO) particle]

With ATO particle (the former テ Network of stone ノ (strain) system, SN-100P, primary particle size 10～30nm), dispersion agent (rising sun electrochemical industry (strain) system, アデカプ Le ロニ Star Network TR-701) and methyl alcohol mix (all solid formation divided content 31%, all inorganic content 29.6%) with the use level of 90/2.78/211 (weight ratio).In the 50ml of coating vibrator polymkeric substance system bottle, (the TOSHINRIKO system, BZ-01) (bead diameter 0.1mm) (volume is about 16ml) and described mixed solution (30g) disperseed 3 hours, had obtained the dispersion colloidal sol of median particle diameter 80nm to add granulated glass sphere 40g.The mixed solution that in this colloidal sol 304g, adds composition (A-1) 5.7g, p-methoxyphenol 0.01g, ion exchanged water 0.12g, after stirring 3 hours under 60 ℃, add original acid A ester 1.3g, and then under same temperature heated and stirred 1 hour, obtained surface modification ATO dispersion of particles liquid 311g.This dispersion liquid 278.3g, composition (A-2) 1.7g, pentaerythritol triacrylate 8.59g, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino propane-1-ketone 0.88g, methyl alcohol 33g, propylene glycol monomethyl ether 1675g are mixed stirring, obtained containing composition (Gu forming branch concentration 5%) 2000g of ATO particle.

Production Example 7

[containing the modulation of the composition of aluminum zinc oxide (Al doping ZnO) particle]

With zinc oxide particle (Sakai chemistry system Al doping ZnO particle, (nanmu originally changes into (strain) system for primary particle size 10～20nm), dispersion agent, Ha イプラ Star De ED151) and propylene glycol monomethyl ether mix (all solid formation divided content 30%, all inorganic content 27.6%) with the use level of 27.6/4.8/67.6 (weight ratio).In the 50ml of coating vibrator polymkeric substance system bottle, add zirconium white pearl 40g (bead diameter 0.1mm) and described mixed solution (30g), disperseed 8 hours, obtained the dispersion colloidal sol of median particle diameter 40nm.In this colloidal sol 290g, add pentaerythritol triacrylate 10g, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino propane-1-ketone 0.5g, propylene glycol monomethyl ether 2138g, mix and stir, obtained containing composition (Gu forming branch concentration 4%) 2438g of zinc oxide particle.

Production Example 8

[manufacturing of hydroxyl fluoropolymer]

In the stainless steel autoclave that has magnetic stirrer that with internal volume is 1.5L, after replacing fully with nitrogen, add vinyl acetic monomer 500g, perfluor (propyl vinyl ether) 43.2g, ethyl vinyl ether 41.2g, hydroxyethyl vinyl ether 21.5g, " アデカリアソ-プ NE-30 " (Asahi Denka Kogyo K. K's system) 40.5g as the nonionic reactive emulsifier, as " VPS-1001 " that contain the azo-group polydimethylsiloxane (Wako Pure Chemical Industries, Ltd.'s system) 6.0g and lauryl peroxide 1.25g, after in dry ice-methyl alcohol, being cooled to-50 ℃, in nitrogen, the oxygen in the system is removed once more.

Add R 1216 97.4g then, begin to heat up.Pressure was shown as 5.3 * 10 when the temperature in the autoclave reached 60 ℃ ⁵Pa., under 70 ℃ 20 hour stirrings continue reaction, be reduced to 1.7 * 10 at pressure thereafter ⁵The moment of Pa is with autoclave water-cooled, stopped reaction.After having reached room temperature, unreacted monomer is emitted, open wide autoclave, obtained solid formation branch concentration and be 26.4% polymers soln.After having separated out polymkeric substance, use washed with methanol the polymers soln of gained being dropped in the methyl alcohol, under 50 ℃, carry out vacuum-drying, obtained the fluoropolymer of 220g.

For the polymkeric substance of gained, confirm that the polystyrene conversion number-average molecular weight (Mn) of utilizing gel permeation chromatography to obtain is 48000, the glass transition temp (Tg) that utilizes DSC to obtain is 26.8 ℃.The fluorine content that utilizes the alizarin complexon method to obtain in addition is 50.3%.

Production Example 9

[silicon-dioxide covers TiO ₂Particle dispersion]

Interpolation is by covered titanium oxide fine powder 350 mass parts of silicon-dioxide, PEP-101 (mean polymerisation degree: be about 20) 80 mass parts, Virahol 1000 mass parts, ethylene glycol butyl ether 1000 mass parts, carry out disperseing in 10 hours with granulated glass sphere, remove granulated glass sphere, obtained silicon-dioxide capping oxidation titanium particle dispersion liquid (S-1) 2430 mass parts.Here, the silicon-dioxide of weighing gained covers TiO on aluminum dish ₂Particle dispersion, drying is 1 hour on 120 ℃ hot-plate, and the whole solid branch concentration (ratio of the composition total amount beyond the solvent in the dispersion liquid) that form of trying to achieve are 17 quality %.In addition, this silicon-dioxide of weighing covers TiO in the magnetic crucible ₂Particle dispersion-1, after having carried out preparing drying in 30 minutes on 80 ℃ the hot-plate, carrying out burning till in 1 hour in 750 ℃ retort furnace, tried to achieve all solid inorganic content that forms in dividing according to the inorganic residues amount of gained and all solid branch concentration that forms, is 82 quality %.

The result of the electron microscope observation of this solid substance is, the minor axis median size is 15nm, and length mean diameter is 46nm, and aspect ratio is 3.1, and number average bead diameter is 15nm.

Embodiment 1, comparative example 1

[modulation of curable liquid resin composition]

(1) manufacturing of curable liquid resin composition (forming 1～5)

The hydroxyl fluoropolymer 2g that obtains in silicon-dioxide capping oxidation titanium dispersion liquid 24g by will obtaining in the Production Example 9 (dividing 4.08g), the Production Example 8, methoxylation methylmelamine " サイメ Le 303 " (the Mitsui サイテ Star Network Co., Ltd. system) 1.2g of cross-linked compound Gu form, as Catalyst 4050 (Mitsui サイテ Star Network (strain) system of curing catalysts, aromatic azochlorosulfonate acid compound) 0.68g is dissolved among methyl ethyl ketone 32g, methyl iso-butyl ketone (MIBK) 24g as solvent, the butyl alcohol-tert 16g, has obtained forming 1.After having measured whole solid in this liquid resin composition in the same manner and form the branch concentration, be 7.5 quality % with Production Example 9.

Similarly,, reach the cooperation ratio shown in the following table 1, obtained forming 2～5 each components matching.And, form in 2～5, replace silicon-dioxide capping oxidation titanium dispersion liquid, use aluminum oxide, zirconium white to cover TiO ₂Particle dispersion (テイカ (strain) system) replaces butyl alcohol-tert, uses propyl carbinol (n-BuOH), and the composition of solvent has used methyl ethyl ketone (MEK)/Virahol (IPA)/methyl iso-butyl ketone (MIBK) (MIBK)/propyl carbinol (n-BuOH)=40/20/30/10.

After having measured particle diameter in the same manner with Production Example 9, number average bead diameter (minor axis median size) is 20nm.

(2) manufacturing of curable liquid resin composition (forming 6)

Except replacing the hydroxyl fluoropolymer that obtains in the Production Example 8, used カイ Na-ADS (エ Le Off アトケ system ジヤパ Application (strain) system.The multipolymer of hexafluoro propylene, tetrafluoroethylene and ethylene difluoride.Do not have hydroxyl and polymerizability unsaturated group.) in addition, obtained curable liquid resin composition (forming 6) in the same manner with the manufacturing of curable liquid resin composition (form 1).

Embodiment 2, comparative example 2

[manufacturing of cured film]

With silicon dioxide granule colloidal sol (methyl ethyl ketone silicon dioxide gel, daily output chemical industry (strain) system MEK-ST, number average bead diameter 0.022 μ m, silica concentration 30%) 98.6g, 1-hydroxycyclohexylphenylketone 2.1g, IRGACURE907 (2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino propane-1-ketone, the CIBASPECIALCHEMICALS system) 1.2g, dipentaerythritol acrylate (DPHA) 33.2g, pimelinketone 7g mix stirring, have obtained containing the hard coat composition of silicon dioxide granule.Use wire bar coating machine (#12), with this contain silicon dioxide granule hard coat with the composition brushing after cellulose triacetate film (LOFO system, thickness 80 μ m) is gone up, in baking oven 80 ℃ dry 1 minute down.Next, by under air, use high pressure mercury vapour lamp, with 0.6J/cm ²Rayed condition irradiation ultraviolet radiation, formed the hard coat.Having measured the thickness of hard coat with contact type film thickness meter, is 5 μ m.

On the hard coat of gained, use wire bar coating machine (#3), brushed the composition 1～6 that obtains in embodiment 1 and the comparative example 1 after, by 120 ℃ of heating 10 minutes down in baking oven, having formed thickness is the solidifying film layer of 0.2 μ m.

Evaluation Example 1

[evaluation of cured film]

With the section of the cured film that obtains in microscopic examination embodiment 2 and the comparative example 2, it is two-layer whether evaluation is separated into.Metewand is as follows.The typical case of each state is shown among Figure 11.

＜metewand 〉

Two separate

Do not separate (localized agglomeration)

Massiveness

Haze (%) is to use the Haze instrumentation to decide the turbidity of the multilayer body of gained (Haze value), estimates based on following benchmark.

Zero: the Haze value is below 1%.

△: the Haze value is below 5%.

*: the Haze value surpasses 5%.

The results are shown in the following table 1.

[table 1]

Composition	Form (quality %)		Form 1 (embodiment)	Form 2 (embodiment)	Form 3 (embodiment)	Form 4 (comparative examples)	Form 5 (embodiment)	Form 6 (comparative examples)
Composition	Form (quality %)		Form 1 (embodiment)	Form 2 (embodiment)	Form 3 (embodiment)	Form 4 (comparative examples)	Form 5 (embodiment)	Form 6 (comparative examples)	(A)	The hydroxyl fluoropolymer	Production Example 8	25.1	46	26	0	26	-
	Fluoropolymer (no hydroxyl)	カイナ-ADS	-	-	-	-	-	25.1	(A)	The hydroxyl fluoropolymer	Production Example 8	25.1	46	26	0	26	-
	Fluoropolymer (no hydroxyl)	カイナ-ADS	-	-	-	-	-	25.1	(B)	Metal oxide particle	Aluminum oxide, zirconium white cover TiO ₂Particle dispersion	-	49	49	49	49	-
Silicon-dioxide covers TiO ₂	51.3	-	-	-	-	51.3						-	49	49	49	49	-
Silicon-dioxide covers TiO ₂	51.3	-	-	-	-	51.3	(E)	The solidified nature compound			サイメル303	15.1	0	20	26	25	15.1
(F)	The hot acid propellant	Catalyst4050	8.5	5	5	26	(E)	The solidified nature compound	0	8.5	サイメル303	15.1	0	20	26	25	15.1
(F)	The hot acid propellant	Catalyst4050	8.5	5	5	26	Layer separation property			8.5	Two separate	Two separate	Two separate	Uniform texture	Two separate	Do not separate (localized agglomeration)
Haze			○	○	○	○	Layer separation property			○	Two separate	Two separate	Two separate	Uniform texture	Two separate	Do not separate (localized agglomeration)	○

The meaning that brevity code in the table 1 is expressed as follows.

(A) fluoropolymer: the fluoropolymer of making in the described Production Example 1.

カイ Na-ADS: エ Le Off アトケ system ジヤパ Application (strain) system; The multipolymer of hexafluoro propylene, tetrafluoroethylene and ethylene difluoride.Do not have hydroxyl and polymerizability unsaturated group.

(B) metal oxide particle

Aluminum oxide, zirconium white cover TiO ₂Particle dispersion: テイカ Co., Ltd. system, all solid formation divided concentration 28%, particle concentration 24%, number average bead diameter 20nm

Silicon-dioxide covers TiO ₂Particle dispersion: the dispersion liquid of making in the Production Example 2.

(E) サイメ Le 303: methoxylation methylmelamine, Mitsui サイテ Star Network Co., Ltd. system

(F) Catalyst 4050: Mitsui サイテ Star Network (strain) system, aromatic azochlorosulfonate acid compound

According to found that of table 1,, also produced two separate (forming 2 and 5) even cooperate (E) solidified nature compound to reach (F) hot acid propellant.

When not having (A) hydroxyl fluoropolymer, then do not produce two separate (forming 4 and 6).

Embodiment 3, comparative example 3

[manufacturing of curable liquid resin composition and cured film]

Solid formation at the composition 3 of embodiment 1 divides in the curable liquid resin composition of proportioning example, and used solvent is changed as shown in table 2ly, has obtained forming 7～10 curable liquid resin composition.

Use and

form

3 and 7～10 curable liquid resin composition, made cured film in the same manner and under same condition with embodiment 2.

(A) solvability of hydroxyl fluoropolymer is that (A) hydroxyl fluoropolymer is added in each solvent, make it to reach 50 quality %, when at room temperature stirring certain hour, utilize visual observation, according to whether being that uniform solution is determined, estimate based on following benchmark.The results are shown in Table 2.

＜metewand 〉

Zero: stirring the back at 2 hours is uniform solution.

△: stirring the back at 8 hours is uniform solution.

*: after stirring in 8 hours is not uniform solution.

(B) TiO ₂Dispersion of particles stability is sheet glass to be impregnated in (B) metal oxide particle dispersion liquid, (B) metal oxide particle is attached on the glass wall, under the sheet glass that this has been adhered to (B) metal oxide particle impregnated in situation in each solvent, with visual observation, in this solvent, whether disperse equably to determine according to (B) metal oxide particle, estimate based on following benchmark.The results are shown in Table 2.

＜metewand 〉

Zero: disperse equably

*: do not disperse equably

In the table 2, solvent is the series arrangement that diminishes according to the relative velocity of evaporation of solvent from left to right.

The brevity code of solvent is represented the following meaning respectively.

MEK: methyl ethyl ketone

MeOH: methyl alcohol

IPA: Virahol

MIBK: methyl iso-butyl ketone (MIBK)

N-BuOH: propyl carbinol

MAK: Methyl amyl ketone

Evaluation Example 2

[evaluation of cured film]

To the cured film that obtains in embodiment 3 and the comparative example 3, layer separation property and Haze have been estimated in the same manner with evaluation Example 1.The results are shown in Table 2.

[table 2]

According to found that of table 2, in order to produce two separate, the solvent of fits best more than 2 kinds, at least a kind needs to select (C) high to the solvability of (A) fluoropolymer, in addition at least a kind needs to select (D) high to the dispersion stabilization of (B) metal oxide particle, and the relative velocity of evaporation of solvent (C) need be greater than the relative velocity of evaporation of solvent (D) in addition.

Embodiment 4, comparative example 4

[making of multilayer body]

(1) making of hard coat

Use wire bar coating machine (#12) with Production Example 3 in the synthetic silicon dioxide granule hard coat that contains brush in cellulose triacetate film (LOFO system with composition (the solid branch concentration 50% that forms), thickness 80 μ m) after on, dry 1 minute under 80 ℃ in baking oven.Next, by under air, use high pressure mercury vapour lamp, with 0.6J/cm ²Rayed condition irradiation ultraviolet radiation, formed solidifying film layer.Having measured the thickness of solidifying film layer with contact type film thickness meter, is 5 μ m.

(2) making of index layer in

Use wire bar coating machine (#3) in Production Example 4 on the synthetic hard coat that contains Zirconia particles composition (solid the branchs concentration 4% that forms) brushing making in (1) after, in baking oven under 80 ℃ drying 1 minute.Next, by under nitrogen atmosphere, use high pressure mercury vapour lamp, with 0.6J/cm ²Rayed condition irradiation ultraviolet radiation, formed solidifying film layer.Calculate the thickness of solidifying film layer with reflection beam splitting, be 65nm.

(3) making of high refractive index layer and low-index layer

After on the middle index layer that the curable liquid resin composition brushing of the composition 1～6 that uses wire bar coating machine (#3) to obtain in embodiment 1 and comparative example 1 is respectively made in (2), heated 10 minutes under 120 ℃ in baking oven, having formed thickness is the solidifying film layer of 0.2 μ m.

Embodiment 5, comparative example 5

[making of multilayer body]

(1) making of hard coat

Make in the same manner with embodiment 4 (1).

(2) making of antistatic backing

Use wire bar coating machine (#3) in Production Example 5 on the synthetic hard coat that contains ITO particle composition (solid the branchs concentration 4% that forms) brushing making in (1) after, in baking oven under 80 ℃ drying 1 minute.Next, by under nitrogen atmosphere, use high pressure mercury vapour lamp, with 0.6J/cm ²Rayed condition irradiation ultraviolet radiation, formed solidifying film layer.Calculate the thickness of solidifying film layer with reflection beam splitting, be 65nm.

(3) making of index layer in

Make in the same manner with embodiment 4 (2).

(4) making of high refractive index layer and low-index layer

After on the middle index layer that the curable liquid resin composition brushing of the composition 1～6 that uses wire bar coating machine (#3) to obtain in embodiment 1 and comparative example 1 is respectively made in (3), heated 10 minutes under 120 ℃ in baking oven, having formed thickness is the solidifying film layer of 0.2 μ m.

Embodiment 6,7, comparative example 6,7

[making of multilayer body]

(1) making of antistatic backing

Replace synthetic ITO particle in the Production Example 5, with the synthetic ATO of containing particle composition in Production Example 6 or 7 (Gu form branchs concentration 5%) or contain Al doping ZnO particle composition (Gu formation branch concentration 4%), use wire bar coating machine (#3) brushing in cellulose triacetate film (LOFO system, thickness 80 μ m) after on, dry 1 minute under 80 ℃ in baking oven.Next, by under nitrogen atmosphere, use high pressure mercury vapour lamp, with 0.6J/cm ²Rayed condition irradiation ultraviolet radiation, formed solidifying film layer.Utilize reflection beam splitting to calculate the thickness of solidifying film layer, be 65nm.

(2) making of hard coat

Use wire bar coating machine (#12) brushed in the Production Example 3 synthetic contain silicon dioxide granule hard coat with composition (solid the branchs concentration 50% that forms) after, in baking oven under 80 ℃ drying 1 minute.Next, by under air, use high pressure mercury vapour lamp, with 0.6J/cm ²Rayed condition irradiation ultraviolet radiation, formed solidifying film layer.

(3) making of index layer in

Make in the same manner with embodiment 4 (2).

(4) making of high refractive index layer and low-index layer

Embodiment 8, comparative example 8

[making of multilayer body]

(1) making of hard coat

Make in the same manner with embodiment 4 (1).

(2) making of high refractive index layer and low-index layer

After on the hard coat that the curable liquid resin composition brushing of the composition 1～6 that uses wire bar coating machine (#3) to obtain in embodiment 1 and comparative example 1 is respectively made in (1), heated 10 minutes under 120 ℃ in baking oven, having formed thickness is the solidifying film layer of 0.2 μ m.

Evaluation Example 3

[evaluation of multilayer body]

With the infiltration type electron microscope observation behind the section of the multilayer body that obtains in embodiment 4～8 and the comparative example 4～8, confirm to form in 1,2,3,5 the multilayer body having used, low-index layer and high refractive index are separated into 2 layers layer by layer.At this moment, low-index layer is the non-existent in fact layer of metal oxide particle, and high refractive index layer is the layer that metal oxide particle exists to high-density.Form in 4 the multilayer body having used, high refractive index layer and low-index layer become uniform texture, and genetic horizon separates.Used and formed in 6 the multilayer body, high refractive index layer and low-index layer localized agglomeration, genetic horizon separates.

Form 1 for having used, 2,3,5 the antireflection antireflection of multilayer body, be to utilize spectral reflectance determinator (the recording spectrophotometer U-3410 of the large-scale sample chamber integrating sphere auxiliary equipment 150-09090 that packed into, Hitachi's (strain) system), measuring the reflectivity of wavelength 550nm estimates.Specifically, be benchmark (100%) with the reflectivity of the vapor-deposited film of aluminum oxide, measured the reflectivity of antireflection with multilayer body (antireflection film).Consequently, the reflectivity of multilayer body under wavelength 550nm all is below 1% arbitrarily.

Utilize possibility on the industry

Form the cured film with the continuous multi-ply construction such as low-index layer and high refractive index layer by making curable liquid resin composition of the present invention solidify the cured film that gets owing to can film by one, therefore the manufacturing process with cured film of multi-ply construction can be simplified. That is, if use curable liquid resin composition of the present invention, then the manufacturing process with laminated body of two-layer above multi-ply construction can be simplified. So curable liquid resin composition of the present invention can advantageously be applied in the formation of the optical materials such as antireflection film, lens, permselective membrane filter especially. In addition, the cured film of gained or laminated body can also be utilized the high situation of fluorine content, are applied to rightly in coating, weatherability film, coating material and other materials on being required the base material of against weather. And this cured film or laminated body are because good with the adhesion of base material, and marresistance is high, and good anti-reflection effect is provided, and is therefore extremely useful as antireflection film, by being applied in the various display unit, can improve its visuognosis degree.

Claims

(A) intramolecularly have hydroxyl fluoropolymer,

(B) number average bead diameter below the 100nm and specific refractory power the metal oxide particle more than a kind or 2 kinds more than 1.50 (below be called " (B) metal oxide particle "),

(C) to (A) have at intramolecularly the high solvent more than a kind or 2 kinds of the solvability of fluoropolymer of hydroxyl (below be called " (C) fast solvent flashing "),

(D) to the dispersion stabilization of (B) metal oxide particle high and with (C) fast solvent flashing be intermiscibility the solvent more than a kind or 2 kinds (below be called " (D) slow-evaporating solvent "),

(E) the solidified nature compound,

(F) hot acid propellant,

2. according to the curable liquid resin composition described in the claim 1, it is characterized in that,

3. according to the curable liquid resin composition described in the claim 1, it is characterized in that,

(B) metal oxide particle is to be selected from titanium oxide, zirconium white, to contain antimony oxidation tin, stanniferous Indium sesquioxide, aluminum oxide, cerium oxide, zinc oxide, to contain aluminum zinc oxide, stannic oxide, contain antimony zinc oxide and the metal oxide more than a kind or 2 kinds that contains in indium zinc oxide, the phosphorous stannic oxide is the particle of principal constituent.

4. according to the curable liquid resin composition described in the claim 3, it is characterized in that,

(B) metal oxide particle is to be the particle of principal constituent with the titanium oxide.

5. according to the curable liquid resin composition described in the claim 1, it is characterized in that,

6. a cured film is characterized in that, is the curable liquid resin composition described in the claim 1 is solidified and to get, and has the multi-ply construction more than 2 layers.

7. according to the cured film described in the claim 6, it is characterized in that,

8. the manufacture method of a cured film is characterized in that, comprises by heating or shining radioactive rays making the curable liquid resin composition solidified operation described in the claim 1.

On the described base material or be formed on the layer on the base material, the curable liquid resin composition of coating described in the claim 1 and forming filmed,

By from this 1 is filmed with solvent evaporation, form the layer more than 2.

10. according to the manufacture method of the multilayer body described in the claim 9, it is characterized in that, each layer of described layer more than 2 is layer or the non-existent in fact layer of metal oxide particle, wherein at least 1 layer of layer that exists to high-density for metal oxide particle that metal oxide particle exists to high-density.

11. the manufacture method according to the multilayer body described in the claim 10 is characterized in that, described layer more than 2 is 2 layers.

12. the manufacture method of multilayer body according to claim 9 is characterized in that, and then by heating described layer more than 2 is solidified.

13. the manufacture method of multilayer body according to claim 9 is characterized in that, multilayer body is the optics parts.

14. the manufacture method of multilayer body according to claim 9 is characterized in that, multilayer body is an antireflection film.

15. the manufacture method according to the multilayer body described in the claim 11 is characterized in that,

Described multilayer body on base material from beginning near the base material side to major general's high refractive index layer and low-index layer antireflection film with this sequential cascade, 2 layers described in the claim 11 are made of high refractive index layer and low-index layer.

16. the manufacture method according to the multilayer body described in the claim 15 is characterized in that,

The specific refractory power of low-index layer under 589nm is 1.20～1.55,

17. the manufacture method according to the multilayer body described in the claim 11 is characterized in that,

Described multilayer body is for index layer, high refractive index layer and low-index layer are with the antireflection film of this sequential cascade to the major general from beginning near the base material side on base material, and 2 layers described in the claim 11 are made of high refractive index layer and low-index layer.

18. the manufacture method according to the multilayer body described in the claim 17 is characterized in that,

The specific refractory power of low-index layer under 589nm is 1.20～1.55,

19. the manufacture method according to claim 15 or 17 described multilayer body is characterized in that, also forms hard coat and/or antistatic backing on base material.

20. multilayer body of utilizing the manufacture method manufacturing of the multilayer body described in the claim 9.